Variation of the Fermi level and the electrostatic force of a metallic nanoparticle upon colliding with an electrode.
When a metallic nanoparticle (NP) comes in close contact with an electrode, its Fermi level equilibrates with that of the electrode if their separation is less than the cut-off distance for electron tunnelling. In the absence of chemical reactions in solution, the charge on the metallic nanoparticle is constant outside this range before or after the collision. However, the double layer capacitances of both the electrode and the NP are influenced by each other, varying as the function of distance. Because the charge on the nanoparticle is constant, the outer potential of the metallic NP and hence its Fermi level varies as the capacitance changes. This effect is more pronounced for small part…
Understanding Digestive Ripening of Ligand-Stabilized, Charged Metal Nanoparticles
Most syntheses of thiolate-protected metal nanoparticles (NPs) include a thermochemical step in which the as-prepared, polydisperse NPs are transformed to a narrower size distribution in a poorly understood process known as digestive ripening (DR). Previous theoretical approaches considered either surface and electrostatic contributions or surface and ligand-binding contributions. We show that the three contributions are needed to obtain theoretical predictions in agreement with experimental observations. Although statistical thermodynamics does not clarify mechanistic details, it certainly provides valuable insights on the DR process. Remarkably, a relatively simple theory with no fitting …
Ionic partition diagram of tetraphenylporphyrin at the water|1,2-dichloroethane interface
diagram of 5,10,15,20-tetraphenyl-21H,23H-porphine (H2TPP) at the water|1,2-dichloroethane interface using a simple Born solvation model. This zone diagram shows under which form this porphyrin is present, i.e. neutral, monoprotonated or diprotonated, and in which phase i.e. either in the aqueous or the organic phase as a function of the aqueous pH and the interface polarisation that can be controlled externally or by the distribution of supporting electrolytes. This diagram explains why the monoprotonated form has been difficult to observe when doing biphasic pH titrations
Dioxygen reduction by cobalt(II) octaethylporphyrin at liquid|liquid interfaces.
Oxygen reduction catalyzed by cobalt(II) (2,3,7,8,12,13,17,18-octaethylporphyrin) [Co(OEP)] at soft interfaces is studied by voltammetry and biphasic reactions. When Co(OEP) is present in a solution of 1,2-dichloroethane in contact with an aqueous acidic solution, oxygen is reduced if the interface is positively polarized (water phase versus organic phase). This reduction reaction is facilitated when an additional electron donor, here ferrocene, is present in excess in the organic phase.
Self-Assembled Molecular Rafts at Liquid|Liquid Interfaces for Four-Electron Oxygen Reduction
The self-assembly of the oppositely charged water-soluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP(4+)) and cobalt tetrasulphonatophenyl porphyrin (CoTPPS(4-)), at the interface with an organic solvent to form molecular "rafts", provides an excellent catalyst to perform the interfacial four-electron reduction of oxygen by lipophilic electron donors such as tetrathiafulvalene (TTF). The catalytic activity and selectivity of the self-assembled catalyst toward the four-electron pathway was found to be as good as that of the Pacman type cofacial cobalt porphyrins. The assembly has been characterized by UV-visible spectroscopy, Surface Second Harmonic Generation, and Scanning …
Evidence of tetraphenylporphyrin monoacids by ion-transfer voltammetry at polarized liquid|liquid interfaces
We present a simple methodology to illustrate the existence of tetraphenylporphyrin monoacid based on ion-transfer voltammetry at a polarized water|1,2-dichloroethane interface and organic pK values are also estimated.
Room temperature ionic liquids based on cationic porphyrin derivatives and tetrakis(pentafluorophenyl)borate anion
A series of 11 low melting ionic liquids based on meso-substituted A3B -porphyrins and A2B2-porphyrins containing one or two pyridyl substituents have been synthesized in high yields. Three of them are liquids at room temperature. All these porphyrinic salts were characterized by1H NMR,19F NMR, MALDI-TOF mass spectrometry, elemental analysis and UV-visible spectroscopy. The thermal properties and conductivity values of these salt derivatives have been also measured. A specific conductivity value of up to 4 mS.cm-1could be obtained for a compound having the counter-anion B(C6F5)4-.
Contact Potentials, Fermi Level Equilibration, and Surface Charging.
This article focuses on contact electrification from thermodynamic equilibration of the electrochemical potential of the electrons of two conductors upon contact. The contact potential difference generated in bimetallic macro- and nanosystems, the Fermi level after the contact, and the amount and location of the charge transferred from one metal to the other are discussed. The three geometries considered are spheres in contact, Janus particles, and core-shell particles. In addition, the force between the two spheres in contact with each other is calculated and is found to be attractive. A simple electrostatic model for calculating charge distribution and potential profiles in both vacuum an…
Interfacial Self-Assembly of Water-Soluble Cationic Porphyrins for the Reduction of Oxygen to Water
Meet at the border: Assembly of the water-soluble cobalt tetrakis(N-methylpyridinium-4-yl)porphyrin [CoTMPyP]4+ at soft interfaces is enhanced and stabilized by its interfacial interaction with the lipophilic anion (C6F5)4B−. The supramolecular structure thus formed (see picture) provides excellent catalytic activity in the four-electron reduction of oxygen.
Correction: Variation of the Fermi level and the electrostatic force of a metallic nanoparticle upon colliding with an electrode.
The nanoparticle potential varies with the distance from the electrode, and sometimes like attracts like.
Fine tuning of the catalytic effect of a metal-free porphyrin on the homogeneous oxygen reduction.
The catalytic effect of tetraphenylporphyrin on the oxygen reduction with ferrocene in 1,2-dichloroethane can be finely tuned by varying the molar ratio of the acid to the catalyst present in the solution. The mechanism involves binding of molecular oxygen to the protonated free porphyrin base, in competition with ion pairing between the protonated base and the acid anion present.
Proton pump for O2 reduction catalyzed by 5,10,15,20-tetraphenylporphyrinatocobalt(II).
The role of 5,10,15,20-tetraphenylporphyrinatocobalt(II) ([Co(tpp)]) as a catalyst on molecular oxygen (O(2)) reduction by ferrocene (Fc) and its two derivatives, 1,1'-dimethylferrocene (DFc) and decamethylferrocene (DMFc) at a polarized water|1,2-dichloroethane (DCE) interface has been studied. The water|DCE interface essentially acts as a proton pump controlled by the Galvani potential difference across the interface, driving the proton transfer from water to DCE. [Co(tpp)] catalyzed O(2) reduction by Fc, DFc and DMFc is then followed to produce hydrogen peroxide (H(2)O(2)). The catalytic mechanism is similar to that proposed by Fukuzumi et al. for bulk reactions. This interfacial system …
Biomimetic oxygen reduction by cofacial porphyrins at a liquid-liquid interface.
Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene−water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyr- in, 4,5-bis(5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl))-9,9-dimethylxanthene, Co2(DPX), actually catalyzes oxygen reduction to hydrogen p…