Search results for " Electron Transfer"
showing 10 items of 80 documents
Hole Localization and Thermochemistry of Oxidative Dehydrogenation of Aqueous Rutile TiO2(110)
2012
Interspecies interactions mediated by conductive minerals in the sediments of the ferruginous Lake La Cruz, Spain
2018
AbstractLake La Cruz is considered a biogeochemical analogue to early Earth marine environments because its water column is depleted in sulfate, but rich in methane and iron, similar to conditions envisaged for much of the Precambrian. In this early Earth analogue environment, we show that conductive particles establish a tight metabolic coupling between electroactive microbial clades. We propose that mineral-based syntrophy is of potential relevance for the evolution of Earth’s earliest complex life forms. We show that the anoxic sediment of Lake La Cruz, which is rich in biogeochemically ‘reactive’ iron minerals, harbors known electroactive species such asGeobacterandMethanothrix,in addit…
Monofunctional pyrenes at carbon nanotube electrodes for direct electron transfer H2O2 reduction with HRP and HRP-bacterial nanocellulose
2021
Abstract The non-covalent modification of carbon nanotube electrodes with pyrene derivatives is a versatile approach to enhance the electrical wiring of enzymes for biosensors and biofuel cells. We report here a comparative study of five pyrene derivatives adsorbed at multi-walled carbon nanotube electrodes to shed light on their ability to promote direct electron transfer with horseradish peroxidase (HRP) for H2O2 reduction. In all cases, pyrene-modified electrodes enhanced catalytic reduction compared to the unmodified electrodes. The pyrene N-hydroxysuccinimide (NHS) ester derivative provided access to the highest catalytic current of 1.4 mA cm−2 at 6 mmol L−1 H2O2, high onset potential …
Rate Theory for Electrocatalytic Systems: Fixed Potential Formulation for General, Electron Transfer, and Proton-Coupled Electron Transfer Reactions
2019
Atomistic modeling of electrocatalytic reactions is most naturally conducted within the grand canonical ensemble (GCE) which enables fixed chemical potential calculations. While GCE has been widely adopted for modeling electrochemical and electrocatalytic thermodynamics, the electrochemical reaction rate theory within GCE is lacking. Molecular and condensed phase rate theories are formulated within microcanonical and canonical ensembles, respectively, but electrocatalytic systems described within the GCE require extension of the conventionally used rate theories for computation reaction rates at fixed electrode potentials. In this work, rate theories from (micro) canonical ensemble are gene…
Unified Rate Theory of Electrochemistry and Electrocatalysis: Fixed Potential Formulation for General, Electron Transfer, and Proton-Coupled Electron…
2019
Atomistic modeling of electrocatalytic reactions is most naturally conducted within the grand canonical ensemble (GCE) which enables fixed chemical potential calculations. While GCE has been widely adopted for modeling electrochemical and electrocatalytic thermodynamics, the electrochemical reaction rate theory within GCE is lacking. Molecular and condensed phase rate theories are formulated within microcanonical and canonical ensembles, respectively, but electrocatalytic systems described within the GCE require extension of the conventionally used rate theories for computation reaction rates at fixed electrode potentials. In this work, rate theories from (micro)canonical ensemble are gener…
Initial Radical Cation Pathway in the Mo2Cl10-Mediated Dehydrogenative Arene Coupling
2015
Experimental (EPR) and theoretical (DFT) evidence is provided for radical cation formation as initial step in the Mo2Cl10-mediated dehydrogenative arene coupling. The initial electron transfer from methoxyarenes to molybdenum proceeds via an inner sphere mechanism.
Long lived photoinduced charges in donor-acceptor anthraquinone substituted thiophene copolymers
2006
The photoinduced charge-transfer properties of a series of polyalkylthiophene copolymers, carrying anthraquinone substituents covalently linked to the conjugated backbone, have been studied in the solid state by photoinduced absorption (PA) and light-induced electron spin resonance (LESR) spectroscopy. The measurements indicate the formation of metastable charges arising from the photoinduced electron transfer from the polythiophene backbone to the anthraquinone moieties. At low temperatures (below 200 K), long-lived persistent charges are formed, exhibiting lifetimes that extend for several minutes; their recombination kinetics has been studied by following the formation and decay of the P…
Probing DNA conductivity with photoinduced electron transfer and scanning tunneling microscopy.
2012
Abstract The possibility that the stacked DNA bases can mediate vectorial electron transfer has been examined using two different approaches. Experiments on photoinduced electron transfer with intercalated donors and acceptors (either randomly bound or linked dyads of ruthenium complex and viologen) indicate that while DNA may be a better medium than acetonitrile for electron transfer over short distances (2-3-base pair, equivalent to 10-14Å centre-to-centre separation), it is a poor medium for transport over larger separations. Attempts to measure conductivity of individual DNA molecules using scanning tunneling microscopy to image mixed monolayers of mercaptohexanol (MCH) and 30-mer or 10…
Tuning of the photoinduced charge transfer process in donor-acceptor "double cable" copolymers
2003
The covalent linking of acceptor molecules to electron donating conjugated polymer is an approach for the development of new photoactive materials for the fabrication of organic photoelectric conversion devices. With this strategy we have designed a polyalkylthiophene copolymer series containing in the side chain anthraquinone molecules as electron acceptor. The peculiar features of the copolymers are the good processability and the ease in tailoring the content of acceptor moieties. Their potential use as photoactive materials is investigated in terms of the photoinduced charge transfer properties, studied by FTIR photoinduced absorption and Light Induced Electron Spin Resonance spectrosco…
Dynamic chemical devices: photoinduced electron transfer and its ion-triggered switching in nanomechanical butterfly-type bis(porphyrin)terpyridines.
2005
A series of butterfly-type molecular constructs has been prepared in good yield by using a double Stille coupling synthetic protocol. They are composed of a terpyridine (terpy) scaffold and two wings composed of appended porphyrins that are capable of switching from an extended W geometry to a compact U geometry upon cation coordination of the terpy unit. The porphyrin moieties exist in the constructs either as free bases or they can be sequentially metallated, thus giving rise to wings of different "colours". Stationary and time-resolved emission studies of the HZn, ZnAu and Zn2Au constructs show that the electronic properties are strongly dependent on the geometry. In the extended W confo…