>Magister Scientiae - MSc / Anode catalysts are one of the key components of direct alcohol fuel cells (DAFCs). They play a huge role in the alcohol oxidation reaction (AOR) that occurs on the anode side. Palladium (Pd) supported on carbon material has been reported to have good catalytic activity towards alcohol oxidation reactions. Better stability and activity has been reported for catalysts supported on conductive polymers like polypyrrole (PPy) when compared to traditional carbon support material. This study investigated the effect of support materials on Pd and PdCo electro-catalysts while concurrently determining the support material that can improve the activity and stability of Pd and PdCo electro-catalysts used as direct alcohol fuel cells catalysts. All Pd and PdCo catalysts supported onPPy (prepared using oxidative polymerization method), reduced graphene oxide (rGO) and prepared using modified Hammers method and multi-walled carbon nanotubes and pre-treated by acid. All the catalysts were synthesized using the modified polyol method.

>Magister Scientiae - MSc / This project focuses on the development of simple, highly sensitive, accurate, and low cost electrochemical sensors based on the modification of pencil graphite electrodes by the electrochemical reduction of graphene oxide-metal salts as nanocomposites (ERGO-MC-PGE; MC = Sb or Au nanocomposite). The electrochemical sensors ERGO-Sb-PGE and ERGO-Au-PGE were used in the determination of paracetamol (PC) in pharmaceutical formulations using adsorptive stripping differential pulse voltammetry. The GO was prepared from graphite via a modified Hummers’ method and characterized by FTIR and Raman spectroscopy to confirm the presence of oxygen functional groups in the conjugated carbon-based structure whilst, changes in crystalline structure was observed after XRD analysis of graphite and GO. / 2023-10-07

Several attempts have been made to combine the unique characteristics of graphene oxide (GO) and commercial polymers for successfully designing and fabricating next-generation membranes in filtration and separation technologies. The first part of the work develops a high flux polyethersulfone ultrafiltration membranes, by embedding GO sheets, starting from the polymer/GO solutions in ionic liquid and N, N dimethylformamide as co-solvents and promoting the pore formation via non-solvent induced phase separation. In the second part of the work, a protic ionic liquid was introduced as a solvent to disperse GO sheets and fabricate GO liquid crystal membranes for nanofiltration. The third part addresses the stability enhancement. GO membranes frequently disintegrate in aqueous environments due to swelling. Ethylenediamine was then used as a crosslinker, and the membranes were tested for organic solvent nanofiltration. Additionally, overcoming the permeation-rejection trade-off is challenging. Hence, the fourth work involved the intercalation of silica nanoparticles to form dual-sized nanochannels. In the final work, GO membranes were fabricated on the surface of hollow fibers to overcome scalability issues, by using a feasible spray coating method for efficient nanofiltration. Hollow fibers were crosslinked with hexamethylene diamine and GO was spray-coated on the crosslinked polymeric fibers for organic solvent nanofiltration. Overall, this study demonstrates the potential of GO in developing high-performance membranes for liquid separations relevant for industrial applications, such as wastewater treatment, food, chemical, petrochemical, and pharmaceutical processing.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21106号 / 工博第4470号 / 新制||工||1695(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 邑瀬 邦明, 教授 山田 啓文 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Reduced graphene oxide (RGO) sheet, a chemically functionalized atomically thin carbon sheet, provides a convenient pathway for producing large quantities of graphene via solution processing. The easy processibility of RGO sheet and its composites offer interesting electronic, chemical and mechanical properties that are currently being explored for advanced electronics and energy based materials. However, a clear understanding of electron transport properties of RGO sheet is lacking which is of great significance for determining its potential application. In this dissertation, I demonstrate fabrication of high-yield solution based graphene field effects transistor (FET) using AC dielectrophoresis (DEP) and investigate the detailed electronic transport properties of the fabricated devices. The majority of the devices show ambipolar FET properties at room temperature. However, the mobility values are found to be lower than pristine graphene due to a large amount of residual defects in RGO sheets. I calculate the density of these defects by analyzing the low temperature (295 to 77K) charge transport data using space charge limited conduction (SCLC) with exponential trap distribution. At very low temperature (down to 4.2 K), I observe Coulomb blockade (CB) and Efros-Shklovskii variable range hopping (ES VRH) conduction in RGO implying that RGO can be considered as a graphene quantum dots (GQD) array, where graphene domains act like QDs while oxidized domains behave like tunnel barriers between QDs. This was further confirmed by studying RGO sheets of varying carbon sp 2 fraction from 55 – 80 % and found that both the localization length and CB can be tuned. From the localization length and using confinement effect, we estimate tunable band gap of RGO sheets with varying carbon sp 2 fraction. I then studied one dimensional RGO nanoribbon iv (RGONR) and found ES VRH and CB models are also applicable to the RGONR. However, in contrast to linear behavior of decrease in threshold voltage (Vt) with increasing temperature (T) in the RGO, sub linear dependence of Vt on T was observed in RGONR due to reduced transport pathways. Finally, I demonstrate synthesis and transport studies of RGO/nanoparticles (CdS and CeO2) composite and show that the properties of RGO can be further tuned by attaching the nanoparticles.

