Supported Ruthenium Nanoparticles Research Articles

MoS2 supported Ruthenium nanoparticles with abundant sulfur vacancies significantly improved hydrogen evolution reaction

The electrochemical hydrogen evolution reaction (HER) has become one of effective ways to produce hydrogen. MoS2 is a promising electrocatalyst for the HER, and loading noble metal atoms on MoS2 support can further enhance its HER activity. In present work, the CO was employed as a structure-directing agent to in situ synthesize MoS2-n (n = 0, 0.5, 1.0, 1.4 and 2.0 MPa, representing the CO pressure). Among them, the MoS2-1.4 with highest amounts of sulfur vacancies and superior alkaline HER performance was selected as the support for Ru loadings. Sulfur vacancies can stabilize Ru nanoparticles, prevent nanoparticles from aggregating, and facilitate the formation of small-sized nanoparticles. By optimizing the loading amounts of Ru, the 5Ru@MoS2-1.4 with the Ru loading of 5 wt.% and nanoparticle size of 2 nm exhibits the best alkaline HER activity by displaying a low overpotential of 55 mV and Tafel slope of 68.6 mV dec−1 at a current density of 10 mA cm−2 in 1.0 M KOH medium. This can be majorly related to the synergistic effect of MoS2-1.4 support and small-sized Ru nanoparticles, wherein the CO plays a significant role in regulating the structure of MoS2-1.4 support that favors dispersion of Ru nanoparticles. Generally, present work provides a strategy to enhance the HER catalytic performance of MoS2, which is favorable for other highly-efficient catalyst design.

Consumer Grade Polyethylene Recycling via Hydrogenolysis on Ultrafine Supported Ruthenium Nanoparticles.

Catalytic hydrogenolysis has the potential to convert high-density polyethylene (HDPE), which comprises about 30 % of plastic waste, into valuable alkanes. Most investigations have focused on increasing activity for lab grade HDPEs displaying low molecular weight, with limited mechanistic understanding of the product distribution. No efficient catalyst is available for consumer grades due to their lower reactivity. This study targets HDPE used in bottle caps, a waste form generated globally at a rate of approximately one million units per hour. Ultrafine ruthenium particles (1 nm) supported on titania (anatase) achieved up to 80 % conversion into light alkanes (C1 -C45 ) under mild conditions (498 K, 20 bar H2 , 4 h) and were reused for three cycles. Small ruthenium nanoparticles were critical to achieving relevant conversions, as activity sharply decreased with particle size. Selectivity commonalities and peculiarities across HDPE grades were disclosed by a reaction modelling approach applied to products. Isomerization cedes to backbone scission as the reaction progresses. Within this trend, low molecular weight favor isomerization whilst high molecular weight favor cleavage. Commercial caps obeyed this trend with decreased activity, anticipating the influence of additives in realistic processing. This study demonstrates effective hydrogenolysis of consumer grade polyethylene and provides selectivity patterns for product control.

Consumer Grade Polyethylene Recycling via Hydrogenolysis on Ultrafine Supported Ruthenium Nanoparticles

AbstractCatalytic hydrogenolysis has the potential to convert high‐density polyethylene (HDPE), which comprises about 30 % of plastic waste, into valuable alkanes. Most investigations have focused on increasing activity for lab grade HDPEs displaying low molecular weight, with limited mechanistic understanding of the product distribution. No efficient catalyst is available for consumer grades due to their lower reactivity. This study targets HDPE used in bottle caps, a waste form generated globally at a rate of approximately one million units per hour. Ultrafine ruthenium particles (1 nm) supported on titania (anatase) achieved up to 80 % conversion into light alkanes (C1−C45) under mild conditions (498 K, 20 bar H2, 4 h) and were reused for three cycles. Small ruthenium nanoparticles were critical to achieving relevant conversions, as activity sharply decreased with particle size. Selectivity commonalities and peculiarities across HDPE grades were disclosed by a reaction modelling approach applied to products. Isomerization cedes to backbone scission as the reaction progresses. Within this trend, low molecular weight favor isomerization whilst high molecular weight favor cleavage. Commercial caps obeyed this trend with decreased activity, anticipating the influence of additives in realistic processing. This study demonstrates effective hydrogenolysis of consumer grade polyethylene and provides selectivity patterns for product control.

