Long-chain alkylbenzenes are industrially synthesized precursors to commercial surfactants such as laundry detergent. The process of benzene alkylation currently utilizes homogeneous acidic catalysts (HF, AlCl3, etc.), which cause a multitude of problems such as production of toxic waste, hazards to workers, and corrosion of expensive industrial equipment. These problems can be avoided by the use of heterogeneous highly acidic catalysts. Solid catalysts do not corrode equipment and are relatively simple to remove from the post-reaction mixture. Phosphotungstic acid (PTA) supported on silica gel could be a possible catalyst due to its high acidity with an estimated pKa ≈ -13. However, it is soluble in many solvents and can be leached from silica gel during the process. The objective of this research is to obtain a superacidic stable heterogeneous catalyst containing covalently immobilized PTA, and evaluate its activity and stability in the alkylation of benzene by long-chain alkenes. The catalyst PTA/SiO2 was prepared via the sol-gel method by co-condensation of PTA with tetraethoxysilane in acidic media. Surfactant Pluronic P123 was used as a template to form porous structure. Then the catalyst was granulated to prevent caking of the powder during reaction. For granulation, the powder PTA/SiO2 was mixed with aluminum oxide (an inert adhesive agent) and pressured at 7 t to make tablets. The tablets were converted to granules of 1-2 mm diameter and calcined at 400 °C to remove moisture. FT-IR spectra confirmed the presence of PTA in the obtained material. Analysis by atomic absorption spectroscopy showed PTA contents of 0.027 mmol/g. The catalyst was mesoporous with BET surface area of 168 m2/g and mean particle size of 856 nm. The reaction of alkylation of benzene by octene-1 and decene-1 was carried out in a fixed bed flow reactor at 200-250 °C where mixtures of benzene and an alkene flowed through the catalyst with constant rate. Products were collected and analyzed on a GC chromatograph. The catalyst demonstrated good catalytic activity at temperatures above 200 °C. In all experiments mixtures of isomeric alkylbenzenes were obtained with 2-phenylalkanes as main products. Decreasing of flow rate and ratio alkene:benzene favored conversion of alkenes. Characterization of the catalyst after the reaction showed little changes in porosity and particle size. No leaching of PTA was observed. However, carbon deposits were found on the catalyst that requires regeneration before next use in catalysis.

The adrenal medulla is the inner part of adrenal glands located above each kidney, that produces catecholamines. Neuroblastoma and pheochromocytoma are the most prevalent malignancies of the adrenal medulla. Quantitative diagnosis of urinary catecholamines using HPLC-coupled Mass detectors is the current method for the diagnosis of neuroblastoma and pheochromocytoma. There are two major problems with this approach, (i) Because the catecholamines concentrations have short half-life (10-100 s), a series of urine tests must be performed throughout 24hr, detecting each catecholamine separately, is inconvenient and time-consuming; (ii) mass detectors are expensive, bulky, and require highly skilled personal. Vanillylmandelic (VMA), and homavanillic acid (HVA) are the by-products of catecholamines and are emerging alternative biomarker for catecholamines due to their high stability. Here, we developed a rapid, sensitive, miniaturized, and cheaper sensing platform for simultaneous quantifications of dopamine (DA), VMA, and HVA, with the aid of iron single-atom catalysts (Fe-SACs), based electrochemical sensor. SACs are atomically distributed metal atoms that have a maximum atomic utility rate of nearly 100%, compared to 30% for traditional metal nanoparticles. MXene sheets are employed to stabilize Fe-SACs, where, the exposed lone pairs of MXene serve as sites covalently linking high-energy single Fe atoms. MXene/Fe-SACs were synthesized by treating Ti3C2TxMXene with Iron chloride via freeze-drying followed by annealing. The successful formation of the material was verified by state-of-the-art characterizations. The MXene/Fe-SACs show superior electrocatalytic performance to the commonly used Fe- nanomaterials. Then, it was coated on the electrode surface and used to analyze DA, VMA, and HVA simultaneously via cyclic voltammetry (CV) and square-wave voltammetry (SWV). Under optimized conditions, the MXene/Fe-SACs electrochemical sensor showed detection limits as low as 1 nM and a linear range between 1 nM-100 μM for DA, LOD of 5 nM & linear range of 10 nM-100 μM VMA, and LOD of 10 nM & linear range of 20 nM-100 μM HAV. The method proved successful in detecting biomarkers in (spiked) synthetic urine and human serum. Furthermore, the method was successfully demonstrated in the determination of DA release from PC12 live cells, suggesting the wide practical use of SACs in sensing catecholamines-related metabolites.

One way of harnessing and storing our most abundant and renewable energy source, sunlight, is by utilizing it to split water for the hydrogen generation as a storable form of fuel. Si, the most investigated material for solar-to-hydrogen technology has great potential as the single photoelectrode. While some success has been achieved in Si-Based photoelectrochemical (PEC) systems, they suffer from low efficiency and short longevity. Moreover, in order for hydrogen to be commercially viable, the existing challenges of electrical, optical, and catalysis management must be addressed concurrently. Herein, we work on the simultaneous improvement in light harvesting, charge carrier separation/transfer, and catalysis management of Si-based photocathodes, achieving best-in-class efficiency with stable electrochemical performance. By decoupling the light harvesting side from the electrocatalytic surface we nullify parasitic light absorption. We developed a Si bifacial (SiBF) PEC photocathode to absorb light on both sides of PEC devices, which exhibits a current density of 39.01 mA/cm2. Unlike conventional monofacial PEC cells, our bifacial design demonstrates excellent omnidirectional light harvesting capability. Furthermore, back buried junction photoelectrochemical (BBJ-PEC) cells were fabricated that can realize efficient decoupling of photon. This scheme enables maximum light-harvesting without any metal contact, which prevents the shadow effect during the water splitting reaction. The highest hydrogen evolution current density (41.76 mA/cm2) was demonstrated based on a single BBJ-PEC device. Additionally, wireless water splitting can be achieved when three BBJ-PEC cells were connected in series. The efficient PEC cell design described herein demonstrates promising performance, taking us a step closer to real-world solar-to-hydrogen production.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18300号 / 工博第3892号 / 新制||工||1597(附属図書館) / 31158 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 村上 正浩, 教授 吉田 潤一, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18814号 / 理博第4072号 / 新制||理||1586(附属図書館) / 31765 / 京都大学大学院理学研究科化学専攻 / (主査)教授 丸岡 啓二, 教授 大須賀 篤弘, 教授 時任 宣博 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19014号 / 工博第4056号 / 新制||工||1624(附属図書館) / 31965 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 杉野目 道紀, 教授 澤本 光男, 教授 辻 康之 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(薬科学) / 甲第18928号 / 薬科博第42号 / 新制||薬||5(附属図書館) / 31879 / 京都大学大学院薬学研究科医薬創成情報科学専攻 / (主査)教授 大野 浩章, 教授 高須 清誠, 教授 竹本 佳司 / 学位規則第4条第1項該当 / Doctor of Pharmaceutical Sciences / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第20475号 / 人博第825号 / 新制||人||197(附属図書館) / 28||人博||825(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 吉田 寿雄, 教授 内本 喜晴, 教授 田部 勢津久, 教授 加藤 立久 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21126号 / 工博第4490号 / 新制||工||1698(附属図書館) / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 村上 正浩, 教授 杉野目 道紀, 教授 松田 建児 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20947号 / 理博第4399号 / 新制||理||1632(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 丸岡 啓二, 教授 依光 英樹, 教授 大須賀 篤弘 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM