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Fullerene-based materials are widely used as acceptor and electron transport layer materials in organic and planar perovskite solar cells. Modeling of electronic properties such as band alignment and charge transport for these applications is typically done using optimized geometries. Here, we estimate the effects of nuclear motions on band structure, and electron and hole transport in two prototypical fullerenes, C60 and C70. We model the dynamics in solid fullerenes using Density Functional Tight Binding and we use the Density Functional Theory based Projection of Monomer Orbitals on Dimer Orbitals (DIPRO) approach to estimate the effects on the charge transfer integral in the Marcus approximation. We show that room-temperature molecular dynamics cause a shift and spread of frontier orbital energies on the order of 0.1 eV, which leads to an increase by more than a factor of two in the Marcus exponent, and can cause a decrease by up to orders of magnitude in the overlap integral, leading, in most cases, to an overall decrease in the charge transport rate.

In this paper, a hybrid modeling approach is proposed to model two-phase flow evaporators. The main procedures for hybrid modeling includes: (1) Based on the energy and material balance, and thermodynamic principles to formulate the process fundamental governing equations; (2) Select input/output (I/O) variables responsible to the system performance which can be measured and controlled; (3) Represent those variables existing in the original equations but are not measurable as simple functions of selected I/Os or constants; (4) Obtaining a single equation which can correlate system inputs and outputs; and (5) Identify unknown parameters by linear or nonlinear least-squares methods. The method takes advantages of both physical and empirical modeling approaches and can accurately predict performance in wide operating range and in real-time, which can significantly reduce the computational burden and increase the prediction accuracy. The model is verified with the experimental data taken from a testing system. The testing results show that the proposed model can predict accurately the performance of the real-time operating evaporator with the maximum error of ±8%. The developed models will have wide applications in operational optimization, performance assessment, fault detection and diagnosis.

It is conventionally believed that there are no self-sustained thermoacoustic oscillations in the absence of acoustic modes in combustors. However, such oscillations (also known as intrinsic thermoacoustic instability) are recently found to occur in a premixed combustor with a mean flow present but no acoustic eigenmodes involved. Practical combustors are associated with entropy waves, pressure jump and mean flow, which are ignored in previous studies without justification. In this work, an entropy-involved energy measure is defined and used to study the stability behaviors of intrinsic thermoacoustic modes. The concepts and methods are exemplified with the classical time-delay n–τ unsteady heat release model. The intrinsic thermoacoustic eigenmodes are found to be related to not only a flame transfer/describing function but also the acoustic impedance at the flame, which is boundary-dependent. It is shown that the predicted frequency ωfr of the intrinsic modes and the critical gain nc depend on the ratio T¯2/T¯1 between the after- and before-combustion temperatures and the inlet mean flow Mach number M¯1. Comparison is then made between the present results and those available in literature. Good agreement is obtained for ωfr. Furthermore, the predicted stability of intrinsic modes based on calculated nc is found to agree well with direct numerical simulations (DNS). It is also interesting to show that as T¯2/T¯1→1, the critical gain as predicted from the previous models is nc→+∞, which means that all intrinsic eigenmodes are stable. However, the present works shows that nc→1.0. Further illustration is then performed by conducting case studies of measured flame transfer and describing functions in premixed combustors. The present work opens up an alternative but more applicable way to study intrinsic thermoacoustic oscillations via the entropy-involved energy measure.

Based on an extensive literature review and research interviews of energy experts, this article asks: what are the remaining impediments to clean energy systems and how can a Post-Kyoto Protocol climate framework be designed to overcome them? The article begins by exploring commercially available 'clean' energy systems and practices relating to energy end-use and infrastructure, energy supply, carbon capture and storage, and non-CO2 related greenhouse gas emissions. The article then examines a selection of persistent financial, market, information and intellectual property barriers. Lastly, it articulates the implication of these barriers for the design of future national and international climate change policies.

Metal-based fuel-borne catalysts (FBCs) have been used with diesel fuels to effectively reduce soot and diesel particulate matter (DPM) emissions from both on-road and off-road applications. However, there is a lack of detailed investigations on the potential changes in the properties of particulates, when FBCs-doped fuels are combusted in diesel engines. This study fully evaluates the potential impacts of ferrocene-doped ultralow sulfur diesel (ULSD) fuels on physical, chemical and toxicological characteristics of the particulates emitted by a single cylinder, direct-injection diesel engine working at a constant speed and at three engine loads. The results indicated that ferrocene-doped fuels could effectively reduce the particulate mass and elemental carbon (EC) emissions, while increasing the proportion of both organic carbon (OC) and water-soluble organic carbon (WSOC) in particles. Particle-phase PAHs and n-alkanes emissions increased with an increase of Fe in the fuels. Ferrocene addition also led to lower soot ignition temperature and activation energy. However, the total number emissions of particles from ferrocene-doped fuels dramatically increased due to the formation of Fe-rich nuclei mode particles. Compared to pure ULSD, the particles emitted from ferrocene-doped fuels showed a slight decline in cell viability. The Fe in the particles and the changes in chemical composition of particulates are thought to be responsible for the variation of cell viability.

The research and development into imidazolium salts (IMSs) and their derivatives (N-heterocyclic carbene, NHCs) for sustainability research in biomass conversion and CO2 capture/utilization is reviewed. Research into using IMSs/NHCs in green synthesis, separation, and green materials has increased steadily over the past few years. Recent work utilizing imidazolium ionic liquids in dissolving and converting biomass are assessed. IMSs are particularly useful for directly processing raw biomass, such as cellulose, as feedstock to produce 5-hydroxymethylfurfural (HMF) under mild conditions. Catalytic activities of N-heterocyclic carbenes in sugar conversion are also studied, with a view towards practical industrialization. Imidazolium ionic liquids for CO2 capture and CO2 utilizations are also assessed. Imidazolium salts (IMSs) and their derivatives provide a promising way for carbon dioxide capture and utilization.

Ph.D ; DOCTOR OF PHILOSOPHY