Highly dispersed Ru/Co catalyst with enhanced activity for catalyzing NaBH4 hydrolysis in alkaline solutions

Ru and Co are highly dispersed on the surface of TiO₂ nanoparticles with an easy coprecipitation method to fabricate a novel Ru-based catalyst (Ru/Co-TiO₂). The fabricated Ru/Co-TiO₂ catalyst exhibits superior catalytic performance for promoting NaBH₄ hydrolysis in alkaline medium, showing an impressive hydrogen generation rate per gram Ru as high as 172 L min⁻¹ g_Ru^-1, which is better than most of recently reported Ru-based catalysts. In addition, the fabricated Ru/Co-TiO₂ catalyst also shows excellent durability in cycle use, with only 2.9% activity loss after being used for 5 cycles. These advantages make the developed Ru/Co-TiO₂ catalyst a potential choice for promoting hydrogen generation from NaBH₄ hydrolysis.     

NiFe水滑石纳米片阵列负载Ru用于提升碱性电催化析氢和析氧性能

通过离子交换的方式将Ru负载到NiFe水滑石(LDH)纳米阵列表面得到(Ru/NiFe LDH),Ru的引入显著提升了NiFe LDH的活性比表面积,暴露了更多的活性位点,同时调控了其电子结构,大大提升了其本征催化活性。在碱性条件下,催化析氢反应时仅需50 mV的过电位即可达到10 mA·cm^-2的电流密度,Tafel斜率为52.3 mV·dec^-1。而相同条件下原始NiFe LDH达到10mA·cm^-2的电流密度则需要226 mV的过电位,Tafel斜率为157.5 mV·dec^-1。同时制备的Ru/NiFe LDH也展现出了良好的析氧催化活性,在50 mA·cm^-2的电流密度下,过电位仅为231 mV,而NiFe LDH则需237 mV。Ru/NiFe LDH在长时间的电催化条件下依然能保持良好的工作稳定性。     

Zirconia prepared from UIO-66 as a support of Ru catalyst for ammonia synthesis

The development of effective Ru catalyst for ammonia synthesis is of important practical value and scientific significance because of the wide application of ammonia as a fertilizer and its promising applications in the renewable energy. Generally, ZrO₂ was regarded as an inferior support for Ru catalyst used in ammonia synthesis. Here we prepare ZrO₂ with monoclinic phase and carbon species from ZrCl₄ following the preparation route of UiO-66 as well as ammonia treatment. Owing to the presence of a larger amount of hydrogen adsorption as well as the easier desorption of hydrogen species, the ill effect of hydrogen species on the nitrogen adsorption-desorption and ammonia synthesis can be effectively alleviated. The resulting ZrO₂-supported Ru catalyst showed 4 times higher ammonia synthesis activity than the conventional Ru/ZrO₂ obtained from zirconium nitrate.     

Ru single atoms induce surface-mediated discharge in Na-O2 batteries

Sodium（Na）O₂ batteries have high energy density and low cost. However, high polarization, complex discharge products, and low Coulombic efficiency（CE） lead to poor cyclability. Here, we proposed an atomically dispersed Ru catalyst on nitrogen-doped graphene for Na-O₂ batteries. The catalysts enable the discharge to proceed via a surface-mediated route, which leads to uniform deposition of Na_2-xO₂ and low polarization during recharge. The first-principl...     

NiFe水滑石纳米片阵列负载Ru用于提升碱性电催化析氢和析氧性能

通过离子交换的方式将Ru负载到NiFe水滑石（LDH）纳米阵列表面得到（Ru/NiFe LDH），Ru的引入显著提升了NiFe LDH的活性比表面积，暴露了更多的活性位点，同时调控了其电子结构，大大提升了其本征催化活性。在碱性条件下，催化析氢反应时仅需50 mV的过电位即可达到10 mA·cm^-2的电流密度，Tafel斜率为52.3 mV·dec^-1。而相同条件下原始NiFe LDH达到10mA·cm^-2的电流密度则需要226 mV的过电位，Tafel斜率为157.5 mV·dec^-1。同时制备的Ru/NiFe LDH也展现出了良好的析氧催化活性，在50 mA·cm^-2的电流密度下，过电位仅为231 mV，而NiFe LDH则需237 mV。Ru/NiFe LDH在长时间的电催化条件下依然能保持良好的工作稳定性。     

