Activation Thermodynamics and H/D Kinetic Isotope Effect of the Hox to HredH+ Transition in [FeFe] Hydrogenase.

Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The Hox→HredH+ reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol-1 and a ∼2.5-fold kinetic isotope effect. Overall, these results support electron injection from CdSe into CaI involving F-clusters, and that the Hox→HredH+ step of catalytic proton reduction in CaI proceeds by a proton-dependent process.

Relationships between Exciton Dissociation and Slow Recombination within ZnSe/CdS and CdSe/CdS Dot-in-Rod Heterostructures.

Type-II and quasi type-II heterostructure nanocrystals are known to exhibit extended excited-state lifetimes compared to their single material counterparts because of reduced wave function overlap between the electron and hole. However, due to fast and efficient hole trapping and nonuniform morphologies, the photophysics of dot-in-rod heterostructures are more rich and complex than this simple picture. Using transient absorption spectroscopy, we observe that the behavior of electrons in the CdS "rod" or "bulb" regions of nonuniform ZnSe/CdS and CdSe/CdS dot-in-rods is similar regardless of the "dot" material, which supports previous work demonstrating that hole trapping and particle morphology drive electron dynamics. Furthermore, we show that the longest lived state in these dot-in-rods is not generated by the type-II or quasi type-II band alignment between the dot and the rod, but rather by electron-hole dissociation that occurs due to fast hole trapping in the CdS rod and electron localization to the bulb. We propose that specific variations in particle morphology and surface chemistry determine the mechanism and efficiency of charge separation and recombination in these nanostructures, and therefore impact their excited-state dynamics to a greater extent than the heterostructure energy level alignment alone.

Observation of trapped-hole diffusion on the surfaces of CdS nanorods.

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-1/2 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.

Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid.

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.

Materials Properties and Solvated Electron Dynamics of Isolated Nanoparticles and Nanodroplets Probed with Ultrafast Extreme Ultraviolet Beams.

We present ultrafast photoemission measurements of isolated nanoparticles in vacuum using extreme ultraviolet (EUV) light produced through high harmonic generation. Surface-selective static EUV photoemission measurements were performed on nanoparticles with a wide array of compositions, ranging from ionic crystals to nanodroplets of organic material. We find that the total photoelectron yield varies greatly with nanoparticle composition and provides insight into material properties such as the electron mean free path and effective mass. Additionally, we conduct time-resolved photoelectron yield measurements of isolated oleylamine nanodroplets, observing that EUV photons can create solvated electrons in liquid nanodroplets. Using photoemission from a time-delayed 790 nm pulse, we observe that a solvated electron is produced in an excited state and subsequently relaxes to its ground state with a lifetime of 151 ± 31 fs. This work demonstrates that femotosecond EUV photoemission is a versatile surface-sensitive probe of the properties and ultrafast dynamics of isolated nanoparticles.

Solvents effects on charge transfer from quantum dots.

To predict and understand the performance of nanodevices in different environments, the influence of the solvent must be explicitly understood. In this Communication, this important but largely unexplored question is addressed through a comparison of quantum dot charge transfer processes occurring in both liquid phase and in vacuum. By comparing solution phase transient absorption spectroscopy and gas-phase photoelectron spectroscopy, we show that hexane, a common nonpolar solvent for quantum dots, has negligible influence on charge transfer dynamics. Our experimental results, supported by insights from theory, indicate that the reorganization energy of nonpolar solvents plays a minimal role in the energy landscape of charge transfer in quantum dot devices. Thus, this study demonstrates that measurements conducted in nonpolar solvents can indeed provide insight into nanodevice performance in a wide variety of environments.

Competition between electron transfer, trapping, and recombination in CdS nanorod-hydrogenase complexes.

Electron transfer from photoexcited CdS nanorods to [FeFe]-hydrogenase is a critical step in photochemical H2 production by CdS-hydrogenase complexes. By accounting for the distributions in the numbers of electron traps and enzymes adsorbed, we determine rate constants and quantum efficiencies for electron transfer from transient absorption measurements.

Electron transfer kinetics in CdS nanorod-[FeFe]-hydrogenase complexes and implications for photochemical H2 generation.

This Article describes the electron transfer (ET) kinetics in complexes of CdS nanorods (CdS NRs) and [FeFe]-hydrogenase I from Clostridium acetobutylicum (CaI). In the presence of an electron donor, these complexes produce H2 photochemically with quantum yields of up to 20%. Kinetics of ET from CdS NRs to CaI play a critical role in the overall photochemical reactivity, as the quantum efficiency of ET defines the upper limit on the quantum yield of H2 generation. We investigated the competitiveness of ET with the electron relaxation pathways in CdS NRs by directly measuring the rate and quantum efficiency of ET from photoexcited CdS NRs to CaI using transient absorption spectroscopy. This technique is uniquely suited to decouple CdS→CaI ET from the processes occurring in the enzyme during H2 production. We found that the ET rate constant (k(ET)) and the electron relaxation rate constant in CdS NRs (k(CdS)) were comparable, with values of 10(7) s(-1), resulting in a quantum efficiency of ET of 42% for complexes with the average CaI:CdS NR molar ratio of 1:1. Given the direct competition between the two processes that occur with similar rates, we propose that gains in efficiencies of H2 production could be achieved by increasing k(ET) and/or decreasing k(CdS) through structural modifications of the nanocrystals. When catalytically inactive forms of CaI were used in CdS-CaI complexes, ET behavior was akin to that observed with active CaI, demonstrating that electron injection occurs at a distal iron-sulfur cluster and is followed by transport through a series of accessory iron-sulfur clusters to the active site of CaI. Using insights from this time-resolved spectroscopic study, we discuss the intricate kinetic pathways involved in photochemical H2 generation in CdS-CaI complexes, and we examine how the relationship between the electron injection rate and the other kinetic processes relates to the overall H2 production efficiency.

Charge transfer dynamics between photoexcited CdS nanorods and mononuclear Ru water-oxidation catalysts.

We describe the charge transfer interactions between photoexcited CdS nanorods and mononuclear water oxidation catalysts derived from the [Ru(bpy)(tpy)Cl](+) parent structure. Upon excitation, hole transfer from CdS oxidizes the catalyst (Ru(2+) → Ru(3+)) on a 100 ps to 1 ns timescale. This is followed by 10-100 ns electron transfer (ET) that reduces the Ru(3+) center. The relatively slow ET dynamics may provide opportunities for the accumulation of multiple holes at the catalyst, which is necessary for water oxidation.

(Ga1-xZnx)(N1-xOx) nanocrystals: visible absorbers with tunable composition and absorption spectra.

Bulk oxy(nitride) (Ga(1-x)Zn(x))(N(1-x)O(x)) is a promising photocatalyst for water splitting under visible illumination. To realize its solar harvesting potential, it is desirable to minimize its band gap through synthetic control of the value of x. Furthermore, improved photochemical quantum yields may be achievable with nanocrystalline forms of this material. We report the synthesis, structural, and optical characterization of nanocrystals of (Ga(1-x)Zn(x))(N(1-x)O(x)) with the values of x tunable from 0.30 to 0.87. Band gaps decreased from 2.7 to 2.2 eV over this composition range, which corresponded to a 260% increase in the fraction of solar photons that could be absorbed by the material. We achieved nanoscale morphology and compositional control by employing mixtures of ZnGa(2)O(4) and ZnO nanocrystals as synthetic precursors that could be converted to (Ga(1-x)Zn(x))(N(1-x)O(x)) under NH(3). The high quality of the resulting nanocrystals is encouraging for achieving photochemical water-splitting rates that are competitive with internal carrier recombination pathways.

Simulation-aided design and synthesis of hierarchically porous membranes.

Free-standing silica membranes with hierarchical porosity (ca. 300 nm macropores surrounded by 6-8 nm mesopores) and controllable mesopore architecture were prepared by a dual-templating method, with the structural design aided by mesoscale simulation. To create a two-dimensional, hexagonal macropore array, polymeric colloidal hemisphere arrays were synthesized by a two-step annealing process starting with non-close-packed polystyrene sphere arrays on silicon coated with a sacrificial alumina layer. A silica precursor containing a poly(ethylene) oxide-poly(propylene oxide)-poly(ethylene) oxide (PEO-PPO-PEO) triblock-copolymer surfactant as template for mesopore creation was spin-coated onto the support and aged and then converted into the free-standing membranes by dissolving both templates and the alumina layer. To test the hypothesis that the mesopore architecture may be influenced by confinement of the surfactant-containing precursor solution in the colloidal array and by its interactions with the polymeric colloids, the system was studied theoretically by dissipative particle dynamics (DPD) simulations and experimentally by examining the pore structures of silica membranes via electron microscopy. The DPD simulations demonstrated that, while only tilted columnar structure can be formed through tuning the interaction with the substrate, perfect alignment of 2D hexagonal micelles perpendicular to the plane of the membrane is achievable by confinement between parallel walls that interact preferentially with the hydrophilic components (PEO blocks, silicate, and solvent). The simulations predicted that this alignment could be maintained across a span of up to 10 columns of micelles, the same length scale defined by the colloidal array. In the actual membranes, we manipulated the mesopore alignment by tuning the solvent polarity relative to the polar surface characteristics of the colloidal hemispheres. With methanol as a solvent, columnar mesopores parallel to the substrate were observed; with a methanol-water mixed solvent, individual spherical mesopores were present; and with water as the only solvent, twisted columnar structures were seen.

Characterization of photochemical processes for H2 production by CdS nanorod-[FeFe] hydrogenase complexes.

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.

Recent Progress in Photocatalysis Mediated by Colloidal II-VI Nanocrystals.

The use of photoexcited electrons and holes in semiconductor nanocrystals as reduction and oxidation reagents is an intriguing way of harvesting photon energy to drive chemical reactions. This review focuses on recent research efforts to understand and control the photocatalytic processes mediated by colloidal II-VI nanocrystalline materials, such as cadmium and zinc chalcogenides. First, we highlight how nanocrystal properties govern the rates and efficiencies of charge-transfer processes relevant to photocatalysis. We then describe the use of nanocrystal catalyst heterostructures for fuel-forming reactions, most commonly H2 generation. Finally, we review the use of nanocrystal photocatalysis as a synthetic tool for metal-semiconductor nano-heterostructures.