Construction of Pd-doped RuO_(2) nanosheets for efficient and stable acidic water oxidation

RuO_(2) has been considered a potential alternative to commercial IrO_(2) for the oxygen evolution reaction(OER)due to its superior intrinsic activity.However,its inherent structure dissolution in acidic environments restricts its commercial applications.In this study,we report a novel Pd-doped ruthenium oxide(Pd–RuO_(2))nanosheet catalyst that exhibits improved activity and stability through a synergistic effect of Pd modulation of Ru electronic structure and the two-dimensional structure.The catalyst exhibits excellent performance,achieving an overpotential of only 204 mVat a current density of 10 mA cm^(-2).Impressively,after undergoing 8000 cycles of cyclic voltammetry testing,the overpotential merely decreased by 5 mV.The PEM electrolyzer with Pd0.08Ru0.92O_(2) as an anode catalyst survived an almost 130 h operation at 200 mA cm^(-2).To elucidate the underlying mechanisms responsible for the enhanced stability,we conducted an X-ray photoelectron spectroscopy(XPS)analysis,which reveals that the electron transfer from Pd to Ru effectively circumvents the over-oxidation of Ru,thus playing a crucial role in enhancing the catalyst's stability.Furthermore,density functional theory(DFT)calculations provide compelling evidence that the introduction of Pd into RuO_(2) effectively modulates electron correlations and facilitates the electron transfer from Pd to Ru,thereby preventing the overoxidation of Ru.Additionally,the application of the two-dimensional structure effectively inhibited the aggregation and growth of nanoparticles,further bolstering the structural integrity of the catalyst.

Hydrous Ruthenium Oxide with High Rate Pseudo-Capacitance Prepared by a New Sol-Gel Process

A kind of ruthenium oxide with smaller particles and higher porosity was prepared by a sol-gel process with RuCl3·xH2O and NaHCO3 solution. Several details concerning this new material, including crystal structure, particle size as functions of the temperature, and electrochemical properties were also reported. The optimal annealing temperature was 210 ℃ and the powder annealed at this temperature had a rate capacitance of 541 F/g. In addition, the rate capacitance of the composite electrode reached 802 F/g after 10% carbon black was added, much higher than any previously reported value. High energy density supercapacitors were built with the newly discovered electrode material. Energy densities as high as 67 J/g were obtained based on the RuO2·xH2O alone. By introducing the highly porous carbon black into the electrode, energy densities great than 100 J/g could be achieved. The power density of the capacitor was enhanced significantly.

Pseudo-capacitance of ruthenium oxide/carbon black composites for electrochemical capacitors

Hydrous ruthenium oxide was formed by a new process. The precursor was obtained by mixing the aqueous solutions of RuCl3xH2O and NaHCO3. The addition of NaHCO3 led to the formation of an oxide with extremely fine RuO2 particles forming a porous network structure in the oxide electrode. Polyethylene glycol was added as a controller to partly inhibit the sol-gel reaction. The rate capacitance of 530 F·g^-1 was measured for the powder formed at an optimal annealing temperature of 210℃. Several details concerning this new material, including crystal structure, particle size as a function of temperature, and electrochemical properties, were also reported. In addition, the rate capacitance of the composite electrode reached 800 F·g^-1 after carbon black was added. By using the modified electrode of a RuO2/carbon black composite electrode, the electrochemical capacitor exhibits high energy density and stable power characteristics. The values of specific energy and maximum specific power of 24 Wh·kg^-1 and 4 kW·kg^-1, respectively, are demonstrated for a cell voltage between 0 and 1 V.