Enhanced Metal-Support Interactions Boost the Electrocatalytic Water Splitting of Supported Ruthenium Nanoparticles on a Ni3N/NiO Heterojunction at Industrial CurrentDensity.

Developing highly efficient and stable hydrogen production catalysts for electrochemical water splitting (EWS) at industrial current densities remains a great challenge. Herein, we proposed a heterostructure-induced-strategy to optimize the metal-support interaction (MSI) and the EWS activity of Ru-Ni3N/NiO. Density function theory (DFT) calculations firstly predicted that the Ni3N/NiO-heterostructures can improve the structural stability, electronic distributions, and orbital coupling of Ru-Ni3N/NiO, compared to Ru-Ni3N and Ru-NiO, which accordingly decreases energy barriers and increases the electroactivity for EWS. As a proof-of-concept, the Ru-Ni3N/NiO catalyst with 2D Ni3N/NiO-heterostructures nanosheet array, uniformly dispersed Ru nanoparticles, and strong MSI, was successfully constructed in the experiment, which owns an excellent HER and OER activity with overpotentials of 190 mV and 385 mV at 1000 mA cm-2, respectively. Furthermore, the Ru-Ni3N/NiO-based EWS device can realize an industrial current density (1000 mA cm-2) at 1.74 V and 1.80 V under alkaline pure water and seawater conditions, respectively. Additionally, it also achieves a high durability of 1000 h (@ 500 mA cm-2) in alkaline pure water.

Enhanced Metal‐Support Interactions Boost the Electrocatalytic Water Splitting of Supported Ruthenium Nanoparticles on a Ni3N/NiO Heterojunction at Industrial Current Density

AbstractDeveloping highly efficient and stable hydrogen production catalysts for electrochemical water splitting (EWS) at industrial current densities remains a great challenge. Herein, we proposed a heterostructure‐induced‐strategy to optimize the metal‐support interaction (MSI) and the EWS activity of Ru‐Ni3N/NiO. Density functional theory (DFT) calculations firstly predicted that the Ni3N/NiO‐heterostructures can improve the structural stability, electronic distributions, and orbital coupling of Ru‐Ni3N/NiO compared to Ru‐Ni3N and Ru‐NiO, which accordingly decreases energy barriers and increases the electroactivity for EWS. As a proof‐of‐concept, the Ru‐Ni3N/NiO catalyst with a 2D Ni3N/NiO‐heterostructures nanosheet array, uniformly dispersed Ru nanoparticles, and strong MSI, was successfully constructed in the experiment, which exhibited excellent HER and OER activity with overpotentials of 190 mV and 385 mV at 1000 mA cm−2, respectively. Furthermore, the Ru‐Ni3N/NiO‐based EWS device can realize an industrial current density (1000 mA cm−2) at 1.74 V and 1.80 V under alkaline pure water and seawater conditions, respectively. Additionally, it also achieves a high durability of 1000 h (@ 500 mA cm−2) in alkaline pure water.

Highly efficient and selective hydrogenation of quinolines at room temperature over Ru@NC-500 catalyst

Selective hydrogenation of quinolines into 1,2,3,4-tetrahydroquinolines under mild conditions holds tremendous promise for the green synthesis of a multitude of fine chemicals. Herein, we describe nitrogen-doped carbon supported ruthenium nanoparticles were robust for the mide and selective hydrogenation of quinolines to the corresponding 1,2,3,4-tetrahydroquinolines with both excellent activity and selectivity at 30∼50 °C and 10 bar H2.

Toward solar-driven photocatalytic CO2 methanation under continuous flow operation using benchmark MIL-125(Ti)–NH2 supported ruthenium nanoparticles

The production of solar fuels from CO2 is currently attracting increasing interest. Herein we describe the development of a benchmark metal–organic framework (MOF) photocatalyst based on MIL-125(Ti)–NH2 supported ruthenium nanoparticles for solar-driven selective photocatalytic CO2 methanation. The optimized RuOx(10 wt%; 1.48 nm)@MIL-125(Ti)–NH2 photocatalyst is exceptionally active (18.5 mmol g−1 at 22 h) and reusable (10 cycles for 220 h) in the CO2 methanation at 200 °C under batch conditions and simulated sunlight irradiation. The photocatalyst can also be employed for continuous-flow CO2 methanation under visible light irradiation at 200 °C for at least 50 h. Evidence in support of the operation of a dual photo-thermal mechanism that combines a photochemical mechanism based on e-/h+ separation and thermochemical contributions in which the energy of photons produces local heating has been obtained for the photocatalytic CO2 methanation. We are confident that this study will contribute to the development of active MOF-based photocatalysts for solar-driven CO2 methanation under continuous flow operations with industrial interest.

