Metal and semiconductor NPs

Examples of electroactive NP materials discussed in the review include Ti02, Mn02, iron oxides, other metal oxides, hydroxides and oxyhydroxides and Prussian Blue. We use the term electroactive N Ps to refer to the faradaic electroactivity in such materials and to distinguish them from NPs comprised of metals (such as Au, Ag, Pt, Co, etc.) or semiconductors (such as CdS, CdSe, etc.). This distinction is based on the ability of many electroactive NPs to undergo faradaic oxidation or reduction of all of the metal (redox) centers in the NP. This is in contrast to the behavior of many metal and semiconductor NPs for which oxidation or reduction is fundamentally an interfacial, double-layer process. This deflnition is somewhat arbitrary, since the smallest metal and semiconductor NPs behave molecularly, blurring the distinction... 

While the variety of NPs used in catalytic and sensor applications is extensive, this chapter will primarily focus on metallic and semiconductor NPs. The term functional nanoparticle will refer to a nanoparticle that interacts with a complementary molecule and facilitate an electrochemical process, integrating supramolecular and redox function. The chapter will first concentrate on the role of exo-active surfaces and core-based materials within sensor applications. Exo-active surfaces will be evaluated based upon their types of molecular receptors, ability to incorporate multiple chemical functionalities, selectivity toward distinct analytes, versatility as nanoscale receptors, and ability to modify electrodes via nanocomposite assemblies. Core-based materials will focus on electrochemical labeling and tagging methods for biosensor applications, as well as biological processes that generate an electrochemical response at their core. Finally, this chapter will shift its focus toward the catalytic nature of NPs, discussing electrochemical reactions and enhancement in electron transfer. 

Polyelectrolytes Linear polyelectrolytes in solution can provide a scaffold for the adsorption of metal ions with opposite charges. Thereafter, the ion-absorbed polyelectrolyte templates can transform to ID metal or semiconductor NP assemblies either by a reduction reaction or by chemical combination of ion pairs. Minko and co-workers explored this strategy to prepare 1D Pd NP assemblies. Colfen and co-workers adopted double-hydrophihc block copolymers (DHBCs) with more complex structures, in which one hydrophilic block interacted strongly with appropriate inorganic materials and the... 

Among all semiconductor NPs, metal selenides have been the focus of great attention due to their importance in various applications such as thermoelectric cooling materials, optical filters and sensors, optical recording materials, solar cells, superionic materials, laser materials and biological labels. Many synthetic methods have been developed for the preparation of relatively monodispersed selenide nanopartides (Murray et al., 1993 Korgel... 

The lure of new physical phenomena and new patterns of chemical reactivity has driven a tremendous surge in the study of nanoscale materials. This activity spans many areas of chemistry. In the specific field of electrochemistry, much of the activity has focused on several areas (a) electrocatalysis with nanoparticles (NPs) of metals supported on various substrates, for example, fuel-cell catalysts comprising Pt or Ag NPs supported on carbon [1,2], (b) the fundamental electrochemical behavior of NPs of noble metals, for example, quantized double-layer charging of thiol-capped Au NPs [3-5], (c) the electrochemical and photoelectrochemical behavior of semiconductor NPs [4, 6-8], and (d) biosensor applications of nanoparticles [9, 10]. These topics have received much attention, and relatively recent reviews of these areas are cited. Considerably less has been reported on the fundamental electrochemical behavior of electroactive NPs that do not fall within these categories. In particular, work is only beginning in the area of the electrochemistry of discrete, electroactive NPs. That is the topic of this review, which discusses the synthesis, interfacial immobilization and electrochemical behavior of electroactive NPs. The review is not intended to be an exhaustive treatment of the area, but rather to give a flavor of the types of systems that have been examined and the types of phenomena that can influence the electrochemical behavior of electroactive NPs. 

Research in our laboratory and by Osa and Fujihira showed that it is possible to covalently attach monolayers of chromo-phores to metal-oxide semiconductor surfaces — with no compromise in quantum efficiency to energy conversion compared with dyes adsorbed from solution (9-11). The quantum efficiency for these systems (ratio of photo-generated current to photons adsorbed in the dye layer, ne/np) is quite low, in the range of 10 5 to 10 4 and argues against device applications of these simple modified electrodes without further improvements, such as linear, multielectrode stacks of dye-modified, semi-transparent electrodes (10). 

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