Promoting effect of chloride ions on selective oxidation of methanol to methyl formate over zirconia-supported ruthenium oxide catalysts

The effect of chloride ions on a monoclinic ZrO2-supported RuOx （RuOx/m-ZrO2） catalyst with a Ru surface density of 0.3 Ru/nm2 was studied in the selective oxidation of methanol to methyl formate （MF） at a low temperature of 373 K. The m-ZrO2 support was Cl-free, and Cl- ions were introduced into the RuOx/m-ZrO2 catalyst by impregnation with zirconium oxychloride or ammonium chloride and subsequent thermal treatment in air at 673 K. The structures of these catalysts were characterized by X-ray diffraction, Raman and X-ray photoelectron spectroscopies. Their reducibility was probed by temperature-programmed reduction in H2. The RuOx domains were present as highly dispersed Rut42- structure on m-ZrO2 with similar reducibility for the RuOx/m-ZrO2 samples irrespective of modification with or without Cl ions. Introduction of appropriate amounts of zirconium oxychloride into RuOx/m-ZrO2 led to a remarkable increase in the methanol oxidation rate and MF selectivity, whereas introduction of ammonium chloride or zirconyl nitrate significantly inhibited the catalytic performance of RuOx/m-ZrO2. The promoting effect of Cl- ions derived from zirconium oxychloride can be tentatively attributed to their roles in facilitating the adsorption of methanol and desorption of MF product or its intermediates. This finding provides novel insights into the promoting effect of Cl- ions on oxides-based catalysts for selective oxidation reactions.

Study on the Characteristics of the Ruthenium Oxide pH Electrode

Ruthenium oxide,which fabricated by radio frequency sputtering is used as the sensitive membrane,which shows that the pH sensitivity is very high and has a linear response in different buffer solutions.The pH electrode,which applies the structure of separative structure EGFET (Extended Gate Field Effect Transistor) insteads of the conventional gate ISFET (Ion Sensitive Field Effect Transistor) for reducing the cost of the fabrication and measurement.Unfortunately,the performance of the pH sensor was falsified by the drift and hysteresis.In addition,the total response is composed of the intrinsic response and drift,and the hysteresis effect combines the slow response with drift.Consequently,we would also investigate the drift in the buffer solutions and hysteresis effect in the different paths.In this way,the more accurate sensing properties are obtained by the RuO_x pH electrode.

Development and Electrochemical Studies of Ruthenium Based Mixed Oxide Catalyst Electrodes for Chlorine Evolution

Experimental results are presented which allow comparison of the electrochemical performance of RuO 2/Ti, Ru 0 3 Sn 0 7 O 2/Ti and Ru 0 3 V 0 7 O 2/Ti catalysts prepared on a titanium substrate by thermal decomposition from respective precursors. The highest activity for chlorine evolution is observed on the Ru 0 3 V 0 7 O 2/Ti electrode, lower on Ru 0 3 Sn 0 7 O 2/Ti and least on RuO 2/Ti. Voltammograms obtained in the polarisable region are used to characterize the different electrodes. Further more an analysis of the catalytic activity and reaction kinetics of the developed electrodes in NaCl are presented.

Composition change and capacitance properties of ruthenium oxide thin film

Ru O2·n H2O film was deposited on tantalum foils by electrodeposition and heat treatment using Ru Cl3·3H2O as precursor.Surface morphology, composition change and cyclic voltammetry from precursor to amorphous and crystalline RuO2·n H2O films were studied by X-ray diffractometer, Fourier transformation infrared spectrometer, differential thermal analyzer, scanning electron microscope and electrochemical analyzer, respectively. The results show that the precursor was transformed gradually from amorphous to crystalline phase with temperature. When heat treated at 300 °C for 2h, RuO2·n H2O electrode surface gains mass of2.5 mg/cm2 with specific capacitance of 782 F/g. Besides, it is found that the specific capacitance of the film decreased by roughly20% with voltage scan rate increasing from 5 to 250 m V/s.

Constructing a hollow core-shell structure of RuO_(2) wrapped by hierarchical porous carbon shell with Ru NPs loading for supercapacitor

