Single crystal RuO2/Ti and RuO2/TiO2 interface: LEED, Auger and XPS study

Atanasoska, Lj.; Atanasoski, Radoslav; Pollak, Fred H.; O’Grady, W.E.

doi:10.1016/0039-6028(90)90019-5

Cited by 34 publications

(12 citation statements)

References 44 publications

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“…As shown in Figure , mixed RuO 2 –TiO 2 nanofibers are much more stable than pure RuO 2 fibers. The improved stabilization of RuO 2 by titanium has been observed on single crystal surfaces of RuO 2 as well, namely, on RuO 2 (110) and RuO 2 (100) . It turned out that Ti deposition substantially improved the thermal stability of both orientations of RuO 2 in UHV which is fully reconciled with the found stabilization of RuO 2 –TiO 2 nanofibers.…”

Section: Reaction Mechanism Of the Deacon Processmentioning

confidence: 65%

“…The improved stabilization of RuO 2 by titanium has been observed on single crystal surfaces of RuO 2 as well, namely, on RuO 2 (110) and RuO 2 (100). 85 It turned out that Ti deposition substantially improved the thermal stability of both orientations of RuO 2 in UHV which is fully reconciled with the found stabilization of RuO 2 −TiO 2 nanofibers. To understand this stabilization effect of Ti, we have to recall the atomic-scale reduction process on RuO 2 (110).…”

Section: Studied the Hcl Oxidation Reaction For Various Transition Me...mentioning

confidence: 77%

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Atomic-Scale Understanding of the HCl Oxidation Over RuO₂, A Novel Deacon Process

Over

2012

J. Phys. Chem. C

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Heterogeneous catalysis of the HCl oxidation by oxygen (Deacon process) over RuO2 is a green chemistry route to recover high purity Cl2 from HCl waste in an almost energy neutral way on a large industrial scale. The outstanding properties of RuO2-based catalysts are long-term stability under such harsh reaction conditions and high catalytic activity, allowing for lower reaction temperatures and hence for higher Cl2 conversions at equilibrium. In this Feature Article, I will be reviewing the atomic-scale insights into this Deacon process gained on single-crystalline RuO2(110) model catalysts. The extraordinary stability of RuO2(110) is traced to the selective and self-limited replacement of bridging surface oxygen by chlorine, thereby transforming active surface sites with basic Brønsted character into inactive sites and thereby suppressing the bulk chlorination of RuO2. The reaction mechanism has been clarified by utilizing experimental surface science techniques together with density functional theory (DFT) calculations. Oxygen adsorption proceeds dissociatively across two neighboring undercoordinated Ru sites, thereby forming two undercoordinated surface on-top O (Oot) atoms (homolytic cleavage). These Oot species are able to accept H from dissociative adsorption of HCl to form on-top Cl (Clot) and on-top hydroxyl groups (OotH). The heterolytic cleavage of HCl requires both acidic (undercoordinated Ru) and basic surface centers (undercoordinated O). Another H-transfer to the hydroxyl groups produces the byproduct water which desorbs at 420 K. The recombination of adjacent adsorbed Clot produces finally the desired product Cl2, an elementary reaction step with the highest activation barrier of 228 kJ/mol. Yet, oxygen adsorption constitutes the rate-determining step in the Deacon process over RuO2(110) under typical reaction conditions since strongly adsorbed Clot blocks dissociative oxygen adsorption. The overall reaction mechanism is governed by a delicate interplay of surface kinetics and thermodynamics, i.e., the adsorption energies of reactants, reaction intermediates and products.

