Synthetic and mechanistic investigations of the reductive electrochemical polymerization of vinyl-containing complexes of iron(II), ruthenium(II), and osmium(II)

Calvert, Jeffrey M.; Schmehl, Russell H.; Sullivan, B. Patrick; Facci, John S.; Meyer, Thomas J.; Murray, Royce W.

doi:10.1021/ic00157a013

Cited by 151 publications

(96 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These complexes are new compounds, but they were prepared using reaction conditions that are very similar to those used for the closely related terpyridine complexes. 48,53,54 Reaction of ruthenium complex 12 with bpy in boiling aqueous EtOH in presence of LiCl afforded the crude complex 13. After purification on silica gel, the product was collected as its PF Single crystals suitable for X-ray were grown by vapour diffusion of diethyl ether into CH 3 CN solution of the complex.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and structural characterization of some polypyridyl and polypyrazolyl Ru(II) complexes

Hartshorn¹,

Zibaseresht²

2005

Arkivoc

View full text Add to dashboard Cite

Section: Resultsmentioning

confidence: 99%

Synthesis and structural characterization of some polypyridyl and polypyrazolyl Ru(II) complexes

Hartshorn¹,

Zibaseresht²

2005

Arkivoc

View full text Add to dashboard Cite

“…2A, peak currents increase with the number of scans. At these potentials, reduction of the vbpy ligands occurs, which induces vinyl polymerization (25,27). The mechanism involves reduction and vinyl radical polymerization in the double layer near the electrode surface by C-C bond formation.…”

Section: Significancementioning

confidence: 99%

“…It involves in sequence: (i) Formation of a polymeric film of poly-[Fe(vbpy) 3 ](PF 6 ) 2 (vbpy is 4-methyl-4′-vinyl-2,2′-bipyridine) by electropolymerization induced by vbpy-based reduction. The electropolymerization procedure has been applied to polymer film formation on a variety of conductive substrates (23)(24)(25)(26) including glassy carbon (GC) electrodes, planar fluorine-doped tin oxide (FTO) slides, reticulated vitreous carbon, and high surface area gas diffusion electrodes. (ii) Addition of cyanide ions which displaces a vbpy ligand from Fe(II) to give poly-Fe(vbpy) 2 (CN) 2 , poly-vbpy.…”

mentioning

confidence: 99%

Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane

Zhang

Kang

Bakir

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

150

118

View full text Add to dashboard Cite

Developing sustainable energy strategies based on CO 2 reduction is an increasingly important issue given the world's continued reliance on hydrocarbon fuels and the rise in CO 2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO 2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO 2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO 2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd-H sites and Cu-CO sites during electrochemical CO 2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO 2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices. solar energy | carbon dioxide reduction | CuPd nanoalloy | electropolymerized film | hydrocarbon D eveloping sustainable energy resources and strategies to combat the hazards associated with the use of fossil fuels, which include global warming due to the increased concentration of greenhouse gases, is an important theme in the current energy and environmental research agenda (1-3). Electrochemical and photoelectrochemical CO 2 reduction to energy-dense hydrocarbon fuels could play a major role and become part of an integrated energy storage strategy, in combination with solar-or wind-generated electricity, as a way to store energy in the chemical bonds of carbon-based fuels (4-12). Metal-based catalysts for CO 2 reduction have been extensively studied over the last three decades. Metallic copper has proven to be the best available catalytic material for CO 2 reduction to hydrocarbons by electrochemical methods (13)(14)(15)(16)(17)(18)(19). Cu foils and single crystals have been extensively investigated but suffer from low surface areas, low catalytic current densities, and rapid deactivation during electrochemical CO 2 reduction (20). Recently, nanoparticle Cu catalysts (nanoCu) have been investigated as a way to increase catalytic current densities and stabilities. However, Faradaic efficiencies for electrocatalytic reduction to hydrocarbons decrease dramatically with particle size falling to ∼10% for particles less than 20 nm in diameter. The size effect has been attributed to an enhanced chemisorption strength for CO at small Cu nanoparticles compared with large particles or bulk Cu electrodes (13). An additional complication arises from the use of surfactants in the syntheses of nanoCu because they can lead to significant contamination issues requiring their rem...

show abstract

“…[30] On the other hand, the complex trans-[RuCl2(vpy)4] (vpy=4-vinylpyridine), [31] composed of four groups, which are easily polymerized producing electroactive adherent films, compared to films made from the linkers vinylpyridine and vinylterpyridine, were also prepared. [32,33] Previous studies have shown that the complex trans-[RuCl2(vpy)4] can be electropolymerized on different substrates, including inert materials such as Pt and Pd, [31] ferrous alloys [34,35] and stainless steel. [36] Studies of cyclic voltammetry, electrochemical crystal microbalance quartz and Raman spectroscopy revealed the results of electropolymerization of the complex trans-[RuCl2(vpy)4] in Au and Pt electrodes in particular the effects of the polymerization potential on the characteristics of the film formed, and especially the understanding of the key processes involved in electropolymerization.…”

Section: Metallopolymersmentioning

confidence: 99%

From Ruthenium Complexes to Novel Functional Nanocomposites: Development and Perspectives

Segala¹,

Pereira²

2012

New Polymers for Special Applications

View full text Add to dashboard Cite

Synthetic and mechanistic investigations of the reductive electrochemical polymerization of vinyl-containing complexes of iron(II), ruthenium(II), and osmium(II)

Cited by 151 publications

References 0 publications

Synthesis and structural characterization of some polypyridyl and polypyrazolyl Ru(II) complexes

Synthesis and structural characterization of some polypyridyl and polypyrazolyl Ru(II) complexes

Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane

From Ruthenium Complexes to Novel Functional Nanocomposites: Development and Perspectives

Contact Info

Product

Resources

About