共浸渍制备高效的Ru/AC氨合成催化剂

通过钌的络合物前驱体和硝酸钡的共浸渍制备的Ru Ba K/AC催化剂氨合成转化效率高,其氨合成转化频率在0.87～1.30 s-1之间,与氯化钌制备的Ru/AC催化剂相比,其转化频率提高幅度在26%～88%。共浸渍法制备的催化剂氨合成转化效率高,其主要原因可能是共浸渍法制备的催化剂钌粒子粒径分布区间较窄,易形成更多的活性位;钌表面氢的吸附受到抑制,氮更易活化,因而催化效率更高。     

Ru纳米团簇/MoO3-x纳米带双功能催化剂的合成及其肼辅助全解水性能

将超小Ru纳米团簇锚定于富含氧空位MoO_3-x纳米带的双功能催化剂（Ru/MoO_3-x）。该催化剂展现出优异的肼氧化（HzOR）和析氢反应（HER）催化性能,10 mA·cm^-2时的过电势分别为-79和-27 mV,所组成的肼辅助电催化全解水（OWS）的电解池电压仅为13 mV,明显优于商业化20% Pt/C和已报道的一些催化剂。如此优异的性能主要归因于Ru纳米团簇有利于HzOR中N₂H₄的脱氢和HER氢中间体的吸/脱附平衡以及MoO_3-x中的氧空位和Ru/MoO_3-x异质结构导致的丰富的电化学活性位点和优化的电子转移动力学。     

Ru/ZSM-5催化葡萄糖选择性加氢制备山梨醇(英)

采用无有机模板剂一步法制备了Ru/ZSM-5催化剂,利用X射线衍射、N₂吸附-脱附、NH₃-程序升温脱附和CO₂-程序升温脱附、扫描电镜和透射电镜等方法对催化剂进行了表征.考察了反应温度、钌负载量和催化剂重复利用等因素对Ru/ZSM-5上葡萄糖加氢反应性能的影响,并与浸渍法制备的Ru/ZSM-5催化剂进行了对比.结果表明,与传统浸渍法相比,一步法制备的Ru/ZSM-5催化剂钌粒子具有更高的分散性和稳定性.在120℃和4 MPa的温和反应条件下,葡萄糖接近完全转化,山梨醇选择性高达99.2%,催化剂可重复利用5次,仍保持较高活性.     

Highly Effective Ru/BaCeO3 Catalysts on Supports with Strong Basic Sites for Ammonia Synthesis

BaCeO₃‐a and BaCeO₃‐b, with strong basic sites, were synthesized by using a co‐precipitation method at different calcination temperatures, and used as supports to evaluate their performance in ammonia synthesis. The ammonia synthesis rate with the 1.25 % Ru/BaCeO₃‐a catalyst is 24 mmol g^?1 h^?1, which is higher than that of 1.25 % Ru/BaCeO₃‐b catalyst (18 mmol g^?1 h^?1) at 3 MPa and 450 °C. Moreover, the performance of the 4 % Cs‐1.25 % Ru/BaCeO₃‐a catalyst was further improved to 28 mmol g^?1 h^?1, and no sign of deactivation was observed after a reaction time of 120 h. The XPS and H₂ temperature‐programmed reduction analyses indicated that the Ru/BaCeO₃‐a catalyst has more oxygen vacancies than the Ru/BaCeO₃‐b catalyst. In addition, the average Ru particle size of the Ru/BaCeO₃‐a catalyst is closer to 2 nm than the Ru/BaCeO₃‐b catalyst, which promotes the generation of B₅‐type sites (the active site for N₂ dissociation). The CO₂ temperature‐programmed desorption analysis indicates that BaCeO₃‐a has a high basic density, which is beneficial for electron transfer to Ru and further facilitates the dissociation of N≡N bonds.     