Hollow core-shell structure nanomaterials have been broadly used in energy storage, catalysis, reactor,and other fields due to their unique characteristics, including the synergy between different materials,a large specific surface area, small density, large charge carrying capacity and so on. However, their synthesis processes were mostly complicated, and few researches reported one-step encapsulation of different valence states of precious metals in carbon-based materials. Hence, a novel hollow core-shell nanostructure electrode material, RuO_(2)@Ru/HCs, with a lower mass of ruthenium to reduce costs was constructed by one-step hydrothermal method with hard template and co-assembled strategy, consisting of RuO_(2) core and ruthenium nanoparticles(Ru NPs) in carbon shell. The Ru NPs were uniformly assembled in the carbon layer, which not only improved the electronic conductivity but also provided more active centers to enhance the pseudocapacitance. The RuO_(2) core further enhanced the material’s energy storage capacity. Excellent capacitance storage(318.5 F·g^(-1)at 0.5 A·g^(-1)), rate performance(64.4%) from 0.5 A·g^(-1)to 20 A·g^(-1), and cycling stability(92.3% retention after 5000 cycles) were obtained by adjusting Ru loading to 0.92%(mass). It could be attributed to the wider pore size distribution in the micropores which increased the transfer of electrons and protons. The symmetrical supercapacitor device based on RuO_(2)@Ru/HCs could successfully light up the LED lamp. Therefore, our work verified that interfacial modification of RuO_(2) and carbon could bring attractive insights into energy density for nextgeneration supercapacitors.

Engineering Ru(IV)charge density in Ru@RuO2 core-shell electrocatalyst via tensile strain for efficient oxygen evolution in acidic media

The design of efficient Ru-based electrocatalysts with high intrinsic activities for acidic water oxidation is highly desirable and challenging for water splitting in proton exchange membrane electrolyzers.Here,for the first time,we engineer the charge density of Ru(IV)by creating tensile strains in the RuO2 shell of Ru@RuO2 core-shell nanoparticles,viz.Ru@RuO2-L.High-resolution spectroscopic characterizations confirm the presence of av.6%tensile strain in Ru-O bonds,which results in an effective reduction of the Ru(IV)charge density.The resultant Ru^X+(4<X<5)active sites greatly accelerate the oxygen evolution reaction(OER)in an acidic electrolyte,leading to a remarkably low overpotential of 191 mV at 10 mA cm^-2.These values are lower than those for the benchmark RuO2 catalyst and are also among the lowest for efficient Ru-based electrocatalysts reported thus far.The specific activity and mass activity are also greatly enhanced 4.2-fold and 17.7-fold compared to those of RuO2,respectively.The acidic OER activity improvement is ascribed to the lowered adsorption energy of*OOH,owing to the reduced charge density of Ru(IV),and the rapid charge transport owing to the Ru core.Ru@RuO2-L also demonstrates high feasibility as the anode catalyst for the overall water splitting in acidic media.

Selective conversion of N_(2) to NH_(3) on highly dispersed RuO_(2) using amphiphilic ionic liquid-anchored fibrous carbon structure

Ammonia (NH_(3)) plays a key role in the agricultural fertilizer and commodity chemical industries and is useful for exploring hydrogen storage carriers.The electrochemical nitrogen reduction reaction (NRR) is receiving attention as an environmentally sustainable NH_(3) synthesis replacement for the traditional Haber–Bosch process owing to its near ambient reaction conditions (<100℃ and 1 atm).However,its NH_(3) yield and faradaic efficiency are extremely low because of the sluggish kinetics of N≡N bond dissociation and the hindrance from competitive hydrogen evolution.To overcome these challenges,we herein introduce a dual-functionalized ionic liquid (1-(4-hydroxybutyl)-3-methylimidazolium hydroxide[HOBIM]OH) for a highly dispersed ruthenium oxide electrocatalyst to achieve a biased NRR.The observed uniform distribution of RuO_(2) on the carbon fiber and increase in the surface area for N_(2) adsorption by limiting proton access can be attributed to the presence of imidazolium ions.Moreover,extensive N_(2) adsorption contributes to enhanced NRR selectivity with an NH_(3) yield of 3.0×10^(-10)mol cm^(-2)s^(-1)(91.8μg h^(-1)mg^(-1)) and a faradaic efficiency of 2.2%at-0.20 V_(RHE).We expect our observations to provide new insights into the design of effective electrode structures for electrochemical NH;synthesis.

