Ag2S sensitized mesoporous Bi2WO6 architectures with enhanced visible light photocatalytic activity and recycling properties

To harvest solar energy more efficiently, novel Ag2S/Bi2WO6 heterojunctions were synthesized by a hydrothermal route. This novel photocatalyst was synthesized by impregnating Ag2S into a Bi2WO6 semiconductor by a hydrothermal route without any surfactants or templates. The as prepared structures were characterized by multiple techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmet-Teller (BET) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDS), UV-vis diffuse reflection spectroscopy (DRS) and photoluminescence (PL). The characterization results suggest mesoporous hierarchical spherical structures with a high surface area and improved photo response in the visible spectrum. Compared to bare Bi2WO6, Ag2S/Bi2WO6 exhibited much higher photocatalytic activity towards the degradation of dye Rhodamine B (RhB). Although silver based catalysts are easily eroded by photogenerated holes, the Ag2S/Bi2WO6 photocatalyst was found to be highly stable in the cyclic experiments. Based on the results of BET, Pl and DRS analysis, two possible reasons have been proposed for the enhanced visible light activity and stability of this novel photocatalyst: (1) broadening of the photoabsorption range and (2) efficient separation of photoinduced charge carriers which does not allow the photoexcited electrons to accumulate on the conduction band of Ag2S and hence prevents the photocorrosion.

Synthesis of Eu3+-activated ZnO superstructures: Photoluminescence, Judd-Ofelt analysis and Sunlight photocatalytic properties

Photoluminescence and photocatalytic properties of Eu-doped ZnO nanoparticles (NPs) were synthesized by facile phyto route. XPS results demonstrated the existence of Eu3+ as dopant into ZnO. Morphologies of the NPs were mainly dependent on Eu3+ and Aloe vera gel. Red shift of energy band gap was due to the creation of intermediate energy states of Eu3+ and oxygen vacancies in the band gap. PL emission of ZnO:Eu3+ (1-11 mol%, 8 ml and 7 mol%, 2-12 ml) exhibit characteristic peaks of D-5(0) -> F-7(2) transitions. From the Judd-Ofelt analysis, intensities of transitions between different.' levels dependent on the symmetry of the local environment of Eu3+ ions. CIE chromaticity co-ordinates confirm reddish emission of the phosphor. Further, NPs exhibit excellent photocatalytic activity for the degradation of Rhodamine B (94%) under Sunlight was attributed to crystallite size, band gap, morphology and oxygen vacancies. In addition, photocatalyst reusability studies were conducted and found that Eu-doped catalyst could be reused several times with negligible decrease in catalytic activity. The present work directs new possibilities to provide some new insights into the design of new phyto synthesized nanophosphors for display devices, photocatalysts with high activity for environmental clean-up and solar energy conversion. (C) 2015 Elsevier B.V. All rights reserved.

Transport properties of solution processed Cu2SnS3/AZnO heterostructure for low cost photovoltaics

Cu2SnS3 thin films were deposited by a facile sot-gel technique followed by annealing. The annealed films were structurally characterized by grazing incidence X-ray diffraction (GIXRD) and transmission electron microscopy (TEM). The crystal structure was found to be tetragonal with crystallite sizes of 2.4-3 nm. Texture coefficient calculations from the GIXRD revealed the preferential orientation of the film along the (112) plane. The morphological investigations of the films were carried out using field emission scanning electron microscopy (FESEM) and the composition using electron dispersive spectroscopy (EDS). The temperature dependent current, voltage characteristics of the Cu2SnS3/AZnO heterostructure were studied. The log I-log V plot exhibited three regions of different slopes showing linear ohmic behavior and non-linear behavior following the power law. The temperature dependent current voltage characteristics revealed the variation in ideality factor and barrier height with temperature. The Richardson constant was calculated and its deviation from the theoretical value revealed the inhomogeneity of the barrier heights. Transport characteristics were modeled using the thermionic emission model. The Gaussian distribution of barrier heights was applied and from the modified Richardson plot the value of the Richardson constant was found to be 47.18 A cm(-2) K-2. (c) 2015 Elsevier B.V. All rights reserved.

