The voltammetric responses of nanometer-sized electrodes in weakly supported electrolyte: A theoretical study

Influence of the diffuse double layer on steady-state voltammetry

“…Activity effects arising from the variation in ionic strength across the double layer will also be considered. In particular, we will consider both a wide range of possible potentials of zero charge for the electrochemical system, as well as a range of reactant charges, allowing for a fuller treatment of double layer effects than in recent, otherwise detailed studies [9,10].…”

“…The development of practical nanoelectrochemical systems in the last decade [5,6] has led to renewed interest in the fundamental theories of electron transfer kinetics and mass transport dynamics, particularly in the context of analytical techniques such as voltammetry [7][8][9][10][11][12][13][14][15][16]. The nanoscale is especially interesting because in this limit the size of a normal depletion layer approaches the Debye length, and so the charged double layer and the depletion layer become interlinked.…”

Electronic structure related electric-double-layer effects on heterogeneous ET kinetics on graphene electrode

“…Numerous recent studies have shown that EDL effect on heterogeneous ET kinetics may be raised even in strongly supported media as the size of an electrode is reduced into nanometer scales [14][15][16][17][18][19][20][29][30][31][32][33][34][35][36][37][38][39][40]. Fig.…”

“…In addition to decreasing the overall DOS overlap with redox molecules, the low DOS near the Fermi level could also impact heterogeneous ET kinetics through the so-called chemical (quantum) capacitance, which results in much distinct electricdouble-layer (EDL) structures at interface of graphene electrodes. In the case when the ET kinetics is significantly affected by the EDL structure, for examples, in weakly supported media [14,15] and on nanometer-sized electrodes [16][17][18][19][20], the chemical capacitance would result in altered EDL effect on ET kinetics from that on metal-based electrodes.…”

Formation of a Single Pinhole on Self‐Assembled Monolayer Modified Nanometer‐Sized Gold Electrode and Its Electrochemical Behaviors

“…Now, the fabrication and application of small electrodes with a critical dimension down to several tens of nanometers have become a routine for electrochemists [6][7][8][9]. When the size of a very small electrode is comparable to the thickness of the electric double layer (EDL) or a Debye length, which is typically smaller than several nanometers, some conditions or factors which can be applied or ignored on a relatively large electrode will not be possible to be applied or ignored anymore [10][11][12][13][14][15][16][17][18][19]. For example, the continuum assumption which is the base of conventional electrochemical theories will not apply if the electrode is small enough [10].…”