John D. Gilbertson

Zero-Reabsorption Doped-Nanocrystal Luminescent Solar Concentrators

Optical concentration can lower the cost of solar energy conversion by reducing photovoltaic cell area and increasing photovoltaic efficiency. Luminescent solar concentrators offer an attractive approach to combined spectral and spatial concentration of both specular and diffuse light without tracking, but they have been plagued by luminophore self-absorption losses when employed on practical size scales. Here, we introduce doped semiconductor nanocrystals as a new class of phosphors for use in luminescent solar concentrators. In proof-of-concept experiments, visibly transparent, ultraviolet-selective luminescent solar concentrators have been prepared using colloidal Mn(2+)-doped ZnSe nanocrystals that show no luminescence reabsorption. Optical quantum efficiencies of 37% are measured, yielding a maximum projected energy concentration of ∼6× and flux gain for a-Si photovoltaics of 15.6 in the large-area limit, for the first time bounded not by luminophore self-absorption but by the transparency of the waveguide itself. Future directions in the use of colloidal doped nanocrystals as robust, processable spectrum-shifting phosphors for luminescent solar concentration on the large scales required for practical application of this technology are discussed.

Kinetic Evaluation of Highly Active Supported Gold Catalysts Prepared from Monolayer-Protected Clusters: An Experimental Michaelis-Menten Approach for Determining the Oxygen Binding Constant during CO Oxidation Catalysis

Thiol monolayer-protected Au clusters (MPCs) were prepared using dendrimer templates, deposited onto a high-surface-area titania, and then the thiol stabilizers were removed under H2/N2. The resulting Au catalysts were characterized with transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy of adsorbed CO. The Au catalysts prepared via this route displayed minimal particle agglomeration during the deposition and activation steps. Structural data obtained from the physical characterization of the Au catalysts were comparable to features exhibited from a traditionally prepared standard Au catalyst obtained from the World Gold Council (WGC). A differential kinetic study of CO oxidation catalysis by the MPC-prepared Au and the standard WGC catalyst showed that these two catalyst systems have essentially the same reaction order and Arrhenius apparent activation energies (28 kJ/mol). However, the MPC-prepared Au catalyst shows 50% greater activity for CO oxidation. Using a Michaelis-Menten approach, the oxygen binding constants for the two catalyst systems were determined and found to be essentially the same within experimental error. To our knowledge, this kinetic evaluation is the first experimental determination of oxygen binding by supported Au nanoparticle catalysts under working conditions. The values for the oxygen binding equilibrium constant obtained from the Michaelis-Menten treatment (ca. 29-39) are consistent with ultra-high-vacuum measurements on model catalyst systems and support density functional theory calculations for oxygen binding at corner or edge atoms on Au nanoparticles and clusters.

Dendrimer-Encapsulated Bimetallic Nanoparticles: Synthesis, Characterization, and Applications to Homogeneous and Heterogeneous Catalysis

We review the preparation, characterization, and properties of dendrimer-templated bimetallic nanoparticles. Polyamidoamine (PAMAM) dendrimers can be used to template and stabilize a wide variety of mono- and bimetallic nanoparticles. Depending on the specific requirements of the metal system, a variety of synthetic methodologies are available for preparing nanoparticles with diameters on the order of 1–3 nm with narrow particle size distributions. The resulting dendrimer-encapsulated nanoparticles, or DENs, have been physically characterized with electron microscopy techniques, as well as UV-visible and X-ray photoelectron spectroscopies.

Ligand-based reduction of CO2 and release of CO on iron(II).

A synthetic cycle for the CO(2)-to-CO conversion (with subsequent release of CO) based on iron(II), a redox-active pydridinediimine ligand (PDI), and an O-atom acceptor is reported. This conversion is a passive-type ligand-based reduction, where the electrons for the CO(2) conversion are supplied by the reduced PDI ligand and the ferrous state of the iron is conserved.

