Mo-Doped Mesoporous RuO2 Spheres as High-Performance Acidic Oxygen Evolution Reaction Electrocatalyst.

The development of highly active and acid-stable electrocatalysts for oxygen evolution reaction (OER) is of great significance for water electrolysis technology. Herein, a highly efficient molybdenum-doped mesoporous ruthenium dioxide sphere (Mo-RuO2 ) catalyst is fabricated by a facile impregnation and post-calcination method using mesoporous carbon spheres to template the mesostructure. The optimal Mo0.15 -RuO2 catalyst with Mo doping amount of 15 mol.% exhibits a significantly low overpotential of 147 mV at 10 mA cm-2 , a small Tafel slope of 38 mV decade-1 , and enhanced electrochemical stability in acidic electrolyte, far superior to the commercial RuO2 catalyst. The experimental results and theoretical analysis reveal that the remarkable electrocatalytic performance can be attributed to the large surface area of the mesoporous spherical structure, the structural robustness of the interconnected mesoporous framework, and the change in the electronic structure of Ru active sites induced by Mo doping. These excellent advantages make Mo-doped mesoporous RuO2 spheres a promising catalyst for highly efficient electrocatalytic OER in acidic media.

Modulating *OOH Adsorption on RuO2 for Efficient and Durable Acidic Water Oxidation Electrocatalysis.

Acidic water electrolysis is of considerable interest due to its higher current density operation and energy conversion efficiency, but its real industrial application is highly limited by the shortage of efficient, stable, and cost-effective acidic oxygen evolution reaction (OER) electrocatalysts. Here, an electrocatalyst consisting of Ni-implanted RuO2 supported is reported on α-MnO2 (MnO2/RuO2-Ni) that shows high activity and remarkable durability in acidic OER. Precisely, the MnO2/RuO2-Ni catalyst shows an overpotential of 198 mV at a current density of 10 mA cm-2 and can operate continuously and stably for 400 h (j = 10 mA cm-2) without any obvious attenuation of activity, making it one of the best-performing acid-stable OER catalysts. Experimental results, in conjunction with density functional theory calculations, demonstrate that the interface electron transfer effect from RuO2 to MnO2, further enhanced by Ni incorporation, effectively modulates the adsorption of OOH* and significantly reduces the overpotential, thereby enhancing catalytic activity and durability.

Highly sensitive hydrolytic nanozyme-based sensors for colorimetric detection of aluminum ions.

Hydrolytic nanozyme-based visual colorimetry has emerged as a promising strategy for the detection of aluminum ions. However, most studies focus on simulating the structure of natural enzymes while neglecting to regulate the rate of hydrolysis-related steps, leading to low enzyme-like activity for hydrolytic nanozymes. Herein, we constructed a ruthenium dioxide (RuO2) in situ embedded cerium oxide (CeO2) nanozyme (RuO2/CeO2) with a Lewis acid-base pair (Ce-O-Ru-OH), which can simulate the catalytic behavior of phosphatase (PPase) and can be quantitatively quenched by Al3+ to achieve accurate and sensitive Al3+ colorimetric sensing detection. The incorporation of Ru into CeO2 nanorods accelerates the dissociation of H2O, followed by subsequent combination of hydroxide species to Lewis acidic Ce-O sites. This synergistic effect facilitates substrate activation and significantly enhances the hydrolysis activity of the nanozyme. The results show that the RuO2/CeO2 nanozyme exhibits a limit of detection as low as 0.5 ng/mL. We also demonstrate their efficacy in detecting Al3+ in various practical food samples. This study offers novel insights into the advancement of highly sensitive hydrolytic nanozyme engineering for sensing applications.

Electrostatic Self-Assembly of MXene on Ruthenium Dioxide-Modified Carbon Cloth for Electrochemical Detection of Kaempferol.

A superior composite material consisting of MXene and ruthenium dioxide-modified carbon cloth is synthesized by pulsed laser deposition and electrostatic self-assembly, which is further utilized to construct a class of novel electrochemical (EC) sensors for kaempferol (KA) detection. The carbon-cloth-based electrodes modified by ruthenium dioxide and then MXene are characterized by X-ray diffraction, scanning electron microscope, and X-ray photoemission spectroscopy. The EC process on the modified electrodes is analyzed by cyclic voltammetry, EC impedance spectroscopy, and differential pulse voltammetry. It is found that positively charged RuO2 not only possesses the remarkable electrical conductivity and electrocatalysis activity but also hampers the restacking of MXene, which accordingly enhances the exposure of the active surface area and greatly boosts the electrocatalysis activity of the entire composite. Consequently, this newly developed composite-based EC sensor exhibits a high sensitivity, selectivity, and remarkable stability to detect KA with two linear ranges of 0.06-1 and 1-15 µM. The inferred limit of detection is 0.039 µM via differential pulse voltammetry. More importantly, this novel EC sensor is found to be applicable for detecting KA in practical traditional Chinese medicines.

