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Catalytic Properties of Defect-Laden 2D Material from First-Principles
Title
Catalytic Properties of Defect-Laden 2D Material from First-Principles.
Creator
Jiang, Tao, Rahman, Talat, Stolbov, Sergey, Blair, Richard, Tetard, Laurene, University of Central Florida
Abstract / Description
Two dimensional (2D) materials offer excellent opportunities for application as catalysts for energy needs. Their catalytic activity depends on the nature of defects, their geometry and their electronic structure. It thus important that the characteristics of defect-laden 2D materials be understood at the microscopic level. My dissertation focuses on theoretical and computational studies of several novel nanoscale materials using state-of-the-art techniques based on density functional theory ...
Show moreTwo dimensional (2D) materials offer excellent opportunities for application as catalysts for energy needs. Their catalytic activity depends on the nature of defects, their geometry and their electronic structure. It thus important that the characteristics of defect-laden 2D materials be understood at the microscopic level. My dissertation focuses on theoretical and computational studies of several novel nanoscale materials using state-of-the-art techniques based on density functional theory (DFT) with the objective of understanding the microscopic factors that control material functionality.My work has helped establish defect-laden hexagonal boron nitride (dh-BN) as a promising metal-free catalyst for CO2 hydrogenation. Firstly, I showed how small molecules (H2, CO, CO2) interacting with several kinds of defects in dh-BN (with nitrogen or boron vacancy, boron substituted for nitrogen, Stone-Wales defect). I analyzed binding energies and electronic structures of adsorption of molecules on dh-BN to predict their catalytic activities. Then by computational efforts on reaction pathways and activation energy barriers, I found that vacancies induced in dh-BN can effectively activate the CO2 molecule for hydrogenation, where activation occurs through back-donation to the ?* orbitals of CO2 from frontier orbitals (defect state) of the h-BN sheet localized near a nitrogen vacancy (VN). Subsequent hydrogenation to formic acid (HCOOH) and methanol (CH3OH), indicating dh-BN (VN) an excellent metal-free catalyst for CO2 reduction, which may serve as a solution for global energy and sustainability.At the same time, I studied critical steps of the catalytic processes from carbon monoxide and methanol to higher alcohol on single-layer MoS2 functionalized with small Au nanoparticle, indicating C-C coupling feasible on MoS2-Au13, which led to production of acetaldehyde (CH3CHO). Whereas a bilayer 31-atom cluster of gold on MoS2 show excellent catalytic performance on CO hydrogenation to methanol through two effective pathways
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Date Issued
2019
Identifier
CFE0007823, ucf:52822
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007823
From Excited Charge Dynamics to Cluster Diffusion: Development and Application of Techniques Beyond DFT and KMC
Title
From Excited Charge Dynamics to Cluster Diffusion: Development and Application of Techniques Beyond DFT and KMC.
Creator
Acharya, Shree Ram, Rahman, Talat, Chow, Lee, Stolbov, Sergey, Wu, Annie, University of Central Florida
Abstract / Description
This dissertation focuses on developing reliable and accurate computational techniques which enable the examination of static and dynamic properties of various activated phenomena using deterministic and stochastic approaches. To explore ultrafast electron dynamics in materials with strong electron-electron correlation, under the influence of a laser pulse, an ab initio electronic structure method based on time-dependent density functional theory (TDDFT) in combination with dynamical mean...
Show moreThis dissertation focuses on developing reliable and accurate computational techniques which enable the examination of static and dynamic properties of various activated phenomena using deterministic and stochastic approaches. To explore ultrafast electron dynamics in materials with strong electron-electron correlation, under the influence of a laser pulse, an ab initio electronic structure method based on time-dependent density functional theory (TDDFT) in combination with dynamical mean field theory (DMFT) is developed and applied to: 1) single-band Hubbard model; 2) multi-band metal Ni; and 3) multi-band insulator MnO. The ultrafast demagnetization in Ni reveal the importance of memory and correlation effects, leading to much better agreement with experimental data than previously obtained, while for MnO the main channels of charge response are identified. Furthermore, an analytical form of the exchange-correlation kernel is obtained for future applications, saving tremendous computational cost. In another project, size-dependent temporal and spatial evolution of homo- and hetero-epitaxial adatom islands on fcc(111) transition metals surfaces are investigated using the self-learning kinetic Monte Carlo (SLKMC) method that explores long-time dynamics unbiased by apriori selected diffusion processes. Novel multi-atom diffusion processes are revealed. Trends in the diffusion coefficients point to the relative role of adatom lateral interaction and island-substrate binding energy in determining island diffusivity. Moreover, analysis of the large data-base of the activation energy barriers generated for multitude of diffusion processes for variety of systems allows extraction of a set of descriptors that in turn generate predictive models for energy barrier evaluation. Finally, the kinetics of the industrially important methanol partial oxidation reaction on a model nanocatalyst is explored using KMC supplemented by DFT energetics. Calculated thermodynamics explores the active surface sites for reaction components including different intermediates and energetics of competing probable reaction pathways, while kinetic study attends to the selectivity of products and its variation with external factors.
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Date Issued
2018
Identifier
CFE0006965, ucf:52910
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0006965
A Theoretical Investigation of Small Organic Molecules on Transition Metal Surfaces
Title
A Theoretical Investigation of Small Organic Molecules on Transition Metal Surfaces.
Creator
Malone, Walter, Kara, Abdelkader, Stolbov, Sergey, Kaden, William, Thomas, Jayan, University of Central Florida
Abstract / Description
With the ever growing number of proposed desnity functional theory (DFT) functionals it becomes necessary to thoroughly screen any new method to determine its merit. Especially relevant methods include a proper description of the van der Waals (vdW) interaction, which can prove vital to a correct description of a myriad of systems of technological importance. The first part of this dissertation explores the utility of several vdW-inclusive DFT functionals including optB86b-vdW, optB88-vdW,...