Diastereoselective hydrogenation of arenes and pyridines using supported ruthenium nanoparticles under mild conditions.

A convenient and practical diastereoselective cis-hydrogenation of multi-substituted pyridines and arenes is reported. Applying a novel heterogeneous ruthenium catalyst, the corresponding piperidines and cyclohexanes are obtained in high yields (typically >80%) with a good functional group tolerance under mild conditions. The robust ruthenium supported catalyst is smoothly prepared and can be reused multiple times without activity loss.

Oxidation of cycloalkene using supported ruthenium catalysts under solvent-free conditions

The present paper employs supported ruthenium nanoparticles alongside catalytic quantities of the radical initiator, which are proven to be capable of cyclooctene oxidation with green conditions, in the absence of solvent, with air as the main oxidant and without sacrificial reductant. The paper examines the effects of a range of radical initiators and how the products are distributed over time. Furthermore, the paper addresses the reaction pathways to the epoxides and allylic alcohol, the latter being the primary by-product, whilst also analysing the impact of the technique of synthesis, reaction time, and various supports. Catalyst activity can be markedly improved by adopting a sol-immobilisation technique to synthesise the catalysts, with retention of selectivity to the epoxide.

Selective upgrading of biomass-derived benzylic ketones by (formic acid)–Pd/HPC–NH2 system with high efficiency under ambient conditions

Selective upgrading of biomass-derived benzylic ketones by (formic acid)–Pd/HPC–NH2 system with high efficiency under ambient conditions

Hexagonal boron nitride supported ruthenium nanoparticles as highly active catalysts for ammonia borane hydrolysis

Ammonia borane (AB) hydrolysis is a comparative strategy for developing the sustainable hydrogen economy. Considering the hydrolysis cannot occur kinetically at low temperature, a suitable catalyst is indispensable. In this work, the dispersed ruthenium nanoparticles are stabilized on hexagonal boron nitride (h-BN) via an adsorption-in situ reduction procedure. Various characterization techniques are adopted for elucidating the structure-performance relationship of the obtained catalysts for the hydrolytic dehydrogenation of AB. In the presence of the resultant Ru/h-BN catalysts, the corresponding turnover frequency (1177.5 min−1) in alkaline solution at 303 K and the apparent activation energy (24.1 kJ mol−1) are superior to most literature previously reported. Our work provides a facile fabrication method for metal-based catalysts, which are highly promising in chemical storage material hydrolysis.

Supported ruthenium nanoparticles on ordered mesoporous carbons using a cyclodextrin-assisted hard-template approach and their applications as hydrogenation catalysts

The present study is concerned with the preparation of ordered mesoporous carbons containing uniform dispersions of ruthenium nanoparticles by a hard-template method, based on the use of RuCl3 and cyclodextrin as respective sources of metal and carbon. The influence of chemical structure of the parent CD [randomly methylated-β-CD (RAME-β-CD) and 2-hydroxypropyl-β-CD (HP-β-CD)] and loading of the ruthenium source are studied in detail. The catalysts are carefully characterized by N2-adsorption, TEM, XRD, CO pulse chemisorption, TG-MS and H2-TPR. The most outstanding effect is obtained when HP-β-CD is used, allowing to stabilize small and reactive Ru particles (1–2 nm) in the carbon matrix, with a good compromise between immobilization, surface availability and hydrogen spillover effect. The catalytic systems prepared from HP-β-CD display remarkably high catalytic activities in the liquid-phase hydrogenation of various substrates while their reusability and robustness are also demonstrated.