Low-energy electron microscopy intensity-voltage data - Factorization, sparse sampling and classification.

Low-energy electron microscopy (LEEM) taken as intensity-voltage (I-V) curves provides hyperspectral images of surfaces, which can be used to identify the surface type, but are difficult to analyse. Here, we demonstrate the use of an algorithm for factorizing the data into spectra and concentrations of characteristic components (FSC3 ) for identifying distinct physical surface phases. Importantly, FSC3 is an unsupervised and fast algorithm. As example data we use experiments on the growth of praseodymium oxide or ruthenium oxide on ruthenium single crystal substrates, both featuring a complex distribution of coexisting surface components, varying in both chemical composition and crystallographic structure. With the factorization result a sparse sampling method is demonstrated, reducing the measurement time by 1-2 orders of magnitude, relevant for dynamic surface studies. The FSC3 concentrations are providing the features for a support vector machine-based supervised classification of the surface types. Here, specific surface regions which have been identified structurally, via their diffraction pattern, as well as chemically by complementary spectro-microscopic techniques, are used as training sets. A reliable classification is demonstrated on both example LEEM I-V data sets.

The Characteristics Analysis of a Microfluid-Based EGFET Biosensor with On-Chip Sensing Film for Lactic Acid Detection.

In this research, a microfluid-based extended gate field-effect transistor (EGFET) biosensor with an on-chip sensing window (OCSW) was fabricated. The detection window was composed of six metal layers, and a ruthenium dioxide (RuO2) film was spattered on the surface and functionalized with lactase to detect lactic acid (LA). To detect LA in a more diversified way, a microfluidic system was integrated with the biosensor. Moreover, a special package was used to seal the sensing window and microfluidic tube and insulate it from other parts to prevent water molecule invasion and chip damage. The sensitivity analysis of the EGFET biosensor was studied by a semiconductor parameter analyzer (SPA). The static and dynamic measurements of the EGFET with sensing windows on a chip were analyzed. The sensing characteristics of the EGFET biosensor were verified by the experimental results. The proposed biosensor is suitable for wearable applications due to the advantages of its low weight, low voltage, and simple manufacturing process.

Advanced RuO2 Thin Films for pH Sensing Application.

RuO2 thin films were prepared using magnetron sputtering under different deposition conditions, including direct current (DC) and radio frequency (RF) discharges, metallic/oxide cathodes, different substrate temperatures, pressures, and deposition times. The surface morphology, residual stress, composition, crystal structure, mechanical properties, and pH performances of these RuO2 thin films were investigated. The RuO2 thin films RF sputtered from a metallic cathode at 250 °C exhibited good pH sensitivity of 56.35 mV/pH. However, these films were rougher, less dense, and relatively softer. However, the DC sputtered RuO2 thin film prepared from an oxide cathode at 250 °C exhibited a pH sensitivity of 57.37 mV/pH with a smoother surface, denser microstructure and higher hardness. The thin film RF sputtered from the metallic cathode exhibited better pH response than those RF sputtered from the oxide cathode due to the higher percentage of the RuO3 phase present in this film.

Highly Sensitive Levodopa Determination by Means of Adsorptive Stripping Voltammetry on Ruthenium Dioxide-Carbon Black-Nafion Modified Glassy Carbon Electrode.

A new, highly sensitive Adsorptive Stripping Voltammetric method for levodopa determination was developed. As a working electrode, the glassy carbon electrode (GCE) modified with carbon black (CB), RuO2·xH2O (RuO2) and Nafion was used (CB-RuO2-Nafion GCE). Levodopa signal obtained on the modified electrode was 12 times higher compared to GCE. During research, instrumental parameters were optimized: sampling time ts = 10 ms, waiting time tw = 10 ms, step potential Es = 5 mV and pulse amplitude ΔE = 50 mV. Preconcentration potential Eprec was equal to 0 mV. The best results were obtained in 0.025 M perchloric acid (approx. pH 1.4). Signal repeatability measured on the CB-RuO2-Nafion modified electrode for 0.2 µM of levodopa was equal to 2.1% (levodopa concentration 1 µM, n = 5). Linearity of the method was achieved in the concentration range from 1 to 8 µM. Limit of detection was equal to 17 nM. Recoveries calculated for pharmaceutical products and tap water measurements were in the range 102-105%, which confirms the accuracy of the developed. The applicability of the method was confirmed by analysis of pharmaceutical products and tap water samples. Based on obtained results, it might be concluded that the developed voltammetric method could be a useful tool in routine drug analysis.