Show moreWith the ever growing number of proposed desnity functional theory (DFT) functionals it becomes necessary to thoroughly screen any new method to determine its merit. Especially relevant methods include a proper description of the van der Waals (vdW) interaction, which can prove vital to a correct description of a myriad of systems of technological importance. The first part of this dissertation explores the utility of several vdW-inclusive DFT functionals including optB86b-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, rPW86-vdW2, and SCAN+rVV10 by applying them to model systems of small organic molecules, pyridine and thiophene, on transition metal surfaces. Overall, we find the optB88-vdW functional gives the best, most balanced description of both thiophene and pyridine on transition metal surfaces while revPBE-vdW, rPW86-vdW2, and SCAN+rVV10 functionals perform especially poorly for these systems. In the second part of this dissertation we change our focus to potential applications of DFT. Specifically, we study the hydrodesulfurization (HDS) process and molecules that could be used in molecular electronics. The removal of sulfur containing molecules from petrochemicals through HDS is an exceptionally important process economically, and the field of molecular electronics is rapidly developing with hopes of competing with and replacing their silicon analogues. First we investigate the hydrodesulfurization of thiophene. In this dissertation we manage to map the HDS rate of thiophene in realistic reaction conditions to the charge transfer and adsorption energy of thiophene on bare transition metal surfaces in hopes of predicting ever more active HDS catalysis. Finally we look at the adsorption of polythiophenes and 5,14-dihydro-5,7,12,14-tetraazapentacene (DHTAP) on Au(111) and Cu(110). We find that polythiophenes may dissociate of Au(111), presenting an issue for their use in molecular electronics. DHTAP, in contrast, proves to a suitable candidate for use practical devices.
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Date Issued
2019
Identifier
CFE0007494, ucf:52653
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007494
Parallel fabrication and transport properties of carbon nanotube single electron transistors
Title
Parallel fabrication and transport properties of carbon nanotube single electron transistors.
Creator
Islam, Muhammad, Khondaker, Saiful, Chow, Lee, Stolbov, Sergey, Zhai, Lei, University of Central Florida
Abstract / Description
Single electron transistors (SET) have attracted significant attention as a potential building block for post CMOS nanoelectronic devices. However, lack of reproducible and parallel fabrication approach and room temperature operation are the two major bottlenecks for practical realization of SET based devices. In this thesis, I demonstrate large scale single electron transistors fabrication techniques using solution processed single wall carbon nanotubes (SWNTs) and studied their electron...
Show moreSingle electron transistors (SET) have attracted significant attention as a potential building block for post CMOS nanoelectronic devices. However, lack of reproducible and parallel fabrication approach and room temperature operation are the two major bottlenecks for practical realization of SET based devices. In this thesis, I demonstrate large scale single electron transistors fabrication techniques using solution processed single wall carbon nanotubes (SWNTs) and studied their electron transport properties. The approach is based on the assembly of individual SWNTs via dielectrophoresis (DEP) at the selected position of the circuit and formation of tunnel barriers on SWNT. Two different techniques: i) metal-SWNT Schottky contact, and ii) mechanical templating of SWNTs were used for tunnel barrier creation.Low temperature (4.2K) transport measurement of 100 nm long metal-SWNT Schottky contact devices show that 93% of the devices with contact resistance (RT) (>) 100 K? show SET behavior. Majority (90%) of the devices with 100 K? (<) RT (<) 1 M?, show periodic, well-de?ned Coulomb diamonds with a charging energy ~ 15 meV, represents single electron tunnelling through a single quantum dot (QD), defined by the top contact. For high RT ((>) 1M?), devices show multiple QDs behaviors, while QD was not formed for low RT ((<) 100 K?) devices. From the transport study of 50 SWNT devices, a total of 38 devices show SET behavior giving an yield of 76%. I also demonstrate room temperature operating SET by using mechanical template technique. In mechanical template method individual SWNT is placed on top of a Al/Al2O3 local gate which bends the SWNT at the edge and tunnel barriers are created. SET devices fabricated with a template width of ~20 nm shows room temperature operation with a charging energy of ~150 meV. I also discussed the detailed transport spectroscopy of the devices.
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Date Issued
2015
Identifier
CFE0006037, ucf:50987
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0006037
Prediction of Optical Properties of Pi-Conjugated Organic Materials for Technological Innovations
Title
Prediction of Optical Properties of Pi-Conjugated Organic Materials for Technological Innovations.
Creator
Nayyar, Iffat, Masunov, Artem, Saha, Haripada, Stolbov, Sergey, Gesquiere, Andre, University of Central Florida
Abstract / Description
Organic ?-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged ...
