Optical transitions in carbon nanotubes are of central importance for nanotube characterization. They also provide insight into the nature of excited states in these one-dimensional systems. Recent work suggests that light absorption produces strongly correlated electron-hole states in the form of excitons. However, it has been difficult to rule out a simpler model in which resonances arise from the van Hove singularities associated with the one-dimensional band [corrected] structure of the nanotubes. Here, two-photon excitation spectroscopy bolsters the exciton picture. We found binding energies of approximately 400 millielectron volts for semiconducting single-walled nanotubes with 0.8-nanometer diameters. The results demonstrate the dominant role of many-body interactions in the excited-state properties of one-dimensional systems.
The splitting of dinitrogen (N2) and reduction to ammonia (NH3) is a kinetically complex and energetically challenging multistep reaction. In the Haber-Bosch process, N2 reduction is accomplished at high temperature and pressure, whereas N2 fixation by the enzyme nitrogenase occurs under ambient conditions using chemical energy from adenosine 5'-triphosphate (ATP) hydrolysis. We show that cadmium sulfide (CdS) nanocrystals can be used to photosensitize the nitrogenase molybdenum-iron (MoFe) protein, where light harvesting replaces ATP hydrolysis to drive the enzymatic reduction of N2 into NH3 The turnover rate was 75 per minute, 63% of the ATP-coupled reaction rate for the nitrogenase complex under optimal conditions. Inhibitors of nitrogenase (i.e., acetylene, carbon monoxide, and dihydrogen) suppressed N2 reduction. The CdS:MoFe protein biohybrids provide a photochemical model for achieving light-driven N2 reduction to NH3.
We have developed complexes of CdS nanorods capped with 3-mercaptopropionic acid (MPA) and Clostridium acetobutylicum [FeFe]-hydrogenase I (CaI) that photocatalyze reduction of H(+) to H(2) at a CaI turnover frequency of 380-900 s(-1) and photon conversion efficiencies of up to 20% under illumination at 405 nm. In this paper, we focus on the compositional and mechanistic aspects of CdS:CaI complexes that control the photochemical conversion of solar energy into H(2). Self-assembly of CdS with CaI was driven by electrostatics, demonstrated as the inhibition of ferredoxin-mediated H(2) evolution by CaI. Production of H(2) by CdS:CaI was observed only under illumination and only in the presence of a sacrificial donor. We explored the effects of the CdS:CaI molar ratio, sacrificial donor concentration, and light intensity on photocatalytic H(2) production, which were interpreted on the basis of contributions to electron transfer, hole transfer, or rate of photon absorption, respectively. Each parameter was found to have pronounced effects on the CdS:CaI photocatalytic activity. Specifically, we found that under 405 nm light at an intensity equivalent to total AM 1.5 solar flux, H(2) production was limited by the rate of photon absorption (~1 ms(-1)) and not by the turnover of CaI. Complexes were capable of H(2) production for up to 4 h with a total turnover number of 10(6) before photocatalytic activity was lost. This loss correlated with inactivation of CaI, resulting from the photo-oxidation of the CdS capping ligand MPA.
The temporal evolution of fluorescence from isolated single-wall carbon nanotubes (SWNTs) has been investigated using optical Kerr gating. The fluorescence emission is found to decay on a time scale of 10 ps. This fast relaxation arises from nonradiative processes, the existence of which explains the relatively low observed fluorescence efficiency in isolated SWNTs. From the measured decay rate and a determination of fluorescence quantum efficiency, we deduce a radiative lifetime of 110 ns.
We have investigated reversible single-wall carbon nanotube (SWNT) oxidation by quantitative analysis of the oxide-induced absorption bleaching and luminescence quenching at low pH. These data, in combination with DFT structure calculations, suggest that the nanotube oxide is a 1,4-endoperoxide. At low pH, the endoperoxide protonates to create a hydroperoxide carbocation, introducing a hole in the SWNT valence band. Nanotube luminescence is extremely sensitive to quenching by hole-doping, while the absorption is relatively robust.
The optical transitions of semiconducting carbon nanotubes have been ascribed to excitons. Here we use two-photon excitation spectroscopy to measure exciton binding energies, as well as band-gap energies, in a range of individual species of semiconducting SWNTs. Exciton binding energies are large and vary inversely with nanotube diameter, as predicted by theory. Band-gap energies are significantly blue-shifted from values predicted by tight-binding calculations.
In CdS nanocrystals, photoexcited holes rapidly become trapped at the particle surface. The dynamics of these trapped holes have profound consequences for the photophysics and photochemistry of these materials. Using a combination of transient absorption spectroscopy and theoretical modelling, we demonstrate that trapped holes in CdS nanorods are mobile and execute a random walk at room temperature. In CdS nanorods of non-uniform width, we observe the recombination of spatially separated electrons and trapped holes, which exhibits a t power-law decay at long times. A one-dimensional diffusion-annihilation model describes the time-dependence of the recombination over four orders of magnitude in time, from one nanosecond to ten microseconds, with a single adjustable parameter. We propose that diffusive trapped-hole motion is a general phenomenon in CdS nanocrystals, but one that is normally obscured in structures in which the wavefunctions of the electron and trapped hole spatially overlap. This phenomenon has important implications for the oxidation photochemistry of CdS nanocrystals.
Time-resolved fluorescence measurements of single-walled carbon nanotubes (SWNTs) reveal rapid electron-hole pair annihilation when multiple electron-hole pairs are present in a nanotube. The process can be understood as Auger recombination with a rate of ϳ1 ps −1 for just two electron-hole pairs in a 380-nm long SWNT. This efficient nonradiative recombination reflects the strong carrier-carrier interactions in the quasione-dimensional SWNTs. In addition to affecting nanotube fluorescence, Auger recombination imposes limitations on the sustained electron-hole density achievable within a SWNT.
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