The cyclic voltammetry of some sulphonated transition metal phthalocyanines in dimethylsulphoxide and in water
TL;DR: In this article, the aqueous voltammetry of Co, Ni, Cu and Zn sulphonated metallophthalocyanines has been examined and compared to the voltamometry in DMSO.
About: This article is published in Journal of Electroanalytical Chemistry.The article was published on 1989-01-01. It has received 46 citations till now. The article focuses on the topics: Cyclic voltammetry & Phthalocyanine.
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TL;DR: The factor that controls the activity of these chelates is not fully understood but parameters such as redox potentials of the metal and electronic structure appear to be crucial as discussed by the authors.
499 citations
274 citations
TL;DR: It is shown that the photoluminescence (PL) emission can be selectively and reversibly engineered through energetically favorable electron transfer from photoexcited TMDCs to MPcs, further supporting the photoinduced charge transfer mechanism.
Abstract: Atomically thin transition metal dichalcogenides (TMDCs) have attracted great interest as a new class of two-dimensional (2D) direct band gap semiconducting materials. The controllable modulation of optical and electrical properties of TMDCs is of fundamental importance to enable a wide range of future optoelectronic devices. Here we demonstrate a modulation of the optoelectronic properties of 2D TMDCs, including MoS2, MoSe2, and WSe2, by interfacing them with two metal-centered phthalocyanine (MPc) molecules: nickel Pc (NiPc) and magnesium Pc (MgPc). We show that the photoluminescence (PL) emission can be selectively and reversibly engineered through energetically favorable electron transfer from photoexcited TMDCs to MPcs. NiPc molecules, whose reduction potential is positioned below the conduction band minima (CBM) of monolayer MoSe2 and WSe2, but is higher than that of MoS2, quench the PL signatures of MoSe2 and WSe2, but not MoS2. Similarly, MgPc quenches only WSe2, as its reduction potential is situ...
143 citations
01 Aug 2021
TL;DR: In this article, the authors report the first electrochemical reaction that converts carbon dioxide and nitrate to methylamine in aqueous media under ambient conditions catalysed by a cobalt β-tetraaminophthalocyanine molecular catalyst supported on carbon nanotubes.
Abstract: The electrochemical reduction of carbon dioxide is an appealing technology that stores renewable electricity in the chemical form and has the potential to transform the way carbon fuels are utilized today. While there have been successes in the electrosynthesis of alkanes, alkenes and alcohols, access to organonitrogen molecules such as alkylamines remains largely beyond the reach of current electrocatalysis. Here we report the first electrochemical reaction that converts carbon dioxide and nitrate to methylamine in aqueous media under ambient conditions catalysed by a cobalt β-tetraaminophthalocyanine molecular catalyst supported on carbon nanotubes. The overall reaction, involving the transfer of 14 electrons and 15 protons to form each methylamine molecule, is an eight-step catalytic cascade process enabled by the coupling of two reactive intermediates near the catalyst surface. The key C–N bond-forming step is found to be the spillover of hydroxylamine from nitrate reduction and its subsequent condensation with formaldehyde from carbon dioxide reduction. This study provides a successful example of sustainable alkylamine synthesis from inorganic carbon and nitrogen wastes, which could contribute to greenhouse gas mitigation for a carbon-neutral future. The electroreduction of CO2 provides a sustainable pathway to value-added fuels and chemicals. Here the authors show a cascade reaction that yields methylamine from CO2 and nitrate. With detailed insight into the multistep catalytic process, the current findings further push the boundaries of this technology.
104 citations
TL;DR: In this article, photoinduced electron transfer (PET) within the nano assembly is revealed by laser flash photolysis, time resolved and steady state fluorescence, as well as UV-vis absorption techniques.
85 citations
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TL;DR: In this article, an indirect method for the reduction of CO/sub 2/ in nonaqueous solutions and involving initial reduction of metal complexes and their subsequent reduction with CO/ sub 2/ is described.
Abstract: An indirect method for the reduction of CO/sub 2/ in nonaqueous solutions and involving initial reduction of metal complexes and their subsequent reduction with CO/sub 2/ is described. The complexes were tetraazamacrocyclic complexes of Ni and Co. The catalytic reduction process was investigated by means of controlled potential coulometry experiments performed in a gas-tight electrolysis cell under a CO/sub 2/ atmosphere. The effects of water, Ar, and N/sub 2/ on the electrolysis process were investigated. The results indicated that the indirect electrochemical reduction of CO/sub 2/ occurred at a potential between -1.3 and -1.6V vs SCE and that the reduction was indeed catalyzed by the metal complexes. Reaction periods of as long as 24 h did not reduce catalytic activity; and in most cases, the catalyst was isolated in its original form at the end of the run. A protic source was found to be necessary for the reaction to yield CO and H/sub 2/; and in the absence of a protic source, simple stoichiometric reduction of the complex was noted. (BLM)
521 citations
131 citations
TL;DR: In this paper, the reduction potentials of a number of metal phthalocyanine complexes have been measured at a dropping mercury electrode in dimethylformamide, and the results of the investigation are discussed in the light of previous spectroscopic work with a view to correlating the electrode process with either ligand or metal reductions.
123 citations