Ru/Ni/MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> catalysts for steam reforming of methane: effects of Ru content on self-activation property

The effects of Ru on the self-reducibility of Ru-doped Ni/MgAl₂O₄ catalysts, which do not need pre-reduction treatment with H₂, were investigated in the steam reforming of methane (SRM). The Ru-promoted Ni/MgAl₂O₄ catalysts with various amounts of Ru (0–0.5 wt%) were prepared by stepwise impregnation and co-impregnation methods using hydrotalcite-like MgAl₂O₄ support. For comparison, Ru/MgAl₂O₄ catalysts with the same amount of Ru were also prepared by the impregnation method. The catalysts were characterized by the N₂-sorption, XRD, H₂-TPR, H₂-chemisorption, and XPS methods. Ni/MgAl₂O₄ catalyst in the presence of even the trace amount of Ru (Ru content ≥0.05 wt%) showed higher conversion without pre-reduction as compared to Ru/MgAl₂O₄ catalysts in SRM under the same conditions. The self-activation of Ru–Ni/MgAl₂O₄ catalysts is mainly attributed to the spillover of hydrogen, which is produced on Ru at first and then reduces NiO species under reaction conditions. Besides, Ru doping makes the reduction of NiO easier. The stepwise impregnated Ru/Ni/MgAl₂O₄ catalyst produced superior performance as compared to co-impregnated Ru–Ni/MgAl₂O₄ catalyst for SRM.     

Catalytic properties of Ru nanoparticles embedded on ordered mesoporous carbon with different pore size in Fischer-Tropsch synthesis

A series of 3 wt% Ru embedded on ordered mesoporous carbon (OMC) catalysts with different pore sizes were prepared by autoreduction between ruthenium precursors and carbon sources at 1123 K. Ru nanoparticles were embedded on the carbon walls of OMC. Characterization technologies including power X-ray diffraction (XRD), nitrogen adsorption-desorption, transmission electron microscopy (TEM), and hydrogen temperature-programmed reduction (H₂-TPR) were used to scrutinize the catalysts. The catalyst activity for Fischer-Tropsch synthesis (FTS) was measured in a fixed bed reactor. It was revealed that 3 wt% Ru-OMC catalysts exhibited highly ordered mesoporous structure and large surface area. Compared with the catalysts with smaller pores, the catalysts with larger pores were inclined to form larger Ru particles. These 3 wt% Ru-OMC catalysts with different pore sizes were more stable than 3 wt% Ru/AC catalyst during the FTS reactions because Ru particles were embedded on the carbon walls, suppressing particles aggregation, movement and oxidation. The catalytic activity and C₅₊ selectivity were found to increase with the increasing pore size, however, CH₄ selectivity showed the opposite trend. These changes may be explained in terms of the special environment of the active Ru sites and the diffusion of products in the pores of the catalysts, suggesting that the activity and hydrocarbon selectivity are more dependent on the pore size of OMC than on the Ru particle size.     

Electrocatalytic reduction of NAD+ at glassy carbon electrode modified with single-walled carbon nanotubes and Ru(III) complexes

A simple procedure was developed to prepare a glassy carbon electrode modified with carbon nanotubes and Ruthenium (III) complexes. First, 25 μl of dimethyl sulfoxide–carbon nanotubes solutions (0.4 mg/ml) was cast on the surface of the glassy carbon electrode and dried in air to form a carbon nanotube film at the electrode surface. Then, the glassy carbon/carbon nanotube-modified electrode was immersed into a Ruthenium (III) complex solution (direct deposition) for a short period of time (10–20 s for multiwalled carbon nanotubes and 20–40 s for single-walled carbon nanotubes). The cyclic voltammograms of the modified electrode in aqueous solution shows a pair of well-defined, stable, and nearly reversible redox couple, Ru(III)/Ru(II), with surface-confined characteristics. The attractive mechanical and electrical characteristics of carbon nanostructures and unique properties and reactivity of Ru complexes are combined. The transfer coefficient (α), heterogeneous electron transfer rate constants (k _s), and surface concentrations (Γ) for the glassy carbon/single-walled carbon nanotubes/Ru(III) complex-, glassy carbon/multiwalled carbon nanotubes/Ru(III) complex-, and glassy carbon/Ru(III) complex-modified electrodes were calculated using the cyclic voltammetry technique. The modified electrodes showed excellent catalytic activity, fast response time, and high sensitivity toward the reduction of nicotinamide adenine dinucleotide in phosphate buffer solutions at a pH range of 4–8. The catalytic cathodic current depends on the nicotinamide adenine dinucleotide concentration. In the presence of alcohol dehydrogenase, the modified electrode exhibited a response to addition of acetaldehyde. Therefore, the main product of nicotinamide adenine dinucleotide electroreduction at the Ru(III) complex/carbon nanotube-modified electrode was the enzymatically active NADH. The purposed sensor can be used for acetaldehyde determination.     