Ceria supported ruthenium nanoparticles: Remarkable catalyst for H2 evolution from dimethylamine borane

Ceria supported ruthenium nanoparticles (Ru0/CeO2) are synthesized by impregnation of Ru3+ ions on CeO2 powders followed by sodium borohydride reduction of Ru3+/CeO2. Their characterization was achieved using analytical methods including TEM, XRD, BET, SEM, and XPS. All the results reveal the formation of ruthenium(0) nanoparticles in 1.8 ± 0.3 nm size on CeO2 support. Ru0/CeO2 nanoparticles show high activity in catalyzing the H2 evolution from dimethylamine borane (DMAB). Ru0/CeO2 nanoparticles with 0.55% wt Ru provide the highest turnover frequency (812 h−1) for releasing H2 from DMAB at 60 °C and a total of 2500 turnovers before deactivation. High activity of Ru0/CeO2 nanoparticles for catalytic dehydrogenation of DMAB is attributable to the reducible nature of CeO2 support. Ce3+ defects formation in ceria under reducing conditions of dehydrogenation causes accumulation of negative charge on the oxide support, which makes oxide surface attractive for the ruthenium(0) nanoparticles. This, in turn, causes an enhancement in the metal-support interaction and thus in catalytic activity. The XPS analysis of bare ceria and Ru0/CeO2 demonstrates the increase in the concentration of Ce3+ defects after catalysis. Ru0/CeO2 nanoparticles are also reusable catalyst for H2 evolution from DMAB retaining 40% of initial activity after 4th run of reaction. The catalytic activity of Ru0/CeO2 nanoparticles and activation energy of catalytic dehydrogenation are compared with those of the other ruthenium based catalysts known in literature.

Polymer-graphene hybrid stabilized ruthenium nanocatalysts for the dimethylamine-borane dehydrogenation at ambient conditions

In this work, we reported a new catalyst consistent of graphene oxide (GO) – poly(N-vinyl-2-pyrrolidone) (PVP) hybrid supported ruthenium nanoparticles and called as Ru@GO-PVP. The GO-coupled PVP nanosheets were prepared with a new and straightforward pathway. The prepared Ru@GO-PVP nanocatalysts were characterized using some advanced analytic measurements such as XPS (X-ray photoelectron spectroscopy), XRD (X-ray diffraction), TEM/HRTEM (Transmission electron microscopy/high resolution transmission electron microscopy), Raman and ICP (Inductively coupled plasma). The mean particle size of the catalyst was found to be 2.09 nm, and this catalyst having small particle size showed one of the highest catalytic activities with a very high TOF value of 896.54 h−1 in dehydrogenation of DMAB at room temperature. Therefore, the proposed hybrid and supported catalyst offer a new pathway to enhance the catalytic dehydrogenation of DMAB greatly, and this study presents a universal and powerful technique for such applications.

Different Crystal Form Titania Supported Ruthenium Nanoparticles for Liquid Phase Hydrodeoxygenation of Guaiacol.

Titania supported Ruthenium-based catalysts were prepared for liquid phase hydrodeoxygenation of guaiacol to cyclohexanol. The catalytic performance is affected by the different crystal forms of titania supports. Anatase and rutile titania supported catalyst 5%Ru/a-r-TiO2 presents higher BET surface area, better dispersion of Ru particles with smaller particle size of 3-4 nm, more acidic centers, and more Ruδ+ located at the boundary between anatase titania and rutile titania. Hence, 5%Ru/a-r-TiO2 gives the best catalytic performance of 95.33% conversion of guaiacol and 79.23% selectivity to cyclohexanol, other products mainly include cyclohexane, benzene, cyclohexanone and 1,2-cyclohexanediol. Based on the results of this work, the possible reaction path for guaiacol hydrodeoxygenation was proposed.

Aerobic oxidation of alcohols using ruthenium supported on DD3 kaolin

Supported ruthenium nanoparticles were prepared through the chemical reduction of aqueous Ru(III) species previously loaded (1 or 5 wt%) onto DD3 kaolin through an ion-exchanged pathway. Resulting nanoporous materials were characterized by XRF, XRD, TEM, EDX, and N2 sorption measurements, and then used as catalysts in the liquid phase aerobic oxidation of benzyl alcohol. Benzaldehyde was obtained as the main product with a 97% yield at 100% alcohol conversion at 100 °C in the presence of Ru-DD3 (5%) using 10 mL/min O2 flow and 10 mol% of tert-butyl hydroperoxide with respect to the substrate. Oxidation tests were more efficient in the case of Ru-DD3 (5%) than with other Ru-based solids such as Ru-HZSM-5 (5%). It was also shown that, in the presence of Ru-DD3 (5%), the aerobic oxidation of benylalcohol in the presence of an amine (aniline) gives rise to the imine instead of the aldehyde through a one-pot oxidation and condensation process.