Ruthenium dioxide nanoparticles as a high-capacity transducer in solid-contact polymer membrane-based pH-selective electrodes.

A new approach is presented for the design of ion selective electrodes. Ruthenium dioxide nanoparticles were incorporated into solid-contact electrodes, and their properties were studied for the case of pH-selective electrodes. The use of the RuO2 is shown to significantly improve the potentiometric response, while no redox response is observed. The use of RuO2 results in a Nernstian slope (59 mV/decade) towards hydrogen ions over a wide linear range (pH 2 to 12). The results obtained by chronopotentiometry reveal small resistance, and the capacitance is as high as 1.12 mF. This results in a good stability of the response and in a low potential drift (0.89 µV∙s-1). The electrodes exhibit properties nearly as excellent as those of a glass electrode, but they are much smaller, less fragile, and easy to use. Graphical abstractSchematic representation of the construction of the new kind of electrodes along with calibration and chronopotentiometric plots compared to non-modified GCD/H+-ISM and modified GCD/RuO2/H+-ISM electrodes, respectively. The use of ruthenium dioxide results in a wide analytical pH range (2-12) and in high electrical capacitance (1.12 mF).

An Efficient Electrochemical Sensor Driven by Hierarchical Hetero-Nanostructures Consisting of RuO2 Nanorods on WO3 Nanofibers for Detecting Biologically Relevant Molecules.

By means of electrospinning with the thermal annealing process, we investigate a highly efficient sensing platform driven by a hierarchical hetero-nanostructure for the sensitive detection of biologically relevant molecules, consisting of single crystalline ruthenium dioxide nanorods (RuO2 NRs) directly grown on the surface of electrospun tungsten trioxide nanofibers (WO3 NFs). Electrochemical measurements reveal the enhanced electron transfer kinetics at the prepared RuO2 NRs-WO3 NFs hetero-nanostructures due to the incorporation of conductive RuO2 NRs nanostructures with a high surface area, resulting in improved relevant electrochemical sensing performances for detecting H2O2 and L-ascorbic acid with high sensitivity.

NiO as a Bifunctional Promoter for RuO2 toward Superior Overall Water Splitting.

Conventional development of nanomaterials for efficient electrocatalysis is largely based on performance-oriented trial-and-error/iterative approaches, while a rational design approach at the atomic/molecular level is yet to be found. Here, inspired by a fundamental understanding of the mechanism for both oxygen and hydrogen evolution half reactions (OER/HER), a unique strategy is presented to engineer RuO2 for superior alkaline water electrolysis through coupling with NiO as an efficient bifunctional promoter. Benefitting from desired potential-induced interfacial synergies, NiO-derived NiOOH improves the oxygen binding energy of RuO2 for enhanced OER, and NiO also promotes water dissociation for enhanced HER on RuO2 -derived Ru. The resulting hybrid material exhibits remarkable bifunctional activities, affording 2.6 times higher OER activity than that of RuO2 and an HER activity comparable to Pt/C. As a result, the simple system requires only 1.5 V to deliver 10 mA cm-2 for overall alkaline water splitting, outperforming the benchmark PtC/NF||IrO2 /NF couple with high mass loading. Comprehensive electrochemical investigation reveals the unique and critical role of NiO on the optimized RuO2 /NiO interface for synergistically enhanced activities, which may be extended to broader (electro)catalytic systems.

Investigation of Sensitivities and Drift Effects of the Arrayed Flexible Chloride Sensor Based on RuO2/GO at Different Temperatures.

We investigate the temperature effect on sensing characteristics and drift effect of an arrayed flexible ruthenium dioxide (RuO2)/graphene oxide (GO) chloride sensor at different solution temperatures between 10 °C and 50 °C. The average sensor sensitivities according to our experimental results were 28.2 ± 1.4 mV/pCl (10 °C), 42.5 ± 2.0 mV/pCl (20 °C), 47.1 ± 1.8 mV/pCl (30 °C), 54.1 ± 2.01 mV/pCl (40 °C) and 46.6 ± 2.1 mV/pCl (50 °C). We found the drift effects of an arrayed flexible RuO2/GO chloride sensor in a 1 M NaCl solution to be between 8.2 mV/h and 2.5 mV/h with solution temperatures from 10 °C to 50 °C.

