Investigations into the catalytic activity of rhodium(III) in red–ox reactions by capillary zone electrophoresis

Aleksenko, Svetlana S.; Gumenyuk, A. P.; Mushtakova, S. P.; Kozhina, L. F.; Timerbaev, Andrei R.

doi:10.1016/s0039-9140(03)00268-6

Cited by 21 publications

(7 citation statements)

References 13 publications

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“…39 Despite the extensive studies of Rh(III) complexes in various environments, there are still unsolved questions, for instance which anionic sulfo complexes might exist when RhCl 3 .xH 2 O is dissolved in sulfuric acid solution as stated in Ref. 38. Nevertheless, in order to understand the spontaneous deposition process, it was of primary importance to observe the structure of the deposit and to define the chemistry of as prepared electrode.…”

Section: Methodsmentioning

confidence: 99%

“…According to the literature data hydrated rhodium trichloride is soluble in aqueous solution giving various [RhCl n (H 2 O) 6−n ] 3−n (n = 0-6) complexes, the proportion of which depends on aging and pH. [38][39][40] The reddish color of freshly prepared depositing solution turns to yellowish after one day of aging. High Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectroscopy (HPLC-ICP-MS) data have shown that in aged acid solutions RhCl 3 (H 2 O) 3 , [RhCl 4 (H 2 O) 2 ] − , and [RhCl 5 (H 2 O)] 2− species are predominantly present.…”

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confidence: 99%

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Spontaneously Deposited Rh on Au(111) Observed by AFM and XPS: Electrocatalysis of Hydrogen Evolution

Štrbac

Smiljanić

Rakočević

2016

J. Electrochem. Soc.

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Rhodium nanoislands were spontaneously deposited on Au(111) up to a full coverage. Obtained Rh/Au(111) bimetallic surface was characterized ex situ by Atomic Force Microscopy imaging and by X-Ray Photoelectron Microscopy, while in situ characterization was performed by Cyclic Voltammetry in 0.1 M NaOH solution. Pronounced catalysis of hydrogen evolution reaction has been observed on Rh modified Au(111) surface compared to bare Au(111). This is ascribed to the suitable geometry of obtained Rh/Au(111) nanostructured electrode surface providing large number of active sites and to the electronic interaction between Au(111) substrate and Rh deposit.Bimetallic electrodes consisting of noble metal substrate modified by a foreign metal deposit are still in the focus of interest in electrocatalysis starting from early publications. 1-4 Tailoring bimetallic electrodes with pronounced electrocatalytic activity compared to the activity of the substrate alone or to the both constituting metals is a demanding task regarding the chemical nature and the structure of the substrate and deposit, which should result in improved surface chemistry and geometry with respect to the active surface sites and/or to the electronic effect. Well-ordered noble metal electrodes modified by submonolayer to a few layers thick deposit of highly active metals from platinum group are the most convenient bimetallic model systems for fundamental studies of the electrocatalytic activity of such various nanostructures for fuel cell reactions. [5][6][7] Structural, electronic and chemical properties of well-defined bimetallic surfaces are examined ex situ by common techniques including Scanning Probe Microscopy (SPM), and X-ray Photoelectron Spectroscopy (XPS). 8,9 With the advent of in situ microscopic and spectroscopic techniques, such as Scanning Tunneling Microscopy (STM), 10 XPS, 11 Surface X-ray Scattering (SXS) and X-ray Absorption Spectroscopy (XAS), 12 it became possible to observe the structure of bimetallic surface and to determine its chemical composition and oxidation state of constituting metals under defined electrochemical conditions or during electrocatalytic reactions.For the preparation of bimetallic electrodes with well-defined structure, various deposition methods were employed including electrochemical deposition on nonreconstructed 13 or reconstructed single crystal surfaces, 14 surface limited redox replacement, 15-18 defectmediated growth, 19 and spontaneous deposition. 20,21 The spontaneous deposition method, which is explored in this work, assumes several processes that occur on the electrode surface during its immersion into the depositing metal ions solution at open circuit potential. These involve either irreversible adsorption of metal ion complexes or electroless deposition in which depositing metal ions are reduced by substrate atoms which are oxidized, or a combination of both. Finally obtained bimetallic surface consists of three-dimensional foreign metal nanoislands with the coverage up to a monolayer. In some cases, w...