Atomic Layer Deposition of Ruthenium Nanoparticles on Electrospun Carbon Nanofibers: A Highly Efficient Nanocatalyst for the Hydrolytic Dehydrogenation of Methylamine Borane.

We report the fabrication of a novel and highly active nanocatalyst system comprising electrospun carbon nanofiber (CNF)-supported ruthenium nanoparticles (NPs) (Ru@CNF), which can reproducibly be prepared by the ozone-assisted atomic layer deposition (ALD) of Ru NPs on electrospun CNFs. Polyacrylonitrile (PAN) was electropsun into bead-free one-dimensional (1D) nanofibers by electrospinning. The electrospun PAN nanofibers were converted into well-defined 1D CNFs by a two-step carbonization process. We took advantage of an ozone-assisted ALD technique to uniformly decorate the CNF support by highly monodisperse Ru NPs of 3.4 ± 0.4 nm size. The Ru@CNF nanocatalyst system catalyzes the hydrolytic dehydrogenation of methylamine borane (CH3NH2BH3), which has been considered as one of the attractive materials for the efficient chemical hydrogen storage, with a record turnover frequency of 563 mol H2/mol Ru × min and an excellent conversion (>99%) under air at room temperature with the activation energy ( Ea) of 30.1 kJ/mol. Moreover, Ru@CNF demonstrated remarkable reusability performance and conserved 72% of its inherent catalytic activity even at the fifth recycle.

Facile production of 2,5-diformylfuran from base-free oxidation of 5-hydroxymethyl furfural over manganese–cobalt spinels supported ruthenium nanoparticles

This work reports manganese–cobalt spinels (MnCo2O4) supported ruthenium (Ru) nanoparticles, Ru/MnCo2O4, efficiently catalyzed 5-hydroxymethyl furfural (HMF) oxidation to 2,5-diformylfuran (DFF) with high yield 98.3% at 130°C and 1.0MPa of O2 pressure in toluene used as solvent under base-free conditions. A new class of spinels MnCo2O4 having multiple valence states of Mn and Co was synthesized by using simple co-precipitation method and used as support with ruthenium nanoparticles as heterogeneous catalyst. The reusability tests of catalyst Ru/MnCo2O4 were also carried out and was found to be recyclable up to several consecutive cycles without significance loss of original activity.

Nanohydrotalcite Supported Ruthenium Nanoparticles: Highly Efficient Heterogeneous Catalyst for the Oxidative Valorization of Lignin Model Compounds

Nanohydrotalcite Supported Ruthenium Nanoparticles: Highly Efficient Heterogeneous Catalyst for the Oxidative Valorization of Lignin Model Compounds

Ruthenium nanoparticles immobilized on surfactant-directed polypyrrole as an effective and reusable catalyst for hydrogen generation

An effective catalyst with high activity and stability is required to produce hydrogen from the hydrolysis of sodium borohydride (NaBH4) for the portable fuel cell applications. In this study, the synthesis of highly effective, stable and reusable polypyrrole (PPy) supported ruthenium nanoparticles (NPs) is presented. PPy powders with porous structure were prepared by the chemical oxidative polymerization, followed by the deposition of Ru NPs using the wet impregnation—reduction method. Due to the synergistic effect of Ru NPs with PPy, the as-synthesized catalyst exerts good catalytic activity, with the hydrogen release rate of 22.74 ± 0.84 L min−1 g Ru −1 and activation energy of 39.08 ± 1.69 kJ mol−1, which is lower than most of the reported activation energy values. This novel Ru/PPy catalyst is a promising candidate for small portable hydrogen generators by NaBH4 hydrolysis. Structural, morphological and textural properties of the catalysts were investigated by analytical techniques. Moreover, the effects of reaction temperature, NaOH and NaBH4 concentrations on catalytic activity were also investigated.