Synthesis and Stabilization of a Monomeric Iron(II) Hydroxo Complex via Intramolecular Hydrogen Bonding in the Secondary Coordination Sphere

Utilizing the pyridinediimine ligand [(2,6-(i)PrC(6)H(3))N═CMe)(N((i)Pr)(2)C(2)H(4))N═CMe)C(5)H(3)N] (didpa), the iron(II) complexes Fe(didpa)Br(2) (1), [Fe(Hdidpa)Br(2)][PF(6)] (2), and [Fe(Hdidpa)CH(3)CN(OH)][2PF(6)] (3) were synthesized and characterized by X-ray diffraction and spectroscopic methods. The X-ray data show that the didpa scaffold is capable of forming intramolecular hydrogen bonds in the solid state located within the secondary coordination sphere of complexes 2 and 3. These hydrogen bonds are responsible for stabilizing the iron(II) hydroxo ligand in 3, which originates from H(2)O.

Pyridinediimine Iron Complexes with Pendant Redox-Inactive Metals Located in the Secondary Coordination Sphere.

A series of pyridinediimine (PDI) iron complexes that contain a pendant 15-crown-5 located in the secondary coordination sphere were synthesized and characterized. The complex Fe((15c5)PDI)(CO)2 (2) was shown in both the solid state and solution to encapsulate redox-inactive metal ions. Modest shifts in the reduction potential of the metal-ligand scaffold were observed upon encapsulation of either Na(+) or Li(+).

Probing the Protonation State and the Redox-Active Sites of Pendant Base Iron(II) and Zinc(II) Pyridinediimine Complexes

Utilizing the pyridinediimine ligand [(2,6-(i)PrC6H3)N═CMe)(N((i)Pr)2C2H4)N═CMe)C5H3N] (didpa), the zinc(II) and iron(II) complexes Zn(didpa)Cl2 (1), Fe(didpa)Cl2 (2), [Zn(Hdidpa)Cl2][PF6] (3), [Fe(Hdidpa)Cl2][PF6] (4), Zn(didpa)Br2 (5), and [Zn(Hdidpa)Br2][PF6] (6), Fe(didpa)(CO)2 (7), and [Fe(Hdidpa)(CO)2][PF6] (8) were synthesized and characterized. These complexes allowed for the study of the secondary coordination sphere pendant base and the redox-activity of the didpa ligand scaffold. The protonated didpa ligand is capable of forming metal halogen hydrogen bonds (MHHBs) in complexes 3, 4, and 6. The solution behavior of the MHHBs was probed via pKa measurements and (1)H NMR titrations of 3 and 6 with solvents of varying H-bond accepting strength. The H-bond strength in 3 and 6 was calculated in silico to be 5.9 and 4.9 kcal/mol, respectively. The relationship between the protonation state and the ligand-based redox activity was probed utilizing 7 and 8, where the reduction potential of the didpa scaffold was found to shift by 105 mV upon protonation of the reduced ligand in Fe(didpa)(CO)2.

Uncoupled Redox-Inactive Lewis Acids in the Secondary Coordination Sphere Entice Ligand-Based Nitrite Reduction

Metal complexes composed of redox-active pyridinediimine (PDI) ligands are capable of forming ligand-centered radicals. In this Forum article, we demonstrate that integration of these types of redox-active sites with bioinspired secondary coordination sphere motifs produce direduced complexes, where the reduction potential of the ligand-based redox sites is uncoupled from the secondary coordination sphere. The utility of such ligand design was explored by encapsulating redox-inactive Lewis acidic cations via installation of a pendant benzo-15-crown-5 in the secondary coordination sphere of a series of Fe(PDI) complexes. Fe(15bz5PDI)(CO)2 was shown to encapsulate the redox-inactive alkali ion, Na+, causing only modest (31 mV) anodic shifts in the ligand-based redox-active sites. By uncoupling the Lewis acidic sites from the ligand-based redox sites, the pendant redox-inactive ion, Na+, can entice the corresponding counterion, NO2-, for reduction to NO. The subsequent initial rate analysis reveals an acceleration in anion reduction, confirming this hypothesis.