Production of Primary Amines by Reductive Amination of Biomass‐Derived Aldehydes/Ketones

Transformation of biomass into valuable nitrogen‐containing compounds is highly desired, yet limited success has been achieved. Here we report an efficient catalyst system, partially reduced Ru/ZrO₂, which could catalyze the reductive amination of a variety of biomass‐derived aldehydes/ketones in aqueous ammonia. With this approach, a spectrum of renewable primary amines was produced in good to excellent yields. Moreover, we have demonstrated a two‐step approach for production of ethanolamine, a large‐market nitrogen‐containing chemical, from lignocellulose in an overall yield of 10 %. Extensive characterizations showed that Ru/ZrO₂‐containing multivalence Ru association species worked as a bifunctional catalyst, with RuO₂ as acidic promoter to facilitate the activation of carbonyl groups and Ru as active sites for the subsequent imine hydrogenation.     

Tuning the hydrogen and hydroxyl adsorption on Ru nanoparticles for hydrogen electrode reactions via size controlling

Controlling the particle size of catalyst to understand the active sites is the key to design efficient electrocatalysts toward hydrogen electrode reactions including hydrogen oxidation and evolution (HOR/HER). Herein, the hydrogen and hydroxyl adsorption on Ru/C could be effectively tuned for HOR/HER by simple controlling the particle sizes. It is found that the metallic Ru (Ru⁰) is the active site for HOR/HER, while oxidized Ru (Ru^x+) will hinder the adsorption and desorption of hydrogen on the catalyst. For the HOR, catalyst with small particles is more efficient, due to it is a three-phase interface reaction of gas on the surface of the catalyst. For the HER, the metallic state of Ru is crucial. The deconvolution of hydrogen peaks indicates that the catalytic sites with low hydrogen binding energy (HBE) shoulder the majority of the HOR activity. CO stripping curve further demonstrates that the stronger hydroxyl species (OH_ad) affinity is beneficial to promote the HOR performance. The results indicate that the design of efficient HOR/HER catalyst should focus on the balance between particle size and metallic states.     

Study of the Ru/Ce system in the oxidation of carbon black and volatile organic compounds

The relationship between the state of Ru on CeO₂ and catalytic activity in the oxidation of carbon black (CB) and some volatile organic compounds (VOCs) was investigated for Ru/CeO₂ catalysts prepared by wet impregnation. It was demonstrated that the addition of ruthenium to ceria significantly improved the reactivity of the latter. The temperature programmed reduction (TPR) experiments of Ru/CeO₂ showed that the oxygen species of RuO₂ was reduced at low temperatures. In addition, Electronic Paramagnetic Resonance (EPR) studies of outgassed samples at different temperatures showed an anisotropic signal indicating that Ru(IV) was reduced to intermediate valence states like Ru(III) before its total reduction to metallic Ru. It was concluded that Ru-O-Ce bonds in the well-dispersed Ru species are highly fragile and its mobile oxygen is the active species in the catalytic oxidation process. Published in Russian in Kinetika i Kataliz, 2007, Vol. 48, No. 6, pp. 893–898. This article was submitted by the authors in English.     

Ru(III)-catalyzed oxidation of pyruvic acid by iodate -A kinetic study

Ru(III) acts as a catalyst in the oxidative decarboxylation of pyruvic acid by iodate. The reaction is found to be first order with respect to [oxidant] and [catalyst] and fractional order in [pyruvic acid]. Increase in the concentration of H₂SO₄ and decrease in the dielectric constant of the medium retard the oxidation process. The product of oxidation is acetic acid. A mechanism involving the formation of a complex between the substrate and the catalyst, which reacts with the oxidant in the slow step is proposed. The formation constant of the complex and the rate constant of the slow step are determined. This revised version was published online in June 2006 with corrections to the Cover Date.     