Show moreOrganic ?-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged (polaronic) excitations. In this work, we investigate the appropriate theoretical methods used for the (a) prediction of 2PA properties for rational design of organic materials with improved NLO properties, and (b) understanding of the essential electronic excitations controlling the energy-transfer and charge-transport properties in organic optoelectronics. Accurate prediction of these electro-optical properties is helpful for structure-activity relationships useful for technological innovations.In Chapter 1 we emphasize on the potential use of the organic materials for these two applications. The 2PA process is advantageous over one-photon absorption for deep-tissue fluorescence microscopy, photodynamic therapy, microfabrication and optical data storage owing to the three-dimensional spatial selectivity and improved penetration depth in the absorbing or scattering media. The design of the NLO materials with large 2PA cross-sections may reduce the optical damage due to the use of the high intensity laser beams for excitation. The organic molecules also possess self-localized excited states which can decay radiatively or nonradiatively to form excitonic states. This suggests the use of these materials in the electroluminescent devices such as light-emitting diodes and photovoltaic cells through the processes of exciton formation or dissociation, respectively. It is therefore necessary to understand ultrafast relaxation processes required in understanding the interplay between the efficient radiative transfer between the excited states and exciton dissociation into polarons for improving the efficiency of these devices. In Chapter 2, we provide the detailed description of the various theoretical methods applied for the prediction as well as the interpretation of the optical properties of a special class of substituted PPV [poly (p-phenylene vinylene)] oligomers. In Chapter 3, we report the accuracy of different second and third order time dependent density functional theory (TD-DFT) formalisms in prediction of the 2PA spectra compared to the experimental measurements for donor-acceptor PPV derivatives. We recommend a posteriori Tamm-Dancoff approximation method for both qualitative and quantitative analysis of 2PA properties. Whereas, Agren's quadratic response methods lack the double excitations and are not suitable for the qualitative analysis of the state-specific contributions distorting the overall quality of the 2PA predictions. We trace the reasons to the artifactual excited states above the ionization threshold. We also study the effect of the basis set, geometrical constraints and the orbital exchange fraction on the 2PA excitation energies and cross-sections. Higher exchange (BMK and M05-2X) and range-separated (CAM-B3LYP) hybrid functionals are found to yield inaccurate predictions both quantitatively and qualitatively. The failure of the exchange-correlation (XC) functionals with correct asymptotic is traced to the inaccurate transition dipoles between the valence states, where functionals with low HF exchange succeed. In Chapter 4, we test the performance of different semiempirical wavefunction theory methods for the prediction of 2PA properties compared to the DFT results for the same set of molecules. The spectroscopic parameterized (ZINDO/S) method is relatively better than the general purpose parameterized (PM6) method but the accuracy is trailing behind the DFT methods. The poor performances of PM6 and ZINDO/S methods are attributed to the incorrect description of excited-to-excited state transition and 2PA energies, respectively. The different semiempirical parameterizations can at best be used for quantitative analysis of the 2PA properties. The ZINDO/S method combined with different orders of multi-reference configuration interactions provide an improved description of 2PA properties. However, the results are observed to be highly dependent on the specific choice for the active space, order of excitation and reference configurations.In Chapter 5, we present a linear response TD-DFT study to benchmark the ability of existing functional models to describe the extent of self-trapped neutral and charged excitations in PPV and its derivative MEH-PPV considered in their trans-isomeric forms. The electronic excitations in question include the lowest singlet (S1) and triplet (T1†) excitons, positive (P+) and negative (P-) polarons and the lowest triplet (T1) states. Use of the long-range-corrected DFT functional, such as LC-wPBE, is found to be crucial in order to predict the physically correct spatial localization of all the electronic excitations in agreement with experiment. The inclusion of polarizable dielectric environment play an important role for the charged states. The particle-hole symmetry is preserved for both the polymers in trans geometries. These studies indicate two distinct origins leading to self-localization of electronic excitations. Firstly, distortion of molecular geometry may create a spatially localized potential energy well where the state wavefunction self-traps. Secondly, even in the absence of geometric and vibrational dynamics, the excitation may become spatially confined due to energy stabilization caused by polarization effects from surrounding dielectric medium.In Chapter 6, we aim to separate these two fundamental sources of spatial localization. We observe the electronic localization of P+ and P- is determined by the polarization effects of the surrounding media and the character of the DFT functional. In contrast, the self-trapping of the electronic wavefunctions of S1 and T1(T1†) mostly follows their lattice distortions. Geometry relaxation plays an important role in the localization of the S1 and T1† excitons owing to the non-variational construction of the excited state wavefunction. While, mean-field calculated P+, P- and T1 states are always spatially localized even in ground state S0 geometry. Polaron P+ and P- formation is signified by the presence of the localized states for the hole or the electron deep inside the HOMO-LUMO gap of the oligomer as a result of the orbital stabilization at the LC-wPBE level. The broadening of the HOMO-LUMO band gap for the T1 exciton compared to the charged states is associated with the inverted bond length alternation observed at this level. The molecular orbital energetics are investigated to identify the relationships between state localization and the corresponding orbital structure.In Chapter 7, we investigate the effect of various conformational defects of trans and cis nature on the energetics and localization of the charged P+ and P- excitations in PPV and MEH-PPV. We observe that the extent of self-trapping for P+ and P- polarons is highly sensitive on molecular and structural conformations, and distribution of atomic charges within the polymers. The particle-hole symmetry is broken with the introduction of trans defects and inclusion of the polarizable environment in consistent with experiment. The differences in the behavior of PPV and MEH-PPV is rationalized based on their orbital energetics and atomic charge distributions. We show these isomeric defects influence the behavior and drift mobilities of the charge carriers in substituted PPVs.
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Date Issued
2013
Identifier
CFE0005110, ucf:50722
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0005110
Theoretical and Computational Studies of the electronic, Structural, Vibrational, and Thermodynamic Properties of Transition Metal Nanoparticles
Title
Theoretical and Computational Studies of the electronic, Structural, Vibrational, and Thermodynamic Properties of Transition Metal Nanoparticles.
Creator
Sadatshafaie, Ghazal, Rahman, Talat, Stolbov, Sergey, Ishigami, Masa, Masunov, Artem, University of Central Florida
Abstract / Description
The main objective of this dissertation is to provide better understanding of the atomic configurations, electronic structure, vibrational properties, and thermodynamics of transition metal nanoparticles and evaluate the intrinsic (i.e. size and shape) and extrinsic (i.e. ligands, adsorbates, and support) effects on the aforementioned properties through a simulational approach. The presented research provides insight into better understanding of the morphological changes of the nanoparticles...
Show moreThe main objective of this dissertation is to provide better understanding of the atomic configurations, electronic structure, vibrational properties, and thermodynamics of transition metal nanoparticles and evaluate the intrinsic (i.e. size and shape) and extrinsic (i.e. ligands, adsorbates, and support) effects on the aforementioned properties through a simulational approach. The presented research provides insight into better understanding of the morphological changes of the nanoparticles that are brought about by the intrinsic factors as well as the extrinsic ones. The preference of certain ligands to stabilize specific sizes of nanoparticles is investigated. The intrinsic and extrinsic effects on the electronic structure of the nanoparticles are presented. The physical and chemical properties of the nanoparticles are evaluated through better understanding of the above effects on the experimentally observed properties as well as the applied techniques. The unexpected experimental results are tested and interpreted by deconvolution of the affecting factors. The application of Debye model to nanoparticles is tested and its shortcomings at nanoscale are discussed. Predictions which can provide insight into intelligent choice of candidates to cater to certain properties are provided. The results of this thesis can be used in the future in design and engineering of functionalized materials. We use ab initio calculations based on Density Functional Theory (DFT) to obtain information about the energetics, atomic configuration, and electronic structure of the nanoparticles. Ab initio Molecular Dynamics (MD) is used to study the evolution of the structures of the nanoparticles. To calculate vibrational frequencies, the finite displacement method is employed.
