Photovoltaic Performance of Ultrasmall PbSe Quantum Dots

We investigated the effect of PbSe quantum dot size on the performance of Schottky solar cells made in an ITO/PEDOT/PbSe/aluminum structure, varying the PbSe nanoparticle diameter from 1 to 3 nm. In this highly confined regime, we find that the larger particle bandgap can lead to higher open-circuit voltages (~0.6 V), and thus an increase in overall efficiency compared to previously reported devices of this structure. To carry out this study, we modified existing synthesis methods to obtain ultrasmall PbSe nanocrystals with diameters as small as 1 nm, where the nanocrystal size is controlled by adjusting the growth temperature. As expected, we find that photocurrent decreases with size due to reduced absorption and increased recombination, but we also find that the open-circuit voltage begins to decrease for particles with diameters smaller than 2 nm, most likely due to reduced collection efficiency. Owing to this effect, we find peak performance for devices made with PbSe dots with a first exciton energy of ~1.6 eV (2.3 nm diameter), with a typical efficiency of 3.5%, and a champion device efficiency of 4.57%. Comparing the external quantum efficiency of our devices to an optical model reveals that the photocurrent is also strongly affected by the coherent interference in the thin film due to Fabry-Pérot cavity modes within the PbSe layer. Our results demonstrate that even in this simple device architecture, fine-tuning of the nanoparticle size can lead to substantial improvements in efficiency

A global map of mangrove forest soil carbon at 30 m spatial resolution

With the growing recognition that effective action on climate change will require a combination of emissions reductions and carbon sequestration, protecting, enhancing and restoring natural carbon sinks have become political priorities. Mangrove forests are considered some of the most carbon-dense ecosystems in the world with most of the carbon stored in the soil. In order for mangrove forests to be included in climate mitigation efforts, knowledge of the spatial distribution of mangrove soil carbon stocks are critical. Current global estimates do not capture enough of the finer scale variability that would be required to inform local decisions on siting protection and restoration projects. To close this knowledge gap, we have compiled a large georeferenced database of mangrove soil carbon measurements and developed a novel machine-learning based statistical model of the distribution of carbon density using spatially comprehensive data at a 30 m resolution. This model, which included a prior estimate of soil carbon from the global SoilGrids 250 m model, was able to capture 63% of the vertical and horizontal variability in soil organic carbon density (RMSE of 10.9 kg m−3). Of the local variables, total suspended sediment load and Landsat imagery were the most important variable explaining soil carbon density. Projecting this model across the global mangrove forest distribution for the year 2000 yielded an estimate of 6.4 Pg C for the top meter of soil with an 86–729 Mg C ha−1 range across all pixels. By utilizing remotely-sensed mangrove forest cover change data, loss of soil carbon due to mangrove habitat loss between 2000 and 2015 was 30–122 Tg C with >75% of this loss attributable to Indonesia, Malaysia and Myanmar. The resulting map products from this work are intended to serve nations seeking to include mangrove habitats in payment-for- ecosystem services projects and in designing effective mangrove conservation strategies

Dealloying of Cobalt from CuCo Nanoparticles under Syngas Exposure

International audienceThe structure and composition of core−shell CuCo nanoparticles were found to change as a result of cleaning pretreatments and when exposed to syngas (CO + H 2) at atmospheric pressure. In situ X-ray absorption and photoelectron spectroscopies revealed the oxidation state of the particles as well as the presence of adsorbates under syngas. Transmission electron microscopy was used for ex situ analysis of the shape, elemental composition, and structure after reaction. The original core−shell structure was found to change to a hollow CuCo alloy after pretreatment by oxidation in pure O 2 and reduction in pure H 2. After 30 min of exposure to syngas, a significant fraction (5%) of the particles was strongly depleted in cobalt giving copper-rich nanoparticles. This fraction increased with duration of syngas exposure, a phenomenon that did not occur under pure CO or pure H 2. This study suggests that Co and Cu can each individually contribute to syngas conversion with CuCo catalysts

Porous Core-Shell Nanostructures for Catalytic Applications

Porous core-shell nanostructures have recently received much attention for their enhanced thermal stability. They show great potential in the field of catalysis, as reactant gases can diffuse in and out of the porous shell while the core particle is protected from sintering, a process in which particles coalesce to form larger particles. Sintering is a large problem in industry and is the primary cause of irreversible deactivation.Despite the obvious advantages of high thermal stability, porous core-shell nanoparticles can be developed to have additional interactive properties from the combination of the core and shell together, rather than just the core particle alone. This dissertation focuses on developing new porous core-shell systems in which both the core and shell take part in catalysis. Two types of systems are explored; (1) yolk-shell nanostructures with reducible oxide shells formed using the Kirkendall effect and (2) ceramic-based porous oxide shells formed using sol-gel chemistry. Of the Kirkendall-based systems, Au@FexOy and Cu@CoO were synthesized and studied for catalytic applications. Additionally, ZnO was explored as a potential shelling material. Sol-gel work focused on optimizing synthetic methods to allow for coating of small gold particles, which remains a challenge today. Mixed metal oxides were explored as a shelling material to make dual catalysts in which the product of a reaction on the core particle becomes a reactant within the shell

