No description available.

No description available.

The need for green and renewable fuels has led to the investigation of ways to exploit renewable resources. Solar among all the renewables is the most powerful and its conversion into usable energy would help in solving the energy problem our society is facing. Photocatalytic water splitting for hydrogen production is an example of solar energy storage into chemical bonds. The hydrogen produced in this way can then be employed as carbon free fuel creating the “Hydrogen Cycle”. This work investigates the structure and the activity of graphitic carbon nitride (g-C₃N₄), an organic semiconductor that proved a suitable photocatalyst for hydrogen production from water. Synthesised by thermal polycondensation of melamine it is a graphitic like material with a band gap of 2.7 eV which makes it a visible light active catalyst. In a first instance the effect of the synthesis conditions on its structure and morphology are investigated to find the optimum parameters. The temperature of condensation is varied from 450°C up to 650°C and the length from 2.5 h to 15 h. The structural changes are monitored via X-ray diffraction (XRD) and elemental analysis while the effect on the morphology and the band gap of g-C₃N₄ are investigated by mean of scanning electron microscopy and UV-Vis absorption. Subsequently, a study of the crystal structure of the catalyst is carried out. Using structures proposed in the literature, X-ray diffraction and neutron scattering simulations are used to narrow down the number of possible 3D structures. After structural characterisation, the activity of g-C₃N₄ for photocatalytic hydrogen evolution is evaluated. It is confirmed that loading 1 wt.% Pt on its surface significantly increases the hydrogen evolution rate. The attention then focuses on the loading procedures, the reduction pre treatments of the co-catalyst and the reasons of the different performances when different procedures are employed. The catalytic system is characterised by mean of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and XRD. By investigating the composition and the morphology of the platinum nanoparticles under different conditions, the main factors responsible for the changes in activity of g-C₃N₄ for hydrogen evolution are identified. Additionally, the role of the co catalyst and its interaction with g-C₃N₄ is also elucidated. Finally, taking forward the knowledge acquired on the Pt-g-C₃N₄ system, the effect on the hydrogen evolution rate of alloying platinum with a second metal (Cu, Ag, Ni and Co) is studied. The nanoparticles are characterised by XRD and TEM. A screening of the loading procedures and bimetallic systems is performed to identify the most promising for photocatalytic hydrogen evolution with the aim of bringing them towards further investigation.

Thesis advisor: Dunwei Wang / Water splitting has been recognized as a promising solution to challenges associated with the intermittent nature of solar energy for over four decades. A great deal of research has been done to develop high efficient and cost-effective catalysts for this process. Among which tantalum nitride (Ta₃N₅) has been considered as a promising candidate to serve as a good catalyst for solar water splitting based on its suitable band structure, chemical stability and high theoretical efficiency. However, this semiconductor is suffered from its special self-oxidation problem under photoelectrochemical water splitting conditions. Several key unique properties of graphitic carbon nitride (g-C₃N₄) render it an ideal choice for the protection of Ta₃N₅. In this work, Ta₃N₅/g-C₃N₄ hybrid photoanode was successfully synthesized. After addition of co-catalyst, the solar water splitting performance of this hybrid photoanode was enhanced. And this protection method could also act as a potential general protection strategy for other unstable semiconductors. / Thesis (MS) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