Cooperative Catalysis of Ru(III)-Porphyrin in CO2-Involved Synthesis of Oxazolidinones

CO₂-transformations into high value-added products have become a fascinating area in green chemistry. Herein, a Ru(III)-porphyrin catalyst (RuCl₃ ⋅ 3H₂O−H₂TPP) was found highly efficient in the three-component reaction of CO₂, aliphatic amines and dichloroethane (or its derivative) for synthesis of oxazolidinones in the yields of 71∼91%. It was indicated by means of the control experiments and UV-vis spectra that CO₂ was stoichiometrically activated by the involved aliphatic amine substrates to form a stable carbamate salt while 1,2-dichloroethane (or its derivative) was independently activated by the involved Ru(III)-porphyrin catalyst. The combination of CO₂-activation by aliphatic amines with 1,2-dichloroethane activation by Ru(III)-porphyrin catalyst cooperatively contributed to this successful transformation.     

Role of ZnNb2O6 in ZnO-promoted amorphous-Nb2O5 supported Ru catalyst for the partial hydrogenation of benzene

Ruthenium catalysts supported on zinc-promoted amorphous-niobium mixed oxides were prepared, characterized, and studied in the additive-free partial hydrogenation of benzene reaction. The amorphous matrix of Nb₂O₅ was responsible for a highly active Ru/Nb₂O₅ catalyst, although less selective than those containing zinc. The ZnO-containing supports were prepared by wet impregnation technique, followed by incipient wetness of ruthenium chloride salt. The catalysts were characterized by textural analysis, X-ray fluorescence, X-ray diffraction, H₂ chemisorption, temperature-programmed reduction (TPR), Scanning electron microscopy, H₂ temperature-programmed desorption, and X-ray photoelectron spectroscopy (XPS) of the calcined-reduced samples. Chlorine retention was observed on zinc-containing samples. An unexpected ZnNb₂O₆ oxide phase, ascribed to a selectivity increase with less activity loss, was obtained for the supports at lower temperatures than those related on the literature. A very complex electronic environment of Ru- and Zn-containing species interactions was observed by TPR. The presence of surface-reduced (Ru⁰) and partially reduced (Ru^δ+) Ru species observed by XPS justified well, respectively, the activity and selectivity achieved with every catalyst. The addition of water as a solvent resulted in very constant yield to cyclohexene, as expected, despite activity diminution due to low solubility of the reactants.     

焙烧气氛对Ru/Al2O3催化剂上甲烷部分氧化制合成气反应性能的影响

采用气相色谱、质谱和原位时间分辨红外光谱等技术对空气和Ar气氛中焙烧的Ru/Al2O3催化剂样品上甲烷部分氧化(POM)制合成气反应进行了跟踪,并采用化学吸附、X射线衍射、拉曼光谱和H2-程序升温还原等技术对催化剂进行了表征.结果表明,在Ru/Al2O3-Air上POM反应出现振荡现象,而在Ru/Al2O3-Ar上则可...     

TI(III) oxidation of alkenes and alkynes and Ru(III) catalysis in the oxidation of alkenes: A kinetic and mechanistic study

The oxidation of trans-stilbene, phenylacetylene, and diphenylacetylene by Tl(OAc)₃ in aqueous acetic acid medium in the presence of HClO₄ follows the rate law in [H⁺] of 0.1–1.0M, the [H⁺] dependence below 0.1M being marginal. The reactions are strongly dielectric dependent. The order of reactivity among the substrates is styrene > phenylacetylene and trans-stilbene > diphenylacetylene. A mechanism involving the oxythallation adduct by the Tl⁺(OAc)₂ species has been discussed. The use of Ru(III) as a homogeneous catalyst brings a change in the kinetic orders for trans-stilbene, the rate law being The formation constants K for the Ru(III)–alkene π complex at 40, 50, and 60°C are 90.14M^?1, 105.2M^?1, and 127.7M^?1, respectively. Interestingly the oxidation of phenylacetylene and diphenylacetylene does not undergo catalysis by Ru(III). The mechanism involving the metal–arene π complex is discussed.