The application of membranes in liquid and gas separation is attractive because of their energy efficiency. Synthesis of membranes with well-defined nanostructure is necessary to achieve highly permeability and selectivity for separation processes. Recently, carbon nanomaterials such as graphene oxide nanoplatelets (GONPs) and carbon nanodots (CNDs) have emerged as an interesting class of nanomaterials due to their unique properties and tailorable functionalities. Incorporation of these nanomaterials in the membranes has been shown to improve membrane selectivity, mechanical robustness, and chemical stability. This dissertation elaborates on developing CNDs or GONPs embedded thin film composite (TFC) membranes using layer-by-layer (LbL) synthesis technique. Regarding the water desalination applications, GONPs were used to enhance the TFC membranes’ selectivity, chlorine resistant properties, and surface hydrophilicity. Incorporation of GONPs in the polyamide layer via LbL method resulted in an increase of surface hydrophilicity and salt rejection properties. Upon exposure to chlorine, GONPs embedded membranes retained salt rejection performance better than the pristine membranes (without GONPs). The LbL assembly was used to synthesize CNDs based TFC membranes for organic solvent nanofiltration (OSN) applications. Using the LbL framework, amineunctionalized CNDs were covalently crosslinked with trimesoyl chloride monomer to obtain nanoscale membranes. The synthesized membranes manifested high selectivity (up to 90%) when tested for dye molecules such as brilliant blue and disperse red in methanol. As the CNDs synthesized here are fluorescent under UV light, the resultant film is also fluorescent. This property can be harnessed for diagnostic purposes, such as tracking mechanical failure and fouling of the membranes. Based on the results, it can be concluded that the incorporation of carbon nanomaterials in the polymeric membranes has enhanced the hydrophilicity, mechanical stability, and chlorine resistant properties of the membranes. Overall, the LbL platform can be considered as a modular method in embedding nanoparticles in TFC membranes.

Accumulation of heavy metals in different environmental compartments and their toxicity even at trace level concentration necessitates the study of their efficient removal. Furthermore, metals could co-exist in the environment which is a complex scenario as there would be competition among the metals in terms of removal efficiency. This study presents the effective removal of trace level toxic metals (Hg2+, Cd2+, Pb2+) in both single and ternary metal solutions through adsorption on the successfully synthesized composite (SC) of pinewood-derived biochar (BC) and graphene oxide (GO) nanomaterials. Moreover, different linear regression tools (Gaussian Process (GP), Random Forest (RF), and Feed Forward Back Propagation (FFBP)) from the machine learning (ML) toolbox were used to make the comparison between actual and their predicted adsorption. The structural and morphological analysis of the SC showed that GO was successfully coated on the surface of the BC. GO coating increased the surface area, porosity, functional groups, and adsorption efficiency of these toxic metals on the SC as compared to the unmodified BC. The factors affecting adsorption efficiency were metal concentration, pH, and the ratio of BC and GO in the SC. The adsorption efficiency in single metal solution was found 94-98% for Hg2+, 92-94% for Cd2+, and 96-99% for Pb2+ and for ternary metal solutions 94-96% for Hg2+, 95-97% for Cd2+, and 97-99% for Pb2+ at pH 6 and SC with BC/GO (w/w) ratio as 1:10. However, for unmodified BC, the adsorption efficiency was less in both single and ternary solutions. Thus, results indicate that modification of BC with GO increases adsorption efficiency as compared to unmodified BC. Furthermore, for all three metals, Freundlich's adsorption isotherm was followed in both single and ternary solutions. Regeneration of the SC was also attained by adsorbate desorption, producing a competent and cost-effective adsorbent for the removal of toxic metals from our environment. Furthermore, from the ML toolbox mean squared error (MSE) values between the actual efficiency and predicted efficiency were calculated which was negligible in the case of GP, with regression coefficient (R2) equal to 1. This implied that GP was the most suitable linear regression model among other models (RF, FFBP) for the available data sets. These predicted values through different ML models could significantly reduce the experimental workload for various parameters in predicting the removal efficiency of the synthesized composite for the target toxic metals. Thus, these models help in reducing experimental time and predicting the most appropriate combination for the best result in the future.

PLA nanofibers were successively produced by thermo-responsive transformation of PLA particles in water. The morphological structure of the nanofibers could be optimized by the heat treatment as well as the incorporation of GO to the fiber surface. PLA/GO fiber demonstrated a more stable morphology and GO provided good compatibility between PLA and starch. Both PLA and PLA/GO fibers incorporated in starch films resulted in increased thermal stability and mechanical properties. However, the most favorable properties were assigned starch films containing high concentration of PLA/GO fibers. These films with completely green components could possibly be utilized in biodegradable packaging applications.