Full Kinetics from First Principles of the Chlorine Evolution Reaction over a RuO2 (110) Model Electrode.

Current progress in modern electrocatalysis research is spurred by theory, frequently based on ab initio thermodynamics, where the stable reaction intermediates at the electrode surface are identified, while the actual energy barriers are ignored. This approach is popular in that a simple tool is available for searching for promising electrode materials. However, thermodynamics alone may be misleading to assess the catalytic activity of an electrochemical reaction as we exemplify with the chlorine evolution reaction (CER) over a RuO2 (110) model electrode. The full procedure is introduced, starting from the stable reaction intermediates, computing the energy barriers, and finally performing microkinetic simulations, all performed under the influence of the solvent and the electrode potential. Full kinetics from first-principles allows the rate-determining step in the CER to be identified and the experimentally observed change in the Tafel slope to be explained.

Controlling selectivity in the chlorine evolution reaction over RuO2-based catalysts.

In the industrially important Chlor-Alkali process, the chlorine evolution reaction (CER) over a ruthenium dioxide (RuO2) catalyst competes with the oxygen evolution reaction (OER). This selectivity issue is elucidated on the microscopic level with the single-crystalline model electrode RuO2(110) by employing density functional theory (DFT) calculations in combination with the concept of volcano plots. We demonstrate that one monolayer of TiO2(110) supported on RuO2(110) enhances the selectivity towards the CER by several orders of magnitudes, while preserving the high activity for the CER. This win-win situation is attributed to the different slopes of the volcano curves for the CER and OER.

High Capacity Nanocomposite Layers Based on Nanoparticles of Carbon Materials and Ruthenium Dioxide for Potassium Sensitive Electrode.

This work presents the new concept of designing ion-selective electrodes based on the use of new composite materials consisting of carbon nanomaterials and ruthenium dioxide. Using two different materials varying in microstructure and properties, we could obtain one material for the mediation layer that adopted features coming of both components. Ruthenium dioxide characterized by high electrical capacity and mixed electronic-ionic transduction and nano-metric carbon materials were reportedly proved to improve the properties of ion-selective electrodes. Initially, only the materials and then the final electrodes were tested in the scope of the presented work, using scanning and transmission electron microscope, contact angle microscope, and various electrochemical techniques, including electrochemical impedance spectroscopy and chronopotentiometry. The obtained results confirmed beneficial influence of the designed nanocomposites on the ion-selective electrodes' properties. Nanosized structure, high capacity (characterized by the electrical capacitance value from approximately 5.5 mF for GR + RuO2 and CB + RuO2, up to 14 mF for NT + RuO2) and low hydrophilicity (represented by the contact angle from 60° for GR+RuO2, 80° for CB+RuO2, and up to 100° for NT + RuO2) of the mediation layer materials, allowed us to obtain water layer-free potassium-selective electrodes, characterized by rapid and stable potentiometric response in a wide range of concentrations-from 10-1 to 10-6 M K+.

Potentiometric Sensor with High Capacity Composite Composed of Ruthenium Dioxide and Poly(3,4-ethylenedioxythiophene) Polystyrene Sulfonate.

This work presents the first-time application of the ruthenium dioxide-poly(3,4-ethylenedioxythiophene) polystyrene sulfonate high-capacity composite material as a mediation layer in potassium selective electrodes, which turned out to significantly enhance the electrical and analytical parameters of the electrodes. The idea was to combine the properties of two different types of materials: a conducting polymer, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate, and a metal oxide, ruthenium dioxide, in order to obtain the material for a solid-contact layer of great electrical and physicochemical parameters. The preparation method for composite material proposed in this work is fast and easy. The mediation layer material was examined using a scanning electron microscope and chronopotentiometry in order to confirm that all requirements for mediation layers materials were fulfilled. Ruthenium dioxide-poly(3,4-ethylenedioxythiophene) polystyrene sulfonate nancomposite material turned out to exhibit remarkably high electrical capacitance (of approximately 17.5 mF), which ensured great performance of designed K+-selective sensors. Electrodes of electrical capacity equal to 7.2 mF turned out to exhibit fast and stable (with only 0.077 mV potential change per hour) potentiometric responses in the wide range of potassium ion concentrations (10-6 M to 10-1 M). The electrical capacity of ruthenium dioxide-poly(3,4-ethylenedioxythiophene) polystyrene sulfonate-contacted electrodes characterized by electrical capacitance parameters was the highest reported so far for this type of sensor.