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Date Issued
2015
Identifier
CFE0006385, ucf:51536
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0006385
Growth and doping of MoS2 thin films for electronic and optoelectronic applications
Title
Growth and doping of MoS2 thin films for electronic and optoelectronic applications.
Creator
Abouelkhair, Hussain, Peale, Robert, Kaden, William, Stolbov, Sergey, Coffey, Kevin, University of Central Florida
Abstract / Description
MoS2 high absorption coefficient, high mobility, mechanical flexibility, and chemical inertness is very promising for many electronic and optoelectronic applications. The growth of high-quality MoS2 by a scalable and doping compatible method is still lacking. Therefore, the suitable dopants for MoS2 are not fully explored yet. This dissertation consists mainly of four main studies. The first study is on the growth of MoS2 thin films by atmospheric pressure chemical vapor deposition. Scanning...
Show moreMoS2 high absorption coefficient, high mobility, mechanical flexibility, and chemical inertness is very promising for many electronic and optoelectronic applications. The growth of high-quality MoS2 by a scalable and doping compatible method is still lacking. Therefore, the suitable dopants for MoS2 are not fully explored yet. This dissertation consists mainly of four main studies. The first study is on the growth of MoS2 thin films by atmospheric pressure chemical vapor deposition. Scanning electron microscope images revealed the growth of microdomes of MoS2 on top of a smooth MoS2 film. These microdomes are very promising as a broadband omnidirectional light trap for light harvesting applications. The second study is on the growth of MoS2 thin films by low pressure chemical vapor deposition (LPCVD). Control of sulfur vapor flow is essential for the growth of a pure phase of MoS2. Turning off sulfur vapor flow during the cooling cycle at 700 (&)#186;C leads to the growth of highly textured MoS2 with a Hall mobility of 20 cm2/Vs. The third study was on the growth of Ti-doped MoS2 thin films by LPCVD. The successful doping was confirmed by Hall effect measurement and secondary ion mass spectrometry (SIMS). Different growth temperatures from 1000 to 700 ? were studied. Ti act as a donor in MoS2. The fourth study is on fluorine-doped SnO2 (FTO) which has many technological applications including solar cells and transistors. FTO was grown by an aqueous-spray-based method. The main objective was to compare the actual against the nominal concentration of fluorine using SIMS. The concentration of fluorine in the grown films is lower than the concentration of fluorine in the aqueous solution.?
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Date Issued
2017
Identifier
CFE0006847, ucf:51767
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0006847
Computational Approach to Electrocatalysis
Title
Computational Approach to Electrocatalysis.
Creator
Dhakal, Nagendra, Stolbov, Sergey, Rahman, Talat, Ishigami, Masa, Masunov, Artem, University of Central Florida
Abstract / Description
The main objective of this work is to understand the theoretical basis of the working principle of the Hydrogen fuel cell. We seek the physical basis of the Rational Design Technique, the smart way of preselecting materials from the material-pool, implemented in our study anticipating highly promising electrocatalysts for promoting the conversion of chemical energy stored in hydrogen molecules into the electrical energy. It needs the understanding of the relationship among the compositions of...
Show moreThe main objective of this work is to understand the theoretical basis of the working principle of the Hydrogen fuel cell. We seek the physical basis of the Rational Design Technique, the smart way of preselecting materials from the material-pool, implemented in our study anticipating highly promising electrocatalysts for promoting the conversion of chemical energy stored in hydrogen molecules into the electrical energy. It needs the understanding of the relationship among the compositions of the materials under consideration, their electronic structure and catalytic activities. We performed the first principle DFT calculations to achieve the goal.Our work is focused first on the issues in hydrogen oxidation reaction taking place in anode compartment of the cell. Next comes up with the issues with Oxygen Reduction Reaction taking place in cathode compartment. Finally, we focus on mechanisms underlying binding of small molecules on substrates.Platinum perfectly catalyzes hydrogen oxidation reaction on the hydrogen fuel cell anodes. However, it has at least two drawbacks: a) it is too expensive; b) it has a low tolerance to CO poisoning. Pt-Ru bi-functional catalysts are more tolerant to CO, but they are still very expensive. In this work, we performed first-principle studies of stability and reactivity of M/W (110) structures, where M = Pd, Ru, Au monolayers. All three systems are found to be stable: formation energy of MLs is significantly higher than cohesive energy of the M-elements. The calculated binding energies of H, H2, OH, CO, and H2O were used to obtain the reaction free energies. Analysis of the free energies suggests that Au-W bonding does not activate sufficiently Au monolayer, whereas Ru/W (110) is still too reactive for the CO removal. Meanwhile, Pd/W (110) is found to catalyze hydrogen oxidation and at the same time to be highly tolerant to the CO poisoning. The latter finding is explained by the fact that CO binds much weaker to Pd on W (110) than to Pt, while the OH binding is strong enough to ensure CO oxidation. The obtained results are traced to the electronic structure of the systems.Oxygen Reduction Reaction (ORR) is the heart core reaction in fuel cells, Proton Exchange Membrane Fuel cell and DEMFC. However, the reaction is not so obvious and need suitable electrocatalyst. Pt or Pt-based catalysts are found to be the best catalyst so far. But, its cost and shortage make it not feasible economically. Moreover, lower onset potential (maximal electrode potential at which the reaction can proceed) of such catalysts is offering another limitation to fuel cell performance. Research has been conducted in many directions for lowering the cost by replacing the Pt with some other elements of lower cost or reducing the Pt-load in the material; and even more finding the material performing better than Pt. In this paper, we've tried to understand the ORR mechanism and look for the material that could be potential option to Pt. Our calculations suggest that for monolayer of Pt on 5 layered slab of Nb or Mo the onset potential is the same as for Pt, while cost of these systems are much lower than that of Pt. Presence of water changes the reaction rate very minimum. Rational design method facilitates the research of selecting the appropriate catalyst and saves time and effort significantly. The result shows that the d-band center model is not accurate to describe the reactivity of the catalyst.For decades, adsorbates' binding energy (????) has been used as an indicator of the adsorbate-substrate bond strength (??????). Thus, although one can compute accurately any ?? models to gauge bond-strength are developed and applied to rationalize and anticipate ????'s because that is a key aspect in the rational search for efficient catalysts. Yet bond-strength alone fails to predict ???? trends. Therefore, quantifying and understanding the difference between ???? and ?????? is essential to catalysts design. Indeed, the adsorbate-substrate bond formation perturbs the substrate's electronic charge density, which reduces ???? by the energy attached to such perturbation: ??????????. Here, with the example of carbon monoxide adsorption on metal-doped graphene, we show that ?????????? may exceed 1 eV and render an unusual situation: although the EB of CO to the Au-doped graphene indicates that binding does not happen, we find evidence of a strong bond between CO and the substrate. Thus, in this case, the large ?????????? totally disrupt the equivalency between ?????? and ???? we also propose a method to compute ?????????? that bypasses dealing with an excited electronic state of the system.
