Physical Chemistry of Semiconductor−Liquid Interfaces

Nozik, Arthur J.; Memming, R.

doi:10.1021/jp953720e

Cited by 894 publications

(750 citation statements)

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“…37 The rate of backward transfer, k ET -, is orders of magnitude slower. [14][15][16][17][18][19][20][21][22]30,31,38 We measured single-molecule interfacial electron transfer rates at specific local environments, providing new insights into the origin of multiexponential behavior.…”

Section: Introductionmentioning

confidence: 99%

Single-Molecule Kinetics of Interfacial Electron Transfer

1997

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Measurements of single-molecule chemical reaction kinetics are demonstrated for interfacial electron transfer from excited cresyl violet molecules to the conduction band of indium tin oxide (ITO) or energetically accessible surface electronic states under ambient conditions by using a far-field fluorescence microscope. In this system, each single molecule exhibits a single-exponential electron transfer kinetics. A wide distribution of sitespecific electron transfer rates is observed for many single cresyl violet molecules examined. This work reveals that the physical origin of multiexponential kinetics of electron transfer in this system is the inhomogeneity of molecular interactions on the semiconductor surface of ITO. We illustrate that the singlemolecule experiments provide detailed information not obtainable from experiments conducted on large ensembles of molecules. Single-molecule kinetics is particularly useful in understanding multiexponential behavior of chemical reactions in heterogeneous systems.

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Section: Introductionmentioning

confidence: 99%

Single-Molecule Kinetics of Interfacial Electron Transfer

1997

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“…The data can be fitted with the linear free energy relationship (LFER) [122] shown in the figure (constants in caption). The numerical values of α and β do not have physical significance, because the fitted rate R (μmol h À1 ) does not convey any information about the value of the rate constant for the process, which depends on the electro-active area of the nanoparticles, the absorbed photons flux, space charge layer effects, and other unknown parameters [30,[124][125][126][127][128].The model provides a physical explanation for the observed correlation between nanosheet energetics and hydrogen evolution rates, and it confirms the dependence of photocatalytic activity on the presence of specifically adsorbed ions.…”

Section: Multiple Exciton Generationmentioning

confidence: 99%

Nanoscale Effects in Water Splitting Photocatalysis

Osterloh

2015

Topics in Current Chemistry

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From a conceptual standpoint, the water photoelectrolysis reaction is the simplest way to convert solar energy into fuel. It is widely believed that nanostructured photocatalysts can improve the efficiency of the process and lower the costs. Indeed, nanostructured light absorbers have several advantages over traditional materials. This includes shorter charge transport pathways and larger redox active surface areas. It is also possible to adjust the energetics of small particles via the quantum size effect or with adsorbed ions. At the same time, nanostructured absorbers have significant disadvantages over conventional ones. The larger surface area promotes defect recombination and reduces the photovoltage that can be drawn from the absorber. The smaller size of the particles also makes electron-hole separation more difficult to achieve. This chapter discusses these issues using selected examples from the literature and from the laboratory of the author.

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“…The study of photoelectrodes in situ and under real or simulated operating conditions in an electrochemical environment is especially important because the properties and characteristics of a photoelectrode are often intimately coupled to the properties of the liquid-phase electrolyte. 20,21 As described in more detail in the review article by Smith et al, 22 the electrolyte can strongly affect the chemical and electronic properties of the surface and space-charge layer of the photoelectrode, and therefore influence catalytic, charge transport, and corrosion processes. Ex situ techniques performed in atmosphere or vacuum can also provide important and complementary information about a photoelectrode material, but cannot substitute for viewing the true physical and chemical state of the material in a photoelectrochemical environment.…”

Section: Introductionmentioning

confidence: 99%