Optimization of Ruthenium Dioxide Solid Contact in Ion-Selective Electrodes.

Ruthenium dioxide occurs in two morphologically varied structures: anhydrous and hydrous form; both of them were studied in the scope of this work and applied as mediation layers in ion-selective electrodes. The differences between the electrochemical properties of those two materials underlie their diverse structure and hydration properties, which was demonstrated in the paper. One of the main differences is the occurrence of structural water in RuO2•xH2O, which creates a large inner surface available for ion transport and was shown to be a favorable feature in the context of designing potentiometric sensors. Both materials were examined with SEM microscope, X-ray diffractometer, and contact angle microscope, and the results revealed that the hydrous form can be characterized as a porous structure with a smaller crystallite size and more hydrophobic properties contrary to the anhydrous form. Potentiometric and electrochemical tests carried out on designed GCD/RuO2/K+-ISM and GCD/RuO2•xH2O/K+-ISM electrodes proved that the loose porous microstructure with chemically bounded water, which is characteristic for the hydrous form, ensures the high electrical capacitance of electrodes (up to 1.2 mF) with consequently more stable potential (with the potential drift of 0.0015 mV/h) and a faster response (of a few seconds).

Wettability-Driven Assembly of Electrochemical Microsupercapacitors.

In this work, we demonstrate a wettability-driven assembly (WDA) process of active particulate materials for microsupercapacitor (MSC) fabrication. Our process uses three-dimensional laser-scribed graphene (LSG), derived from polyimide, as a current collector. We exploit the drastic wettability difference between LSG and unconverted polyimide toward water to assemble various electrodes on the LSG collectors. The WDA process is demonstrated using porous carbon and RuO2 nanoparticles, which are spontaneously and selectively assembled onto the LSG finger electrodes. The MSCs assembled using the WDA process with porous carbon as active material deliver a much higher areal capacitance (41.2 mF cm-2) compared to MSCs using LSG-only electrodes (1.2 mF cm-2). Thus, they deliver a high areal energy density of 5.71 µWh cm-2 with an areal power density of 4.0 mW cm-2. The capacitance and energy density of these porous carbon MSCs outperform most recently reported carbon-based MSCs. In comparison, the MSCs assembled using the WDA process with RuO2 nanoparticles as active material deliver an areal capacitance of 70.3 mF cm-2 and an areal energy density of 9.71 µWh cm-2. All in all, the WDA process is green, simple, and well suited for the fabrication of MSCs using many types of active materials.

Drift and Hysteresis Characteristics of Drug Sensors Based on Ruthenium Dioxide Membrane.

The drug sensing properties of procaine and berberine drug sensors based on ruthenium dioxide thin film were investigated. Ruthenium dioxide (RuO2) membrane prepared using a sputtering method was used as substrates for the drug sensors. The procaine and berberine drug sensors were prepared using a drug-sensitive membrane that measured the procaine and berberine concentration in a linear range from 1×10-2 M to 1×10-6 M and from 1×10-2 M to 1×10-7 M, respectively. The drift rates and hyteresis widths of these ruthenium dioxide based drug sensors were also investigated.

Electrochemical oxidation of cyanide on 3D Ti-RuO2 anode using a filter-press electrolyzer.

The novelty of this communication lies in the use of a Ti-RuO2 anode which has not been tested for the oxidation of free cyanide in alkaline media at concentrations similar to those found in wastewater from the Merrill Crowe process (100 mg L-1 KCN and pH 11), which is typically used for the recovery of gold and silver. The anode was prepared by the Pechini method and characterized by SEM. Linear sweep voltammetries on a Ti-RuO2 rotating disk electrode (RDE) confirmed that cyanide is oxidized at 0.45 < E < 1.0 V vs SHE, while significant oxygen evolution reaction (OER) occurred. Bulk oxidation of free cyanide was investigated on Ti-RuO2 meshes fitted into a filter-press electrolyzer. Bulk electrolyzes were performed at constant potentials of 0.85 V and 0.95 V and at different mean linear flow rates ranging between 1.2 and 4.9 cm s-1. The bulk anodic oxidation of cyanide at 0.85 V and 3.7 cm s-1 achieved a degradation of 94%, with current efficiencies of 38% and an energy consumption of 24.6 kWh m-3. Moreover, the degradation sequence of cyanide was also examined by HPLC.