Tailored specular reflectance properties of bulk Cu based novel intermetallic alloys

Significant research has been pursued to develop solar selective metallic coatings using a variety of coating deposition techniques, with limited attempts to assess the properties of bulk metallic materials for solar energy applications. In developing bulk solar reflectors with good reflectance in the entire solar range, we report a new class of reflector materials based on Cu-Sn intermetallics with tailored substitution of aluminium or zinc. Our experimental results suggest that the arc melted-suction cast Cu (78.8 at%)-Al (21.2 at%) alloy with nanoscale surface roughness can exhibit a combination of 89% bulk specular reflectance and 83% bulk solar reflectance, together with a hardness of 2 GPa. We show that the present alloy design approach paves the way for further opportunities of tuning the spectral properties of this new class of solar reflector material. (C) 2016 Elsevier B.V. All rights reserved.

A Nanomechanical Device Based on Light-Driven Proton Pumps

In this paper, a hybrid device based on a microcantilever interfaced with bacteriorhodopsin (bR) is constructed. The microcantilever, on which the highly oriented bR film is self-assembled, undergoes controllable and reversible bending when the light-driven proton pump protein, bR, on the microcantilever surface is activated by visible light. Several control experiments are carried out to preclude the influence of heat and photothermal effects. It is shown that the nanomechanical motion is induced by the resulting gradient of protons, which are transported from the KCl solution on the cytoplasmic side of the bR film towards the extracellular side of the bR film. Along with a simple physical interpretation, the microfabricated cantilever interfaced with the organized molecular film of bR can simulate the natural machinery in converting solar energy to mechanical energy.

Lightweight deformable mirrors for future space telescopes

This thesis presents a concept for ultra-lightweight deformable mirrors based on a thin substrate of optical surface quality coated with continuous active piezopolymer layers that provide modes of actuation and shape correction. This concept eliminates any kind of stiff backing structure for the mirror surface and exploits micro-fabrication technologies to provide a tight integration of the active materials into the mirror structure, to avoid actuator print-through effects. Proof-of-concept, 10-cm-diameter mirrors with a low areal density of about 0.5 kg/m² have been designed, built and tested to measure their shape-correction performance and verify the models used for design. The low cost manufacturing scheme uses replication techniques, and strives for minimizing residual stresses that deviate the optical figure from the master mandrel. It does not require precision tolerancing, is lightweight, and is therefore potentially scalable to larger diameters for use in large, modular space telescopes. Other potential applications for such a laminate could include ground-based mirrors for solar energy collection, adaptive optics for atmospheric turbulence, laser communications, and other shape control applications.

The immediate application for these mirrors is for the Autonomous Assembly and Reconfiguration of a Space Telescope (AAReST) mission, which is a university mission under development by Caltech, the University of Surrey, and JPL. The design concept, fabrication methodology, material behaviors and measurements, mirror modeling, mounting and control electronics design, shape control experiments, predictive performance analysis, and remaining challenges are presented herein. The experiments have validated numerical models of the mirror, and the mirror models have been used within a model of the telescope in order to predict the optical performance. A demonstration of this mirror concept, along with other new telescope technologies, is planned to take place during the AAReST mission.

A tale of two cobalts

There are important problems to overcome if solar energy or other renewable energy sources are to be used effectively on a global scale. Solar photons must not only be harvested and converted into a usable form, but they must also be efficiently stored so that energy is available for use on cloudy days and at night. In this work, both the energy conversion and energy storage problems are addressed. Specifically, two cobalt complexes were designed and their reactivity probed for applications in energy conversion and storage. The first chapter describes a cobalt complex that is the first example of a dimeric cobalt compound with two singly proton-bridged cobaloxime units linked by a central BO4--bridge. Using electrochemical methods, the redox properties of the dimer were evaluated and it was found to be an electrocatalyst for proton reduction in acetonitrile.

Because hydrogen gas is difficult to handle and store, the hydrogenation of CO2 and later dehydrogenation of the liquid product, formic acid, has been proposed as a hydrogen storage system. Thus, a second complex, described in chapter two, supported by a triphosphine ligand framework was used as a catalyst precursor for this key dehydrogenation step. The studies here demonstrate the efficacy of the complex as a precatalyst for the desired reaction, with good conversion of starting formic acid to CO2 and H2. In order to better understand the properties of the triphosphine cobalt complex, a synthetic procedure for substituting electron donating groups (e.g., methoxy groups) onto the ligand was investigated, yielding a novel diphosphine cobalt(II) complex.