Mixed B-site ruddlesden-popper phase Sr_(2)(Ru_(x)Ir_(1-x))O_(4) enables enhanced activity for oxygen evolution reaction

Development of high performance electrocatalysts for oxygen evolution reaction (OER) in acidic media remains a challenge for direct water splitting using an electrolyzer.Recently,Ruddlesden-Popper phase Sr_(2)IrO_(4)was discovered to be an efficient OER catalyst because of its unique structure,which consists of layers of both rock salt and perovskite phases simultaneously.In this study,we prepared a series of B-site mixed,Ruddlesden-Popper phase of Sr_(2)(Ru_(x)Ir_(1-x))O_(4) and examined their electrocatalytic properties for OER in acidic media.Through partial substitution of Ru in the B-site of Ruddlesden-Popper phase materials,we achieved much enhanced OER performance for this series of Sr_(2)(Ru_(x)Ir_(1-x))O_(4)electrocatalysts,among which Sr_(2)(Ru_(0.5)Ir_(0.5))O_(4)exhibited the best catalytic activity with a current density of 8.06 m A/cm^(2) at 1.55 V and a Tafel slope of 47 m V/dec.This current density is three times higher than that of Sr_(2)Ir O_(4).The B-site mixed Sr_(2)(Ru_(0.5)Ir_(0.5))O_(4)retained good stability in acidic conditions for>24 h at 10 m A/cm^(2).A range of techniques were used to characterize the crystal and electronic structures of the Sr_(2)(Ru_(x)Ir_(1-x))O_(4)samples.Our data indicate that the improved OER performance can be correlated to the formation of high level of hydroxyl groups and the enhanced overlap between Ir/Ru 4d and O_(2)p orbitals,revealing a new way for the design of efficient OER electrocatalysts by regulating their composition and electronic structures.

Structural Description of Polyaromatic Nucleus in Residue

The proton nuclear magnetic resonance spectroscopy （1H-NMR）, the synchronous fluorescence spectrometry （SFS） and the ruthenium ions catalyzed oxidation （RICO） method were used to determine the chemical structure of polyaromatic nucleus in Oman residue fractions. The results of 1H-NMR analyses showed that the average numbers of aromatic rings in the aromatics, resins and asphaltenes units were 3.2, 5.6 and 8.2, respectively. SFS was used to investigate the distribution of aromatic rings in residue fractions, the main distribution range of aromatic rings in aromatics, resins and asphaltenes were 3 4 rings, 3--5 rings and more than 5 rings, respectively. The aromatic network in residue fractions was oxidized to produce numerous carboxylic acids. The types and content of benzenepolycarboxylic acids, such as phthalic acid, benzenetricarboxylic acids, benzenetetracarboxylic acids, benzenepentacarboxylic acid and benzenehexacarboxylic acid disclosed the condensed types of aromatic nuclei in the core. The biphenyl fraction （BIPH）, the cata-condensed fraction （CATA）, the peri-condensed fraction （PERI） and the condensed index （BCI） were calculated based on the benzenepolycarboxylic acids formed. The results implied that there was less biphenyl type structures in all residue fractions. The aromatics fraction was almost composed of the cata-condensed type system, and the asphaltenes fraction was wholly composed of the peri-condensed type system, while in the resins fraction co-existed the two types, herein the peri-con- densed type was predominant over the cata-condensed type. Based on the analytical results obtained in the study, the components --aromatics, resins and asphaltenes -- were given the likely structural models.

Improved kinetics of OER on Ru-Pb binary electrocatalyst by decoupling proton-electron transfer

The acidic oxygen evolution reaction(OER)is central to water electrolysis using proton‐exchange membranes.However,even as benchmark catalysts in the acidic OER,Ru‐based catalysts still suffer from sluggish kinetics owing to the scaling relationship that arises from the traditional concerted proton‐electron transfer(CPET)process.Motivated by the knowledge that a charged surface may be favorable for accelerating the OER kinetics,we posited the incorporation of elements with pseudocapacitive properties into Ru‐based catalysts.Herein,we report a RuPbOx electrocatalyst for efficient and stable water oxidation in acid with a low overpotential of 191 mV to reach 10 mA cm^(−2) and a low Tafel slope of 39 mV dec^(−1).The combination of electrochemical analysis,X‐ray photoelectron spectroscopy,and in situ Raman spectroscopy demonstrated that the improved OER kinetics was associated with the formation of superoxide precursors on the strongly charged surface after Pb incorporation,indicating a non‐concerted proton‐electron transfer mechanism for the OER on RuPbOx.