The question of whether the small bandgaps of semiconductors play a significant role in their secondary electron emission properties is investigated by studying evaporated graphitic amorphous carbon, which has a roughly 0.5 eV bandgap, in comparison with microcrystalline graphite, which has zero bandgap. The graphitic amorphous carbon is found to have a 30% increase in its maximum secondary electron yield over that of two microcrystalline graphite samples with comparable secondary electron yields: highly oriented pyrolytic graphite and colloidal graphite. The potentially confounding influence of the vacuum level has been isolated through the measurement of the photoelectron onset energy of the materials. Other less significant materials parameters are also isolated and discussed. Based on these measurements, it is concluded the magnitude of bandgap may have an appreciable effect on the magnitude of the secondary electron yield and further studies of this effect with annealed graphitic amorphous carbon are warranted. In support of this work, a hemispherical two-grid, retarding field electron energy analyzer has been designed, constructed, and characterized for the present work. The advantages and disadvantages of the analyzer are discussed in comparison to other methods of measuring secondary electron emission. The analyzer has a resolution of ±(1.5 eV + 4% of the incident electron energy). A novel effort to derive theoretical, absolute correction factors that compensate for electron losses within the analyzer, mainly due to the grid transmission, is presented. The corrected secondary electron yield of polycrystalline gold is found to be 30% above comparable experimental studies. The corrected backscattered electron yield of polycrystalline gold is found to be 14% above comparable experimental studies. Corrected secondary yields for the microcrystalline graphite samples are found to range from 35-70% above those found in five experimental studies in the literature. The theoretical correction factors are estimated to have a 4-6% uncertainty. Reasons for the large discrepancy in yield measurements with the analyzer are discussed and thought to be due mainly to the lack of similar corrective factors in the previous studies. The supporting instrumentation is fully characterized, including a detailed error analysis.

Photocatalytic solar fuel generation is the most green, sustainable and viable approach to deal with both the ever-growing energy crisis and environmental issues, simultaneously. The work presented in this thesis is focused on the development of new organic carbonaceous semiconductors, typically, carbon quantum dots (CQDs) and graphitic carbon nitride (g-C3N4), and porphyrin small molecules and their hybrids with graphitic carbon nitride, meanwhile, their application in the field of photocatalytic solar fuel generation. In the chapter 1, a general review about background and mechanism of photocatalytic solar fuel generation are introduced first. Next, the features and developments of porphyrin and graphitic carbon nitride for the photocatalytic redox reaction are discussed. In chapter 2, the synthesis, characterization methods and photocatalytic experiment in details are described. In chapter 3, gram-scale CQDs are facilely synthesized by simple thermal treatment of citric acid monohydrate, and microporous 1D nanorods of g-C3N4 are prepared through template-free chemical approach. The photocatalytic properties of 1D protonated g-C3N4 (HCN) modified with different amount of CQDs were evaluated by the rate of H2- evolution under visible light irritation. The results demonstrate that g-C3N4/CQDs with the optimal CQDs amount of 0.25 wt.% afford the highest H2-production rate of 382 μmol h-1 g-1 with apparent quantum yield (AQY) of 1.9% which was about 3-fold of pure g- C3N4. The composite g-C3N4/CQDs show a remarkable stability against the photocorrosion within a continuous experiment period over 12h. The enhanced photocatalytic H2-production activity could be attribute to the intimate interface between CQDs and g-C3N4, which not only significantly improves the visible-light absorption, but also prolongs the lifetime of charge carriers and suppresses the recombination of photogenerated electron-hole pairs. This work showed that low-cost and metal-free CQDs could be an efficient photosensitizer to promote photocatalytic hydrogen generation. In chapter 4, we reported a new array of push-pull isomeric naphthalimide- porphyrins (ZnT(p-NI)PP) to investigate the effect of naphthalimide and molecular constitution on light driven hydrogen evolution from water splitting. These compounds were synthesized by integration of four naphthalimide moieties on meso-substituion of porphyrin macrocycle through para phenyl linker. Porphyrins were characterized by UV- Vis, Fluorescence and DFT calculations and compared with those of zinc tertapheylporphyrin (ZnTPP). When these porphyrins were employed as photocatalyst for the photocatalytic hydrogen production (PHP) with platinum co-catalyst, they delivered high hydrogen efficiency compared to that of ZnTPP. Particularly, ZnT(p-NI)PP exhibited 203 times higher hydrogen efficiency than the ZnTPP. This could be ascribed to the efficient exciton dissociation into holes and electrons at the photoexcited state of ZnT(p-NI)PP and then electrons were transferred to the proton through platinum. These results indicate that introduction of naphthalimide at meso-position of porphyrin through para phenyl linker is a versatile strategy to improve the photocatalytic hydrogen evolution of porphyrin based materials. In addition, the other two isomeric naphthalimide conjugated porphyrins through meta-and ortho-phenyl linker, ZnT(m-NI)PP and ZnT(o-NI)PP are also developed for photocatalytic H2 production. The para-linked isomer, ZnT(p-NI)PP delivered a much higher H2 production rate of 973 μmol h−1g -1 compared to that of ZnT(m-NI)PP (597 μmol h−1g −1) and ZnT(o-NI)PP (54 μmol h−1g −1), respectively. This could be attributed to the efficient intramolecular energy transfer from the naphthalimide to the porphyrin ring. In chapter 5, a series of NP/g-C3N4 hybrids of graphitic carbon nitride (g-C3N4) with naphthalimide-porphyrin (ZnT(p-NI)PP, labelled as NP) have been developed for photocatalytic hydrogen production. Planar naphthalimide-porphyrins are adsorbed onto flexible two-dimensional g-C3N4 through π-π stacking, which are characterized by scanning electronic microscopy and X-ray photoelectron spectroscopy. Except for its function as photosensitizer, NP in the hybrids could efficient inhibit the charge recombination by electron transfer for the lower lowest unoccupied molecular orbital of NP than g-C3N4, whereas facilitate energy transfer from g-C3N4 donor to NP acceptor for efficient overlap of emission spectrum of NP and absorption of g-C3N4. As a result, the hybrid containing weigh ratio of 2% NP (2%NP/g-C3N4) exhibits an enhanced photocatalytic hydrogen production rate (HPR) of 2297 μmol g−1 h −1, while pristine g- C3N4 shows a HPR of 698 μmol g−1 h −1. The 2%NP/g-C3N4 shows the best performance when compared with the reported hybrids of g-C3N4 with Zn(II) -tetrakis(4- carboxylphenyl) porphyrin (ZnTCPP/g-C3N4) and Zn(II)-tetrakis(4- hydroxyphenyl)porphyrin (ZnTHPP/g-C3N4) in photocatalytic hydrogen production under the same conditions. In the chapter 6, the future work on photocatalytic CO2 reduction, perspectives and conclusions are included

abstract: Photocatalytic water splitting over suspended nanoparticles represents a potential solution for achieving CO2-neutral energy generation and storage. To design efficient photocatalysts, a fundamental understanding of the material’s structure, electronic properties, defects, and how these are controlled via synthesis is essential. Both bulk and nanoscale materials characterization, in addition to various performance metrics, can be combined to elucidate functionality at multiple length scales. In this work, two promising visible light harvesting systems are studied in detail: Pt-functionalized graphitic carbon nitrides (g-CNxHys) and TiO2-supported CeO2-x composites. Electron energy-loss spectroscopy (EELS) is used to sense variations in the local concentration of amine moieties (defects believed to facilitate interfacial charge transfer) at the surface of a g-CNxHy flake. Using an aloof-beam configuration, spatial resolution is maximized while minimizing damage thus providing nanoscale vibrational fingerprints similar to infrared absorption spectra. Structural disorder in g-CNxHys is further studied using transmission electron microscopy at low electron fluence rates. In-plane structural fluctuations revealed variations in the local azimuthal orientation of the heptazine building blocks, allowing planar domain sizes to be related to the average polymer chain length. Furthermore, competing factors regulating photocatalytic performance in a series of Pt/g-CNxHys is elucidated. Increased polymer condensation in the g-CNxHy support enhances the rate of charge transfer to reactants owing to higher electronic mobility. However, active site densities are over 3x lower on the most condensed g-CNxHy which ultimately limits its H2 evolution rate (HER). Based on these findings, strategies to improve the cocatalyst configuration on intrinsically active supports are given. In TiO2/CeO2-x photocatalysts, the effect of the support particle size on the bulk/nanoscale properties and photocatalytic performance is investigated. Small anatase supports facilitate highly dispersed CeO2-x species, leading to increased visible light absorption and HERs resulting from a higher density of mixed metal oxide (MMO) interfaces with Ce3+ species. Using monochromated EELS, bandgap states associated with MMO interfaces are detected, revealing electronic transitions from 0.5 eV up to the bulk bandgap onset of anatase. Overall, the electron microscopy/spectroscopy techniques developed and applied herein sheds light onto the relevant defects and limiting processes operating within these photocatalyst systems thus suggesting rational design strategies. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2019