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Date Issued
2017
Identifier
CFE0006583, ucf:51336
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0006583
Optical and Magnetic properties of nanostructures
Title
Optical and Magnetic properties of nanostructures.
Creator
Nayyar, Neha, Rahman, Talat, Stolbov, Sergey, Ishigami, Marsahir, Hernandez, Florencio, University of Central Florida
Abstract / Description
In this thesis, Density Functional Theory and Time-Dependent Density-Functional Theory approaches are applied to study the optical and magnetic properties of several types of nanostructures. In studies of the optical properties we mainly focused on the plasmonic and excitonic effects in pure and transition metal-doped noble metal nanochains and their conglomerates. In the case of pure noble metal chains, it was found that the (collective) plasmon mode is pronounceable when the number of atoms...
Show moreIn this thesis, Density Functional Theory and Time-Dependent Density-Functional Theory approaches are applied to study the optical and magnetic properties of several types of nanostructures. In studies of the optical properties we mainly focused on the plasmonic and excitonic effects in pure and transition metal-doped noble metal nanochains and their conglomerates. In the case of pure noble metal chains, it was found that the (collective) plasmon mode is pronounceable when the number of atoms in the chain is larger than 5. The plasmon energy decreases with further with increasing number of atoms (N) and is almost N-independent when N is larger than 20. In the case of coupled pure chains it was found that the plasmon energy grows as square root of the number of chains, and reaches the visible light energy 1.8eV for the case of three parallel chains. Doping of pure Au chains with transition-metal atoms leads in many cases to formation of additional plasmon peaks close in energy to the undoped chain peak. This peak comes from the local charge oscillations around the potential minima created by the impurity atom. The effect is especially pronounced for Ni-doped chains. In the multiple-chain case, we find an unusual hybridization of the two different (local and collective) plasmon modes. Changing the chain size and chemical composition in the array can be used to tune the absorption properties of nanochains. The case of coupled finite (plasmonic) and infinite (semiconductor, excitonic) chains was also analyzed. We find that one can get significant exciton-plasmon coupling, including hybridized modes and energy transfer between these excitations, in the case of doped chains. The impurity atoms are found to work as attraction centers for excitons. This can be used to transform the exciton energy into local plasmon oscillations with consequent emission at desired point (at which the impurity is located). In a related study the optical properties of single layer MoS2 was analyzed with a focus on the possibility of ultrafast emission, In particular, it was found that the system can emit in femto-second regime under ultrafast laser pulse excitations. Finally, we have studied the magnetic properties of FeRh nanostructures to probe whether there is an antiferromagnetic to ferromagnetic transition as a function of the ratio of Fe and Rh atoms, as in the bulk alloy.. Surprisingly, the ferromagnetic phase is found to be much more stable for these nanostructures as compared to the bulk, which suggests that band-type effects may be responsible for this transition in the bulk, i.e. the transition cannot be described in terms of modification of the Heisenberg model parameters.
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Date Issued
2014
Identifier
CFE0005221, ucf:50650
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0005221
Fundamental core effects in Co-Cr-Fe-Ni based high entropy alloys
Title
Fundamental core effects in Co-Cr-Fe-Ni based high entropy alloys.
Creator
Mehta, Abhishek, Sohn, Yongho, Coffey, Kevin, Kushima, Akihiro, Jiang, Tengfei, Stolbov, Sergey, University of Central Florida
Abstract / Description
High entropy alloys (HEAs) are near equiatomic multi-principal-element-alloys (MPEAs) which are different from traditional solvent-based multicomponent alloys. Based on initial work by Yeh and Co-workers, they were proposed to exhibit four (")core(") effects: high entropy, sluggish diffusion, lattice distortion, and cocktail effect. Present work investigates two of the four (")core(") effects, i.e. high entropy and sluggish diffusion effects, in Co-Cr-Fe-Ni based transition metal high entropy...