Functional nucleic acids (FNAs), which include both DNA/RNA aptamers and DNA enzymes, have emerged as promising biological recognition elements for biosensors. These species typically require immobilization on or within a solid support, which is usually interfaced to some kind of signal transducer and readout system when use in biosensor. Our group has successfully immobilized several functional nucleic acids in the past, including fluorescence-signalling DNA enzymes, DNA aptamers and RNA aptamers by entrapping them into porous silica or organosilica materials prepared by the sol-gel method using percursors such as sodium silicate (SS), diglyceryl silane (DGS), tetrametylorthosilicate (TMOS) and trimethoxymethysilane (MTMS). While the earlier work established the ability of entrapped FNAs to retain binding and catalytic activity, only limited information was obtained on how different factors affect the performance of immobilized FNAs, and no information was obtained on the effects of aging and storage conditions on FNA performance. The initial objective of this thesis was to employ advanced fluorescence methods to better understand the nature of immobilized DNA and RNA aptamers, and in particular how entrapment in different sol-gel based materials affected FNA performance for detection of small molecule analytes. It was found that the ability of the entrapped aptamer reporters to remain fully hybridized was the most important factor in terms of signalling capability for both DNA and RNA aptamer reporters. It was also observed that more polar materials derived from SS were optimal for both types of aptamer reporters, since these allowed the entrapped aptamers to remain hydridized to their complementary strands and still retain the dynamic motion needed to undergo structure switching, while providing a minimum degree of leaching. The second objective of my research was to develop a paper-based biosensing device incorporating immobilized DNA and RNA aptamers that could be used in the fields of point-of-care diagnostics to further expand the utility of structure-switching aptamer reporters to real world application. A dual response (fluorescence / colorimetric) paper-based sensor utilized printed graphene oxide to immobilize both a RNA and a DNA aptamer in a recognition zone. Upon target addition, the aptamer desorbed and eluted to an amplification zone where rolling circle amplification was used to generate a colorimetric output. This sensor could function with clinical samples such as serum and stool, and allowed detection of key bacterial markers (ATP and glutamate dehydrogenase) at clinically relevant levels. / Thesis / Doctor of Philosophy (PhD)

Solid-state nuclear magnetic resonance (ssNMR) spectroscopy was used to anal- yse numerous graphene-sheet based materials in an attempt to study their effects on the performance of polymer electrolyte membrane fuel cell (PEM-FC) mate- rials. It has been noted in the literature that fuel cells which incorporated these materials (e.g. functionalized graphene, doped carbon nanotubes (CNTs), etc.) displayed increased performance over a wider range of environmental conditions, chiefly temperature and relative humidity. The inter-material interactions behind this phenomenon are poorly described at best. Due to its extreme site speci ficity and sensitivity to minute differences in nuclear electromagnetic environments, ss- NMR is an ideal tool for investigating the complicated interactions at work in these systems. While the electronically conductive, amorphous, non-stoichiometric, and low spin-density nature of these materials presented challenges to the collection of NMR spectra, the results presented here display the remarkable utility of this method in the study of analogues and derivatives of graphene. Graphene Oxide (GO), a derivative of graphene, has intrinsic proton conduc- tivity which is similar to Na fon, the most popular proton exchange membrane material currently used in fuel cells. Research into acid-functionalized graphene oxides and determining the role of acidic groups in increasing proton conductivity will help to improve polymer electrolyte membrane performance in fuel cell sys- tems. Multinuclear solid-state NMR (ssNMR) spectroscopy was used to analyse the structure and dynamics of GO and a number of sulfonic acid derivatives of GO, both novel and previously reported. 13C spectra showed the disappearance of surface-based oxygen groups upon GO functionalization, and can be used to identify linker group carbon sites in previously synthesized and novel functional- ized GO samples with high speci city. Dehydration of these samples allows the collection of 1H spectra with resolved acidic proton and water peaks. The effect of dehydration on the proton spectrum is partially reversible through rehydration. Deuteration of the acidic groups in high temperature and acidic conditions was virtually unsuccessful, indicating that only the surface and not the intercalated functional groups play a role in the enhanced proton conductivity of ionomer / functionalized GO composites. Increased surface area and increased delamination of functionalized GO is suggested to be important to improved PEM-FC perfor- mance. This synthesis and method of analysis proves the utility of ssNMR in the study of structure and dynamics in industrially relevant amorphous carbon ma- terials, despite the obvious di culties caused by naturally broad signals and low sensitivity. Graphene and carbon nanotubes (CNTs) have been investigated closely in re- cent years due to their apparent positive effect on the electrochemical performance of new fuel cell and battery systems as catalyst stabilizers, supports, or as metal- free catalysts. This is particularly true for doped graphene and CNTs, where only a small amount of doping with nitrogen and/or phosphorus can have a re- markable effect on materials performance. A direct link between structure and function in these materials is, as of yet, unclear. Doped graphene and CNTs were synthesized using varied chemical vapour deposition (CVD)-based methods, and ssNMR was used to unambiguously identify dopant atom sites, revealing that these particular synthesis methods result in highly homogeneous populations of installed phosphorus and nitrogen atoms. We present the first experimental 15N spectrum for graphitic nitrogen in N-doped graphene. 15N-labeled nitrogen doped graphene synthesized as reported here produces mainly graphitic nitrogen sites located on the edges of sheets and around defect sites. 1H-1H and 1H-15N corre- lations were also used to probe dopant nitrogen sites in labelled and unlabelled N-doped graphene. A nearly homogeneous population of phosphorus in P-doped graphene is found, with an overwhelming majority of graphitic phosphorus and a small amount of phosphate oligomer. Similar findings are noted for the phos- phorus sites in phosphorus and nitrogen co-doped CNTs with a minor change in chemical shift, as would be expected from two chemically similar phosphorus sites in carbon allotropes (CNTs versus graphene sheets) with signifi cantly different electronic structures. Ionomeric sulfonated polyether ether ketone (SPEEK) membranes were doped with functionalized graphenes, and the proton conductivities of these composite membranes was measured at fuel cell operational temperatures and percent relative humidities (%RH). The differences in proton conductivity between pure SPEEK membranes and composites with different dopants and doping levels at varied conditions were investigated through high-fi eld 1H ssNMR. It was found that high- speed MAS was able to dehydrate membranes under water-saturated conditions, and so lower %RH conditions were better able to produce reliable ssNMR results. The addition of graphitic dopants appeared to have an overall detrimental effect on the bulk proton conductivity of membranes, while concurrently these doped membranes had a broadened operational temperature window. In an attempt to explore the positive influence of nitrogen doping on the effec- tive lifetime of carbon-supported platinum catalysts used in automotive hydrogen fuel cell systems, solid-state NMR was employed to probe the difference (if any) between doped catalyst supports made from different carbon and nitrogen sources. 1H spectroscopy showed a variety of sites present in the doped samples; some likely from residual starting material but others from novel sites within the doped cat- alyst supports. Double-quantum and 2D 1H experiments were used to examine the structure of these catalysts, while 13C CPMG experiments (see Chapter 2) revealed subtle differences in the nuclear relaxation rates of these materials, poten- tially related to their electronic conductivity. The results of the ssNMR analysis were insuffcient to provide an unambiguous picture of the dopant sites within these carbon black samples; this was due in equal parts to the lack of isotopically labelled dopants, the effects of electronic induction and ring current shifts on data acquisition and analysis, and the broad array of different 13C chemical shift en- vironments present in the carbon black itself. While the data is still interesting spectroscopically, suggestions are made at the end of this chapter to expand upon the lessons learned through this study to produce more useful results from similar samples in the future. / Thesis / Doctor of Philosophy (PhD) / Solid-state nuclear magnetic resonance (ssNMR) spectroscopy was used to anal- yse numerous graphene-sheet based materials in an attempt to study their effects on the performance of polymer electrolyte membrane fuel cell (PEM-FC) materials. It has been noted in the literature that fuel cells which incorporated these materials (e.g. functionalized graphene / graphite, doped carbon nanotubes (CNTs), etc.) displayed increased performance over a wider range of environmental conditions, chiefly temperature and relative humidity. The inter-material interactions behind this phenomenon are poorly described at best. Due to its extreme site specifi city and sensitivity to minute differences in nuclear electromagnetic environments, ss- NMR is an ideal tool for investigating the complicated interactions at work in these systems. While the electronically conductive, amorphous, non-stoichiometric, and low spin-density nature of these materials presented challenges to the collection of NMR spectra, the results presented here display the remarkable utility of this method in the study of analogues and derivatives of graphene. Covalently functionalized graphene / graphite was synthesized, and the struc- tures of several derivatives were recorded with remarkable resolution, such that functional group carbons were resolvable. The proton dynamics of this material were remarkably slow, and so improvements in composite PEM ion conductiv- ity were proposed to be caused by surface interactions between dopant and poly- mer. The proton dynamics of ionomer graphene composites were also investigated through ssNMR. A number of graphene and CNT samples doped with phosphorus and 15N-labelled nitrogen were also analysed, and the synthesis methods employed were found to produce chemically homogeneous dopant sites with few by-products. Absent isotopic labelling, nitrogen dopant sites in carbon black samples were found to affect the relaxation properties of protons within nitrogen doped carbon black.