Colloid chemistry of nanocatalysts: A molecular view

Recent advances of a colloidal chemistry can offer great opportunities to fabricate and design nanocatalysts. Comprehensive understanding of a basic concept and theory of the colloidal synthetic chemistry facilitates to engineer elaborate nano-architectures such as bi- or multi-metallic, heterodimers, and core/shell. This colloidal solution technique not only enables to synthesize high surface mesoporous materials, but also provides a versatile tool to incorporate nanoparticles into mesoporous materials or onto substrates. For green chemistry, catalysis research has been pursued to design and fabricate a catalyst system that produces only one desired product (100% selectivity) at high turnover rates to reduce the production of undesirable wastes. Recent studies have shown that several molecular factors such as the surface structures, composition, and oxidation states affect the turnover frequency and reaction selectivity depending on the size, morphology, and composition of metal nanoparticles. Multipath reactions have been utilized to study the reaction selectivity as a function of size and shape of platinum nanoparticles. In the past, catalysts were evaluated and compared with characterizations before and after catalytic reaction. Much progress on in situ surface characterization techniques has permitted real-time monitoring of working catalysts under various conditions and provides molecular information during the reaction. © 2011 Elsevier Inc..close323

Near-Infrared Localized Surface Plasmon Resonances Arising from Free Carriers in Doped Quantum Dots

Quantum confinement of electronic wavefunctions in semiconductor quantum dots (QDs) yields discrete atom-like and tunable electronic levels, thereby allowing the engineering of excitation and emission spectra. Metal nanoparticles, on the other hand, display strong resonant interactions with light from localized surface plasmon resonance (LSPR) oscillations of free carriers, resulting in enhanced and geometrically tunable absorption and scattering resonances. The complementary attributes of these nanostructures lends strong interest toward integration into hybrid nanostructures to explore enhanced properties or the emergence of unique attributes arising from their interaction. However, the physicochemical interface between the two components can be limiting for energy transfer and synergistic coupling within such a hybrid nanostructure. Therefore, it is advantageous to realize both attributes, i.e., LSPRs and quantum confinement within the same nanostructure. Here, we describe well-defined LSPRs arising from p-type carriers in vacancy-doped semiconductor quantum dots. This opens up possibilities for light harvesting, non-linear optics, optical sensing and manipulation of solid-state processes in single nanocrystals

Hexameric Octahedral Clusters of PbSe Nanocrystals Grown from Amorphous Lead(II) Carboxylate Nanoparticles

We describe the synthesis and three-dimensional structure of a new single-crystalline “hexameric” nanocrystal composed of six near-spherical PbSe nanocrystals arranged at the vertices of an octahedron. We examine the detailed three-dimensional structure of these nanocrystals using electron tomography and demonstrate single-crystal to single-crystal cation exchange to CdSe. We reveal that the growth of these nanocrystals, which form under conditions similar to other anisotropic PbSe nanocrystals, depends on the initial presence of lead oleate particles with approximate diameters of 1.7–3.1 nm that form upon heating lead­(II) acetate hydrate in the presence of oleic acid. These lead oleate particles, which are visible by transmission electron microscopy, constitute the beginning of nearly every synthesis of anisotropic PbSe nanocrystals. We show that the lead oleate particles play a definitive role in determining the morphology of the resultant PbSe nanocrystals. We note that the acetate anion, which was previously identified as the key factor in achieving anisotropic PbSe growth, greatly accelerates the formation of the lead oleate particles, and thus appears to be responsible for the subsequent PbSe morphology. However, we demonstrate that acetate is not required for lead oleate particle formation, nor indeed for anisotropic PbSe growth. The potential role of these new particles in other PbSe synthetic preparations from lead­(II) oleate is of high interest for future study

Dealloying of Cobalt from CuCo Nanoparticles under Syngas Exposure

International audienceThe structure and composition of core−shell CuCo nanoparticles were found to change as a result of cleaning pretreatments and when exposed to syngas (CO + H 2) at atmospheric pressure. In situ X-ray absorption and photoelectron spectroscopies revealed the oxidation state of the particles as well as the presence of adsorbates under syngas. Transmission electron microscopy was used for ex situ analysis of the shape, elemental composition, and structure after reaction. The original core−shell structure was found to change to a hollow CuCo alloy after pretreatment by oxidation in pure O 2 and reduction in pure H 2. After 30 min of exposure to syngas, a significant fraction (5%) of the particles was strongly depleted in cobalt giving copper-rich nanoparticles. This fraction increased with duration of syngas exposure, a phenomenon that did not occur under pure CO or pure H 2. This study suggests that Co and Cu can each individually contribute to syngas conversion with CuCo catalysts