Study of Drift Behavior for RuO_x Sensing Membrane with Penicillinase Immobilized by GPTS

The ruthenium oxide(RuO_x) thin film was prepared by using the R.F.sputtering system.The RuO_x pH-sensitive electrode possesses a nearly-Nernstian pH sensitivity(about 57 mV/pH).For the enzyme penicillinase was immobilized directly onto a RuO_x pH-sensitive surface by 3-glycidoxypropyltrimethoxysilane(GPTS).Some characteristics of the biosensor, such as sensitivity,linear range,and drift,are investigated and the difference between penicillinase immobilized and without are compared.According to the time-constant model,we can extract the time constant and amplitude at the response curve of the drift.Subsequently,the extracted parameters were used to simulate the mechanism of the drift behavior.

Super-capacitive Properties of Thick RuO_2·xH_2O Electrodes:Effect of Thickness,Binder and Carbon Black Addition

Hydrous ruthenium oxide,RuO2·xH2O,was synthesized through a sol-gel reaction of ruthenium chloride aqueous solution.The annealed RuO2·xH2O powders are aggregate of very small particles in nano-size of 70-80 nm and have abundant porous structure as observed by SEM.The effect of electrode thickness,PTFE binder and carbon black addition on the super-capacitive properties of thick RuO2·nH2O electrodes was investigated.At low scan rate of 5 mV/s,the specific capacitance of RuO2·xH2O (SCR,based on the weight of RuO2·xH2O only) for pure RuO2·xH2O and RuO2·xH2O-PTFE-CB electrodes can reach 665 F/g.Increasing electrode thickness and mixing PTFE into RuO2·xH2O lead to a degradation of SCR and rate capacity.By adding carbon black into RuO2·xH2O-PTFE mixture,the rate capacity of the thick electrode (RuO2·xH2O-PTFE-CB) can be improved close to the thick pure RuO2·xH2O electrode.However,mixing with PTFE and carbon black leads to a loss of the overall mass-specific capacitance.The reason for the dependence of SCR and rate capacity on electrode thickness,binder and carbon black addition was discussed based on the relation between the resistance and utilization rate of electrodes.

Scanning tunnelling microscope studies of growth of RuO2（110） thin layer on Ru（0001）

This paper reports that the growth of RuO2（110） thin layer growth on Ru（0001） has been investigated by means of scanning tunnelling microscope （STM）. The STM images showed a domain structure with three rotational domains of RuO2（110） rotated by an angle of 120°. The as-grown RuO2（110） thin layer is expanded from the bulk-truncated RuO2（110） due to the large mismatch between RuO2（110） and the Ru（0001） substrate. The results also indicate that growth of RuO2（110） thin layer on the Ru（0001） substrate by oxidation tends first to formation of the Ru-O （oxygen） chains in the [001] direction of RuO2 （110）.

Core-shell structured Ru-Ni@SiO_2: Active for partial oxidation of methane with tunable H_2/CO ratio

This study demonstrated that a Ru-Ni bimetallic core-shell catalyst（0.6%Ru-Ni）@Si O2with a proper surface Ru concentration is superior in achieving better catalytic activity and tunable H2/CO ratio at a comparatively lower reaction temperature（700℃）.Compared to the impregnation method,the hydrothermal approach leads to a highly uniform Ru distribution throughout the core particles.Uniform Ru distribution would result in a proper surface Ru concentration as well as more direct Ru-Ni interaction,accounting for better catalyst performance.Enriched surface Ru species hinders surface carbon deposition,but also declines overall activity and H2/CO ratio,meanwhile likely enhances Ni oxidation to certain degree under the applied reaction conditions.Over the current（m%Ru-Ni）@Si O2catalyst,the formation of fibrous carbon species is suppressed,which accounts for good stability of catalyst within a TOS of 10 h.