Show moreHigh entropy alloys (HEAs) are near equiatomic multi-principal-element-alloys (MPEAs) which are different from traditional solvent-based multicomponent alloys. Based on initial work by Yeh and Co-workers, they were proposed to exhibit four (")core(") effects: high entropy, sluggish diffusion, lattice distortion, and cocktail effect. Present work investigates two of the four (")core(") effects, i.e. high entropy and sluggish diffusion effects, in Co-Cr-Fe-Ni based transition metal high entropy alloys. Solid-to-solid diffusion couple approach was adopted to investigate, these core effects. Experimental results contradicts the (")high entropy(") effect based on thermodynamics analysis: that the HEAs with low entropy of mixing may be thermodynamically more stable than the HEA of similar constituent elements with high entropy of mixing. In such cases, enthalpy of mixing can also play a vital role in stabilizing the HEA with lower entropy of mixing. Measurement of diffusion coefficients (i.e. both interdiffusion and tracer diffusion coefficients) in HEAs and its comparison with conventional solvent-based multicomponent alloys suggests that diffusion is not always sluggish in high entropy alloys. Contrary to previous findings, larger fluctuations in lattice potential energy (LPE) of an alloy may not always result in anomalously slow diffusion, in comparison to alloy systems which exhibits smaller fluctuation in LPE. Findings from his dissertation provide a (")controversial(") understanding of high entropy alloys, and alloy development strategies in the future for the most aggressive applications such as those found in gas turbines and nuclear reactors. As these applications will certainly require the knowledge of high temperature stability and nature of diffusion under extreme application environment.
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Date Issued
2019
Identifier
CFE0007501, ucf:52645
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007501
Electronic and Optoelectronic Transport Properties of Carbon Nanotube/Organic Semiconductor Devices
Title
Electronic and Optoelectronic Transport Properties of Carbon Nanotube/Organic Semiconductor Devices.
Creator
Sarker, Biddut, Khondaker, Saiful, Schulte, Alfons, Stolbov, Sergey, Gesquiere, Andre, University of Central Florida
Abstract / Description
Organic field effect transistors (OFETs) are of significant research interest due to their promising applications in large area, low-cost electronic devices such as flexible displays, sensor arrays, and radio-frequency identification tags. A major bottleneck in fabricating high-performance OFET is the large interfacial barrier between the metal electrodes and organic semiconductors (OSC) which results in an inefficient charge injection. Carbon nanotubes (CNTs) are considered to be a promising...
Show moreOrganic field effect transistors (OFETs) are of significant research interest due to their promising applications in large area, low-cost electronic devices such as flexible displays, sensor arrays, and radio-frequency identification tags. A major bottleneck in fabricating high-performance OFET is the large interfacial barrier between the metal electrodes and organic semiconductors (OSC) which results in an inefficient charge injection. Carbon nanotubes (CNTs) are considered to be a promising electrode material which can address this challenge.In this dissertation, we demonstrate fabrication of high-performance OFETs using aligned array CNT electrodes and investigate the detailed electronic transport properties of the fabricated devices. The OFETs with CNT electrodes show a remarkable enhancement in the device performance such as high mobility, high current on-off ratio, higher cutoff frequency, absence of short channel effect and better charge carrier injection than those OFETs with metal electrodes. From the low temperature transport measurements, we show that the charge injection barrier at CNT/OSC interface is smaller than that of the metal/OSC interface. A transition from direct tunneling to Fowler-Nordheim tunneling observed in CNT/OSC system shows further evidence of low injection barrier. A lower activation energy measured for the OFETs with CNT electrodes gives evidence of lower interfacial trap states. Finally, OFETs are demonstrated by directly growing crystalline organic nanowires on aligned array CNT electrodes.In addition to investigating the interfacial barrier at CNT/OSC interface, we also studied photoconduction mechanism of the CNT and CNT/OSC nanocomposite thin film devices. We found that the photoconduction is due to the exciton dissociations and charge carrier separation caused by a Schottky barrier at the metallic electrode/CNT interface and diffusion of the charge carrier through percolating CNT networks. In addition, it is found that photoresponse of the CNT/organic semiconductor can be tuned by changing the weight percentage of CNT into the organic semiconductors.
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Date Issued
2012
Identifier
CFE0004596, ucf:49217
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0004596
Electronic Structure of Metal (Al, Cu) Doped Carbon Nanotubes and the Resultant Conduction of the Hybrid Materials
Title
Electronic Structure of Metal (Al, Cu) Doped Carbon Nanotubes and the Resultant Conduction of the Hybrid Materials.
Creator
Jiang, Jingyin, Chen, Quanfang, Zhai, Lei, Fang, Jiyu, Bai, Yuanli, Stolbov, Sergey, University of Central Florida
Abstract / Description
Due to the exceptional strength, stiffness and excellent electrical and thermal properties, carbon nanotubes (CNTs) have been regarded as promising candidates for advanced nanoelectronics and multifunctional nanocomposites. In this dissertation, the interaction of CNTs with metals have been investigated and the resultant electrical conduction have been analyzed, aiming to develop innovative avenues to best utilize CNTs' potential. In order to do so, quantum mechanics calculations have been...