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Section: Reaction Mechanism Of the Deacon Processmentioning

confidence: 65%

Section: Studied the Hcl Oxidation Reaction For Various Transition Me...mentioning

confidence: 77%

Atomic-Scale Understanding of the HCl Oxidation Over RuO₂, A Novel Deacon Process

Over

2012

J. Phys. Chem. C

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“…RuO 2 −TiO 2 solid solution is more widely investigated and has been commercially applied in chlorine evolution known as dimensionally stable anode (DSA), because TiO 2 not only dilutes the noble elements, but also increases the stability during decomposition and the electrolysis process. 30,31 In the present work, we reported a highly selective (88.86%) method to electrochemically hydrogenate CAL to COL by employing RuO 2 −SnO 2 −TiO 2 /Ti as the cathode. It was verified that RuO 2 are the active center for COL formation, while the doping of SnO 2 is facile to improve the Faradaic efficiency (FE) by decreasing the hydrogen evolution reaction (HER).…”

Section: Introductionmentioning

confidence: 98%

“…Similar to PtM alloys, the positively charged Ru could be more attractive to CO than CC, making it a potential candidate for the selective conversion of CAL. RuO 2 –TiO 2 solid solution is more widely investigated and has been commercially applied in chlorine evolution known as dimensionally stable anode (DSA), because TiO 2 not only dilutes the noble elements, but also increases the stability during decomposition and the electrolysis process. , …”

Section: Introductionmentioning

confidence: 99%

High Selective Electrochemical Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol on RuO₂–SnO₂–TiO₂/Ti Electrode

Huang

Zhang

et al. 2019

ACS Catal.

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Electrocatalytic hydrogenation is a promising method to synthesize high value-added chemicals under mild conditions. However, in the case of converting cinnamaldehyde (CAL) into cinnamyl alcohol (COL), this approach is accompanied by the competitive side reactions, including hydrodimerization, CC saturation, and hydrogen evolution. In this work, a high selectivity to cinnamyl alcohol of 88.86% at 58.00% conversion was successfully achieved on a thermally decomposed RuO2–SnO2–TiO2/Ti cathode with a rutile sosoloid crystal structure, which surpasses the low selectivity (<15%) over various metal electrodes. Density functional theory calculation findings demonstrate that CAL interacts with the active RuO2 sites preferentially via CO rather than CC, with the energy barrier of CAL hydrogenation toward COL being significantly reduced. The introduction of SnO2 is efficient to improve the Faradaic efficiency by restraining hydrogen evolution, but would result in dimers as the main products at high content. In addition, low pH value and high electrode overpotential benefit the generation of COL and the inhibition of dimerization products.

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“…The Ru binding energies for RuO 2 ·2H 2 O are found to be 281.2 and 285.6 eV [34]. However, the existence of RuO 3 has been the subject of controversy in many XPS studies [35,36]. Because RuO 2 ·2H 2 O is a metallic oxide with partially filled conduction band, core-hole coupling may occur on this surface.…”

Section: Surface Chemistry Characterizationmentioning

confidence: 98%

Surface characteristics of ruthenium in periodate-based slurry during chemical mechanical polishing

Cheng

Wang

Jiang

et al. 2015

Applied Surface Science

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Single crystal RuO2/Ti and RuO2/TiO2 interface: LEED, Auger and XPS study

Cited by 34 publications

References 44 publications

Atomic-Scale Understanding of the HCl Oxidation Over RuO₂, A Novel Deacon Process

Atomic-Scale Understanding of the HCl Oxidation Over RuO₂, A Novel Deacon Process

High Selective Electrochemical Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol on RuO₂–SnO₂–TiO₂/Ti Electrode

Surface characteristics of ruthenium in periodate-based slurry during chemical mechanical polishing

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Single crystal RuO2/Ti and RuO2/TiO2 interface: LEED, Auger and XPS study

Cited by 34 publications

References 44 publications

Atomic-Scale Understanding of the HCl Oxidation Over RuO2, A Novel Deacon Process

Atomic-Scale Understanding of the HCl Oxidation Over RuO2, A Novel Deacon Process

High Selective Electrochemical Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol on RuO2–SnO2–TiO2/Ti Electrode

Surface characteristics of ruthenium in periodate-based slurry during chemical mechanical polishing

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Resources

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Atomic-Scale Understanding of the HCl Oxidation Over RuO₂, A Novel Deacon Process

Atomic-Scale Understanding of the HCl Oxidation Over RuO₂, A Novel Deacon Process

High Selective Electrochemical Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol on RuO₂–SnO₂–TiO₂/Ti Electrode