Boosting electrochemical oxidation of As(Ⅲ)on Fe-doped RuO_(2)/PEDOT/SnO_(2) nanocomposite anode:Fabrication,performance and mechanism

Design of electrode materials for stable and efficient electrocatalytic oxidation of As(Ⅲ)in arsenic-contaminated groundwater poses a great challenge due to the rapid deactivation of catalysts resulting from the high oxygen evolution potential(OEP)and considerable barrier to generating reactive oxygen species(ROS).Herein,an innovative TNAs/SnO_(2)/PEDOT/Fe(Ⅲ)-RuO_(2) multilayer electrode was synthesized by utilizing a PEDOT-coated SnO_(2) interlayer as a supportive framework to combine Fe-doped amorphous RuO_(2) catalytic layer with TiO_(2) nanotube array substrate.Such electrode exhibited high activity and sta-bility for the oxidation of As(Ⅲ)to As(V)due to the large surface area provided by the TiO_(2) nanotube arrays and the SnO_(2)/PEDOT interlayer for facilitating the growth of the catalytic layer.The electrochem-ically active surface area of the electrode reached as high as 31.7 mF/cm^(2).Impressively,the doping of Fe into RuO_(2) layer led to a remarkable increase in the OEP value to 3.12 V,which boosted the indirect oxidation process mediated by ROS at a lower potential to achieve the As(Ⅲ)oxidation ratio of 98.5%.DFT calculations revealed that the Fe-doped amorphous RuO_(2) weakened the adsorption strength of·OH and.SO4-intermediates and lowered the energy barrier for generating ROS.Combined with ESR results,the formation of·OH and·SC4-with strong oxidizing properties was fully verified,providing further evi-dence for the involvement of ROS as the main mediator of the oxidation mechanism of As(Ⅲ).This work may provide valuable perspectives into the design of catalytic layer structures and heteroatom doping modifications for composite-coated electrodes.

Enriched electrophilic oxygen species facilitate acidic oxygen evolution on Ru-Mo binary oxide catalysts

The polymer electrolyte membrane(PEM)electrolyzers are burdened with costly iridium(Ir)-based catalysts and high operation overpotentials for the oxygen evolution reaction(OER).The development of earth-abundant,highly active,and durable electrocatalysts to replace Ir is a critical step in reducing the cost of green hydrogen production.Here we develop a Ru5Mo4Ox binary oxide catalyst that exhibits high activity and stability in acidic OER.The electron-withdrawing property of Mo enriches the electrophilic surface oxygen species,which promotes acidic OER to proceed via the adsorbate evolution pathway.As a result,we achieve a 189 mV overpotential at 10 mA·cm^(-2) and a Tafel slope of 48.8 mV·dec^(-1).Our catalyst demonstrates a substantial 18-fold increase in intrinsic activity,as evaluated by turnover frequency,compared to commercially available RuO_(2) and IrO_(2) catalysts.Moreover,we report a stable OER operation at 10 mA·cm^(-2) for 100 h with a low degradation rate of 2.05 mV·h^(-1).

Ruthenium Oxide/Reduced Graphene Oxide Nanoribbon Composite and Its Excellent Rate Capability in Supercapacitor Application

Chemical oxidation is used to cut and unzip multi-walled carbon nanotubes in the transverse direction and the axial direction to form graphene oxide nanoribbon （GONR）. Ruthenium oxide/reduced graphene oxide nanoribbon composite （RuO2/rGONR） with a 72.5 wt% RuO2 loading is synthesized through an aqueous-phase reaction, in which GONR is served as starting material, followed by mild thermal treatment in ambient air. The resulting RuO2/rGONR composite achieves specific capacitance up to 677 F.g l at the current density of 1 A·g^-1 in three-electrode system using 1 mol·L^-1 H2SO4 as electrolyte. The resultant electrode exhibits an excellent rate capability （91.8% retention rate at 20 A·g^-1）. Especially, the symmetric supercapacitor assembled on the basis of RuO2/rGONR electrode delivers high energy density （16.2 Wh·kg^-1） even at the power density of 9885 W·kg^-1, which is very essential for supercapacitors.