Show moreDue to the exceptional strength, stiffness and excellent electrical and thermal properties, carbon nanotubes (CNTs) have been regarded as promising candidates for advanced nanoelectronics and multifunctional nanocomposites. In this dissertation, the interaction of CNTs with metals have been investigated and the resultant electrical conduction have been analyzed, aiming to develop innovative avenues to best utilize CNTs' potential. In order to do so, quantum mechanics calculations have been carried out to study that how to obtain greater electrical conduction by doping metals (Cu, Al) which tailor the electronic structure of three different types of metal-CNT interactions, : 1) encapsulation of atoms inside the CNTs, 2) adsorption of atoms onto CNT surface, and 3) substitutional doping. Models of different doping methods were built and optimized with Density Functional Theory (DFT). And in conjunction with non-equilibrium Green's function, the electronic structure and the conducting properties were then calculated.Through this study, both metallic and semiconducting CNTs have been used. Metallic CNT (5, 5) encapsulated with copper chains have been first investigated with an emphasis on the electronic structure and the resultant conductance. The Density of States (DOS) have showed that the encapsulation of Cu effectively introduced more states around the fermi level. And due to the interaction between copper and CNTs, the conductance of the metallic CNTs-Cu system can be significantly increased.In addition to copper, aluminum has been also introduced for the study. The electronic structure and transport properties of hybrid nanowires consisting of aluminum chains adsorbed on a single-wall semiconducting CNT (10, 0) have been calculated. The band structure and DOS of the hybrid nanowires have showed that the adsorption of Al can effectively reduce the band gap. And with more than 4 Al chains adsorbed, the CNT has transformed from semiconducting to conducting. The transmission eigenstates further indicated that both Al chains and the modified nanotube were responsible for the increased conduction in the hybrid nanowires. The resultant conductance of CNT (10, 0)/Al hybrid nanowire is about 40% greater than that of pure Cu nanowire with the same diameter. In order to utilize the extraordinary conductance in CNT(10,0)/Al hybrid nanowire, it is also important to investigate the end-contact between the hybrid nanowire with Al electrodes. During this work the transmission spectrum at different bias voltage were calculated to study the I-V characteristics and the electrical contact resistances at the interfaces. The results have suggested that the electrical contact resistances between Al electrodes and the hybrid nanowire is significantly lower than that of Al-pure CNT contacts, although the actual contact resistance is directional dependent that the contact resistance is reduced to 20% of that Al-pure CNT along the longitudinal direction.The possibility of substitutional doping of Cu and Al in both metallic and semiconducting CNTs were also investigated. The formation energies have showed that Al doping was more energy favorable than Cu doping in both cases. And by doping of Al or Cu, a metallic tube experienced a higher conductance and a semiconducting tube has transited to conducting.In summary, different doping methods could modify the conducting property of nanotubes. Encapsulation of Cu in metallic CNT results in a significant conductance increment. Adsorption of Al transforms semiconducting CNT to conducting and reduces the contact resistance between the nanowire and Al electrode. Substitutional doping of Cu or Al transits semiconducting nanotube to conducting and enhance the conductance of metallic nanotube.
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Date Issued
2017
Identifier
CFE0006607, ucf:51274
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0006607
Model Nanocatalysts with Tunable Reactivity: Tailoring the Structure and Surface Chemistry of Nanomaterials for Energy and Alternative Fuels Catalysis
Title
Model Nanocatalysts with Tunable Reactivity: Tailoring the Structure and Surface Chemistry of Nanomaterials for Energy and Alternative Fuels Catalysis.
Creator
Mistry, Hemma, Roldan Cuenya, Beatriz, Chow, Lee, Stolbov, Sergey, Zhai, Lei, University of Central Florida
Abstract / Description
One of the most pressing challenges of our time is meeting growing global energy demands while limiting human impact on the environment. To meet this challenge, new catalysts are needed to enable carbon neutral energy production processes and low cost synthesis of alternative fuels. In order to design new catalysts for such processes, fundamental understanding is needed on how the structural and chemical properties of nanostructured materials influences their surface chemistry. In this...
Show moreOne of the most pressing challenges of our time is meeting growing global energy demands while limiting human impact on the environment. To meet this challenge, new catalysts are needed to enable carbon neutral energy production processes and low cost synthesis of alternative fuels. In order to design new catalysts for such processes, fundamental understanding is needed on how the structural and chemical properties of nanostructured materials influences their surface chemistry. In this dissertation, I explore how the properties of nanoparticles, such as particle size, shape, composition, and chemical state, can be used to tune their reactivity. For this work, model nanoparticles were synthesized with well-defined structural and chemical properties, and a variety of surface science approaches were used for catalyst characterization. In particular, emphasis was placed on understanding the changes which may occur in the catalyst structure and chemical state during a reaction using advanced in situ techniques and correlating these changes to reactivity. After exploring how nanostructuring the catalyst surface can be used to tune reactivity and how dynamic changes can occur to nanocatalysts in reactive environments, these general principles are applied to a model reaction, the electroreduction of carbon dioxide, which is a promising process for synthesizing valuable products using renewable energy while consuming waste carbon dioxide. I explore the mechanisms behind how catalyst particle size, composition, and oxidation state can be used to improve activity and tune selectivity towards different carbon dioxide reduction products. Such fundamental mechanistic insights are critically needed to design efficient catalysts for this reaction.
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Date Issued
2016
Identifier
CFE0006482, ucf:51440
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0006482
Theoretical Studies of Nanostructure Formation and Transport on Surfaces
Title
Theoretical Studies of Nanostructure Formation and Transport on Surfaces.
Creator
Aminpour, Maral, Rahman, Talat, Stolbov, Sergey, Roldan Cuenya, Beatriz, Blair, Richard, University of Central Florida
Abstract / Description
This dissertation undertakes theoretical and computational research to characterize and understand in detail atomic configurations and electronic structural properties of surfaces and interfaces at the nano-scale, with particular emphasis on identifying the factors that control atomic-scale diffusion and transport properties. The overarching goal is to outline, with examples, a predictive modeling procedure of stable structures of novel materials that, on the one hand, facilitates a better...
Show moreThis dissertation undertakes theoretical and computational research to characterize and understand in detail atomic configurations and electronic structural properties of surfaces and interfaces at the nano-scale, with particular emphasis on identifying the factors that control atomic-scale diffusion and transport properties. The overarching goal is to outline, with examples, a predictive modeling procedure of stable structures of novel materials that, on the one hand, facilitates a better understanding of experimental results, and on the other hand, provide guidelines for future experimental work. The results of this dissertation are useful in future miniaturization of electronic devices, predicting and engineering functional novel nanostructures. A variety of theoretical and computational tools with different degrees of accuracy is used to study problems in different time and length scales. Interactions between the atoms are derived using both ab-initio methods based on Density Functional Theory (DFT), as well as semi-empirical approaches such as those embodied in the Embedded Atom Method (EAM), depending on the scale of the problem at hand. The energetics for a variety of surface phenomena (adsorption, desorption, diffusion, and reactions) are calculated using either DFT or EAM, as feasible. For simulating dynamic processes such as diffusion of ad-atoms on surfaces with dislocations the Molecular Dynamics (MD) method is applied. To calculate vibrational mode frequencies, the infinitesimal displacement method is employed. The combination of non-equilibrium Green's function (NEGF) and DFT is used to calculate electronic transport properties of molecular devices as well as interfaces and junctions.