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Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Spontaneously Deposited Rh on Au(111) Observed by AFM and XPS: Electrocatalysis of Hydrogen Evolution

Štrbac

Smiljanić

Rakočević

2016

J. Electrochem. Soc.

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“…Redox reaction, which is concerned with the transfer of electrons between species, is widely found in life processes such as photosynthesis, 1,2 respiratory chain 3,4 and biological metabolism, 5,6 etc. More recently, some novel capillary electrophoresis (CE) methods relying on in-capillary redox reaction have been developed for the investigation of enzymatic reaction 7 and coenzymes determination, 8 elemental speciation 9 and carbohydrates analyses. [10][11][12] In these methods, the reactants are dissolved in solvents with different conductivities.…”

Section: Introductionmentioning

confidence: 99%

Model creation of moving redox reaction boundary in agarose gel electrophoresis by traditional potassium permanganate method

Xie

Liu

et al. 2013

Analyst

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A novel moving redox reaction boundary (MRRB) model was developed for studying electrophoretic behaviors of analytes involving redox reaction on the principle of moving reaction boundary (MRB). Traditional potassium permanganate method was used to create the boundary model in agarose gel electrophoresis because of the rapid reaction rate associated with MnO(4)(-) ions and Fe(2+) ions. MRB velocity equation was proposed to describe the general functional relationship between velocity of moving redox reaction boundary (V(MRRB)) and concentration of reactant, and can be extrapolated to similar MRB techniques. Parameters affecting the redox reaction boundary were investigated in detail. Under the selected conditions, good linear relationship between boundary movement distance and time were obtained. The potential application of MRRB in electromigration redox reaction titration was performed in two different concentration levels. The precision of the V(MRRB) was studied and the relative standard deviations were below 8.1%, illustrating the good repeatability achieved in this experiment. The proposed MRRB model enriches the MRB theory and also provides a feasible realization of manual control of redox reaction process in electrophoretic analysis.

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“…Recently developed CE techniques play an increasingly important role in discriminating the speciation pattern of a diversity of chemical forms of metals (chromium [79,83,94,95,105,232,233], including characterization of hydrolyzed Cr(III) species regarding the degree of oligomerization [234], iron [79,177,187,235,236], mercury [237,238], cobalt [154,189,190], vanadium [79,239], nickel [113,114], rhodium [240][241][242], rhenium [243]), metalloids (arsenic [78,104,146,180,211,244,245], with one of the best CE performance examples on the number of separated As species [211], selenium [88,102,104,118,147,[246][247][248], antimony [147], tellurium [104]), and nonmetals (nitrogen [156,…”

Section: Speciation Analysismentioning

confidence: 99%

Capillary electrophoresis of inorganic ions: An update

Timerbaev

2004

Electrophoresis

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This review as a sequel of three earlier similar reports gives a summary of the progress and significant methodological developments, starting from 2002, in the use of capillary electrophoresis (CE) for inorganic ion analysis. As substantiated by the illustrative number of relevant references, improvements in sensitivity achieved both in and outside a CE system, advances in manipulating the separation selectivity, novel hardware configurations, and system performance innovations are continually being reported over the review period. Specifically viewed are the recent advancements in elemental (bio)speciation analysis, which remains one of the most fertile areas of CE research, as well as in three recently booming research topics: contactless conductivity detection, separations on microchips, and transient isotachophoretic preconcentration. A state-of-the-art picture of technique's potentialities within the field of interest presented here demonstrates that CE has become recognized and is growing in acceptance as a reliable alternative to traditional analytical methods such as high-performance liquid chromatography (HPLC).

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Investigations into the catalytic activity of rhodium(III) in red–ox reactions by capillary zone electrophoresis

Cited by 21 publications

References 13 publications

Spontaneously Deposited Rh on Au(111) Observed by AFM and XPS: Electrocatalysis of Hydrogen Evolution

Spontaneously Deposited Rh on Au(111) Observed by AFM and XPS: Electrocatalysis of Hydrogen Evolution

Model creation of moving redox reaction boundary in agarose gel electrophoresis by traditional potassium permanganate method

Capillary electrophoresis of inorganic ions: An update

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