Yes / A highly porous carbon was synthesized using a coordination complex as an unusual precursor. During controlled pyrolysis, a trinuclear copper complex, [CuII3Cl4(H2L)2]·CH3OH, undergoes phase changes with melt and expulsion of different gases to produce a unique morphology of copper-doped carbon which, upon acid treatment, produces highly porous graphitic carbon with a surface area of 857 m2 g–1 and a gravimetric hydrogen uptake of 1.1 wt % at 0.5 bar pressure at 77 K. / EPSRC (EP/R01650X/1 for VPT, and EP/E040071/1 for MT) and the University of Bristol

Student Number : 0303610W - PhD thesis - School of Chemistry - Faculty of Science / Mesoporous MCM-48 was synthesized and used as a template to synthesize mesoporous carbon (MC) materials. Polystyrene, the carbon source, together with sulfuric acid and toluene were added to the template (160 oC for 6 h) and this procedure generated a low surface area carbon supported/MCM-48 material. A repeat addition and carbonization step was needed to form the precursor carbon/MCM-48 material that was pyrolysed at 900 oC to generate graphitic mesoporous carbon materials. After removal of the silica template, mesoporous carbons were characterized by XRD, HR-TEM, Raman spectroscopy and surface area analysis. The effect of the amount of polystyrene as well as the role of the pyrolysis temperature on the final product was investigated. This synthesis methodology can readily be controlled to produce partially ordered graphitic mesoporous carbon supports with predictable pore width and surface area. The methane selectivity was low (below 6%) and stable, and the overall olefin fraction was found to be good for all the supported catalysts studied. The potassium promoter increased the hydrocarbon chain growth to C68 giving α-1 and α-2 both between 0.79 and 0.90 for all supported catalysts with an exception of MCM-48 supported Fe catalyst that selectively produced hydrocarbons up to C28.

<p>Oxidative stress can be defined as a state of disturbance in the pro-oxidant/antioxidant balance in favour of the former, leading to potential damage. Processes associated with oxidative stress involve reactive oxygen species and radicals and can result in elevated levels of oxidatively modified or toxic molecules that can cause cellular malfunction, and even cell death. Destruction of membrane lipids, lipid peroxidation, caused by reactive oxygen species and radicals has been coupled to many diseases and also normal ageing. </p><p>The measurement of low molecular weight biomarkers of oxidative stress present in complex matrices such as brain tissue, plasma, urine or cerebrospinal fluid is a delicate and difficult task and there is a need for improved analytical tools in this field of research. </p><p>The major foci of this thesis and the work underlying it are the development of analytical techniques and methods for determining biomarkers for oxidative stress and lipid peroxidation. Aspects of particular concern include the effects of sample treatments prior to analysis, evaluation of the developed methods with respect to possible artefacts, and the scope for results to be misinterpreted. The specific research goals and issues addressed are detailed in five papers, which this thesis is based upon.</p><p><b>Paper I</b> focuses on malondialdehyde, describing and evaluating two new simplified sample pre-treatment regimes for the determination of malondialdehyde in rat brain tissue by capillary electrophoresis with UV detection. The effects of sample storing and handling are also considered.</p><p><b>Paper II</b> describes the synthesis, characterization and implementation of a new internal standard for the determination of malondialdehyde in biological samples using electrophoretic or chromatographic separation techniques. The usefulness of the internal standard is demonstrated in analyses of rat brain tissue samples.</p><p><b>Paper III</b> presents a method for the determination of 4-hydroxynon-2-enal in brain tissue from rats employing micellar electrokinetic chromatography separation and laser-induced fluorescence detection. </p><p><b>Paper IV</b> is focused on the development of a new methodology for determining the stereoisomeric F2-isoprostanes in human urine samples employing chromatographic separation on porous graphitic carbon and detection by electrospray ionization-tandem mass spectrometry. The results from this study conflict with the hypothesis that peripheral isoprostanes are elevated in patients with Alzheimer’s disease.</p><p><b>Paper V</b> describes porous graphitic carbon chromatography-tandem mass spectrometry for the determination of isoprostanes in human cerebrospinal fluid. A new simplified sample pre-treatment regime, involving a column switching technique, is presented that allows direct injection of a relatively large volume of CSF into the chromatographic system.</p>