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Date Issued
2013
Identifier
CFE0005298, ucf:50504
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0005298
Electronic transport and correlations in single magnetic molecule devices
Title
Electronic transport and correlations in single magnetic molecule devices.
Creator
Romero, Javier, Mucciolo, Eduardo, Del Barco, Enrique, Stolbov, Sergey, Hernandez, Florencio, University of Central Florida
Abstract / Description
In this dissertation, we study the most important microscopic aspects that grant molecules such as Single Molecule Magnets (SMMs) their preferential spin direction. We do so by proposing and solving a model that includes correlations between electrons occupying atomic orbitals. In addition, we study the relation between the non-equilibrium electronic transport signatures in a SMM model weakly coupled to a three-terminal single electron transistor device, and the interference features of the...
Show moreIn this dissertation, we study the most important microscopic aspects that grant molecules such as Single Molecule Magnets (SMMs) their preferential spin direction. We do so by proposing and solving a model that includes correlations between electrons occupying atomic orbitals. In addition, we study the relation between the non-equilibrium electronic transport signatures in a SMM model weakly coupled to a three-terminal single electron transistor device, and the interference features of the SMM model in the presence of a magnetic field. Finally, we investigate the equilibrium transport features in a giant-spin model of a SMM in the Kondo regime. We study how the magnetic field modulation of the energy in a highly anisotropic molecule can affect the conductance of the molecule in the Kondo regime.
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Date Issued
2014
Identifier
CFE0005407, ucf:50420
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0005407
Computational Approach to the Problems of Electro- and Photo-Catalysis
Title
Computational Approach to the Problems of Electro- and Photo-Catalysis.
Creator
Zuluaga, Sebastian, Stolbov, Sergey, Schelling, Patrick, Roldan Cuenya, Beatriz, Masunov, Artem, University of Central Florida
Abstract / Description
The main objective of this work is to gain basis for rational design of catalysts used in fuel cells for conversion of chemical energy stored in hydrogen molecules into electric energy, as well as photo-catalysts used for hydrogen production from water under solar irradiation. This objective is achieved by applying the first principles computational approach to reveal relationship among compositions of materials under consideration, their electronic structure and catalytic activity. A major...
Show moreThe main objective of this work is to gain basis for rational design of catalysts used in fuel cells for conversion of chemical energy stored in hydrogen molecules into electric energy, as well as photo-catalysts used for hydrogen production from water under solar irradiation. This objective is achieved by applying the first principles computational approach to reveal relationship among compositions of materials under consideration, their electronic structure and catalytic activity. A major part of the work is focused on electro-catalysts for hydrogen fuel cells. Platinum (Pt) is widely used in the electrodes of fuel cells due to its good catalytic properties. However, Pt is an expensive and scarce element, its catalytic activity is not optimal and also it suffers from CO poisoning at anode. Therefore the search for new catalytic materials is needed for large scale implementation of fuel cells. The main direction of search of more efficient electro-catalysts is based in the design in which an active element monoatomic layer (AE) is deposited on a metal substrate (MS) made of a cost-effective material. Two goals are achieved by doing this: on the one hand, the cost of the catalytic system is reduced by reducing the amount of the AE in the system and on the other hand the catalytic properties of the AE can be tuned through its interactions with the MS. In the first part of this work the Pd-based alloys and layered structures have been studied as promising electro-catalysts for the ORR on the fuel cell cathodes, more precisely Pd-Co alloys and Pd/M/Pd (M=Co,Fe). There exists a robust model linking the activity of a surface toward ORR to computable thermodynamic properties of the system and further to the binding energies of the ORR intermediates on the catalyst surface. A more challenging task is to find how to tune these binding energies through modification of the surface electronic structure that can be achieved by varying the surface composition and/or morphology. To resolve this challenge, the electronic structure, binding energies of intermediates and the ORR free energies have been calculated within the density functional theory (DFT) approximation. The results presented in this work show that in contrast to the widely accepted notion, the strain exerted by a substrate on AE hardly affects the surface activity toward ORR, while the hybridization of the electronic states of the AE-and MS-electronic states is the key factor controlling the catalytic properties of these systems. Next it is shown that the catalytic activity of the promising anode electrocatalysts, such as Pt/M, M=Au, Ru and Pd, is also determined by the AE-MS hybridization with a minor effect of the strain. Furthermore, we have shown that, if AE is weakly bound to the substrate (as it is for Pt/Au), surface reconstruction occurs. This leads to the breaking of the relation between the electronic structure of the clean surface and the reactivity of the sytem. Other kind of promising ORR catalysts is designed in the form of Ru nanoparticles modified by chalcogens. In this work, I present the results obtained for small Ru clusters and flat Ru facets modified with chalcogens (S, Se and Te). The O and OH binding energies are chosen as descriptors of the ORR. The results on the two systems are compared, concluding that large clusters with relative large flat facets have higher catalytic activity due to the absence of low coordinated and thus high reactive Ru atoms. Regarding the problem of the hydrogen production via photo-catalytic splitting of water, one of the challenges is tuning the band gap of the photo-anodes to optimal levels. Graphitic carbon nitride (g-C3N4) is a promising material to be used as a photo-anode, however, a reduction of the band gap width by rational doping of the material would improve the efficiency significantly. This issue is addressed in the last chapter of this work. Two problems are considered: a) the stability of the doped system and b) the band gap width. To address the first problem the ab-initio thermodynamics approach has been used, finding that the substitution of C and N with the doping agent (B, C, N, O, Si and P) is thermodynamically preferred over the interstitial addition of dopant to the g-C3N4 structure. However, due to high kinetic energy barriers for the detachment of C and N atoms, involved in the substitution doping, the interstitial addition found to be kinetically more favorable. Since the density functional theory fails to reproduce the band gap of semiconductors correctly, the GW approximation was used to study the band gap of the system. The results indicate that the g-C3N4 system maintain its semiconductor character if doped with B, O and P under certain conditions, while reducing the band gap.
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Date Issued
2013
Identifier
CFE0005288, ucf:50546
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0005288