Direct simulation of quantum dynamics in complex systems

Accurate simulation of quantum dynamics in complex systems poses a fundamental theoretical challenge with immediate application to problems in biological catalysis, charge transfer, and solar energy conversion. The varied length- and timescales that characterize these kinds of processes necessitate development of novel simulation methodology that can both accurately evolve the coupled quantum and classical degrees of freedom and also be easily applicable to large, complex systems. In the following dissertation, the problems of quantum dynamics in complex systems are explored through direct simulation using path-integral methods as well as application of state-of-the-art analytical rate theories.

Análise da aplicação do regulamento técnico da qualidade do nível de eficiência energética no prédio do IBAM

A racionalização do uso da energia elétrica nas edificações é um assunto atual e de grande importância face ao grande impacto ambiental produzido. O consumo de energia elétrica no Brasil nas edificações residenciais, comerciais, de serviços e públicas é bastante significativo. Calcula-se que quase 50% da energia elétrica produzida no país seja consumida não só na operação e manutenção das edificações como também nos sistemas artificiais, que proporcionam conforto ambiental para seus usuários como iluminação, climatização e aquecimento de água. O Regulamento Técnico de Qualidade do Nível de Eficiência Energética de Edifícios Comerciais e Serviços e Públicos, RQT-C do INMETRO surge como uma contribuição à etiquetagem do nível de eficiência energética das edificações de uso coletivo. Para a determinação da eficiência são considerados três requisitos: envoltória da edificação, sistema de iluminação e sistema de condicionamento de ar. Todos os requisitos têm cinco níveis de eficiência que variam de A (mais eficiente) até E (menos eficiente), que associados com algumas bonificações (uso da energia solar, ventilação natural, etc.) tornam possível a atribuição de uma classificação geral para o edifício em seu todo. Neste trabalho objetivou-se avaliar esse desempenho energético para o prédio do Instituto Brasileiro de Adminstração Municipal -IBAM, situado na cidade do Rio de Janeiro, de concepção modernista. Foi mostrado como as decisões arquitetônicas tomadas e o uso da ventilação natural podem influenciar na avaliação de sua eficiência energética.

Optimisation of the first principle code Octopus for massive parallel architectures: application to light harvesting complexes

150 p.

暖温带落叶阔叶混交林能量生态学研究

本文是首篇研究中国暖温带落叶阔叶混交林能量生态学的论文。在文中，笔者以详实的第一手资料从能量环境、能量流动、能量组合以及能量平衡几个方面，全面、系统地阐述、分析了辽东栎林——这一暖温带落叶阔叶混交林典型自然群落代表的能量生态学特征。 在能量环境一章中，笔者从能量流动，能量平衡的角度出发重点研究了辽东栎群落的辐射能量环境特征。笔者以1991-1993年的观测资料为基础，从乔木、灌木和草本三个层次分析了生长季总辐射、散射辐射、直射辐射、反射辐射、净辐射、先合有效辐射、透射辐射、吸收辐射以及乔木层和灌木层反射率的季节动态和日进程特征，并从天文因子、气象因子和群落自身发育特征几方面解释分析了辐射能量环境的这种时空动态特征，同时，分析了这种变化特征对群落能量流动、分配和平衡过程可能产生的影响。 另外，笔者也对群落湿度和风速环境的时空动态特征进行了分析。 在能量流动一章，笔者以1992-1993年的野外实验资料为依据，沿季节动态、月际变化和日进程的时间轴，从群落、乔木层、灌木层、草本层以及各乔、灌木种群的空间尺度详细分析、阐述了太阳辐射能在森林群落内的流动和转化特征，并从能量环境和群落发育的角度解释分析了能量在群落内的这种时空分布和转化特征。所讨论的能流对象包括群落、乔、灌、草各层及各乔、灌木种群的总能流固定量、叶片呼吸耗能量、剩余能流固定量以及沿枯枝落叶流出的能流量。 与分析能流过程同步，笔者从上述的时、空尺度分别以生长季内太阳总辐射和光合有效辐射为基础计算、分析了森林群落的光能转化率特征。 在这一章的最后，笔者概述性地介绍了辽东栎群落的能量平衡特征 在第四章，笔者从能值的角度出发，以能量密度为标准讨论了能量沿群落各层及各乔、灌木种群的积累、分配和组合特征，并讨论了能量流动和光能转化率与热值和能量密度的关系。 辽东栎群落能量生态学的研究不但为了解暖温带落叶阔叶林生态系统的结构和功能，为恢复和重建退化的森林生态系统提供了丰富详实的理论信息，而且，也为山区人工林优化模式的组建提供了理论依据和实践指南。