Chemical Engineering / Kimya Mühendisliği
Permanent URI for this collectionhttps://hdl.handle.net/11147/14
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Article Citation - WoS: 13Citation - Scopus: 11Bottom-Up Synthesis of Platinum Dual-Atom Catalysts on Cerium Oxide(American Chemical Society, 2024) Mekkering, Martijn J.; Laan, Petrus C. M.; Troglia, Alessandro; Bliem, Roland; Kızılkaya, Ali Can; Rothenberg, Gadi; Yan, NingWe present here the synthesis and performance of dual-atom catalysts (DACs), analogous to well-known single-atom catalysts (SACs). DACs feature sites containing pairs of metal atoms and can outperform SACs due to their additional binding possibilities. Yet quantifying the improved catalytic activity in terms of proximity effects remains difficult, as it requires both high-resolution kinetic data and an understanding of the reaction pathways. Here, we use an automated bubble counter setup for comparing the catalytic performance of ceria-supported platinum SACs and DACs in ammonia borane hydrolysis. The catalysts were synthesized by wet impregnation and characterized using SEM, HAADF-STEM, XRD, XPS, and CO-DRIFTS. High-precision kinetic studies of ammonia borane hydrolysis in the presence of SACs show two temperature-dependent regions, with a transition point at 43 degrees C. Conversely, the DACs show only one regime. We show that this is because DACs preorganize both ammonia borane and water at the dual-atom active site. The additional proximal Pt atom improves the reaction rate 3-fold and enables faster reactions at lower temperatures. We suggest that the DACs enable the activation of the water-O-H bond as well as increase the hydrogen spillover effect due to the adjacent Pt site. Interestingly, using ammonia borane hydrolysis as a benchmark reaction gives further insight into hydrogen spillover mechanisms, above what is known from the CO oxidation studies.Review Citation - WoS: 39Citation - Scopus: 37Engineered Liposomes in Interventional Theranostics of Solid Tumors(American Chemical Society, 2023) Kommineni, Nagavendra; Chaudhari, Ruchita; Conde, Joao; Cecen, Berivan; Chandra, Pranjal; Prasad, Rajendra; Tamburacı, SedefEngineered liposomal nanoparticles have unique characteristicsas cargo carriers in cancer care and therapeutics. Liposomal theranosticshave shown significant progress in preclinical and clinical cancermodels in the past few years. Liposomal hybrid systems have not onlybeen approved by the FDA but have also reached the market level. Nanosizedliposomes are clinically proven systems for delivering multiple therapeuticas well as imaging agents to the target sites in (i) cancer theranosticsof solid tumors, (ii) image-guided therapeutics, and (iii) combinationtherapeutic applications. The choice of diagnostics and therapeuticscan intervene in the theranostics property of the engineered system.However, integrating imaging and therapeutics probes within lipidself-assembly liposome may compromise their overalltheranostics performance. On the other hand, liposomal systems sufferfrom their fragile nature, site-selective tumor targeting, specificbiodistribution and premature leakage of loaded cargo molecules beforereaching the target site. Various engineering approaches, viz., grafting,conjugation, encapsulations, etc., have been investigated to overcomethe aforementioned issues. It has been studied that surface-engineeredliposomes demonstrate better tumor selectivity and improved therapeuticactivity and retention in cells/or solid tumors. It should be notedthat several other parameters like reproducibility, stability, smoothcirculation, toxicity of vital organs, patient compliance, etc. mustbe addressed before using liposomal theranostics agents in solid tumorsor clinical models. Herein, we have reviewed the importance and challengesof liposomal medicines in targeted cancer theranostics with theirpreclinical and clinical progress and a translational overview.Article Citation - WoS: 17Citation - Scopus: 16Development of Cissus Quadrangularis-Loaded Poss-Reinforced Chitosan-Based Bilayer Sponges for Wound Healing Applications: Drug Release and in Vitro Bioactivity(American Chemical Society, 2023) Değer Aker, Sibel; Tamburacı, Sedef; Tıhmınlıoğlu, FundaNowadays, antibiotic-loaded biomaterials have been widelyusedin wound healing applications. However, the use of natural extractshas come into prominence as an alternative to these antimicrobialagents in the recent period. Among natural sources, Cissus quadrangularis (CQ) herbal extract is usedfor treatment of bone and skin diseases in ayurvedic medicine dueto its antibacterial and anti-inflammatory effects. In this study,chitosan-based bilayer wound dressings were fabricated with electrospinningand freeze-drying techniques. CQ extract-loaded chitosan nanofiberswere coated on chitosan/POSS nanocomposite sponges using an electrospinningmethod. The bilayer sponge is designed to treat exudate wounds whilemimicking the layered structure of skin tissue. Bilayer wound dressingswere investigated with regard to the morphology and physical and mechanicalproperties. In addition, CQ release from bilayer wound dressings and in vitro bioactivity studies were performed to determinethe effect of POSS nanoparticles and CQ extract loading on NIH/3T3and HS2 cells. The morphology of nanofibers was investigated withSEM analysis. Physical characteristics of bilayer wound dressingswere determined with FT-IR analysis, swelling study, open porositydetermination, and mechanical test. The antimicrobial activity ofCQ extract released from bilayer sponges was investigated with a discdiffusion method. Bilayer wound dressings' in vitro bioactivity was examined using cytotoxicity determination, woundhealing assay, proliferation, and the secretion of biomarkers forskin tissue regeneration. The nanofiber layer diameter was obtainedin the range of 77.9-97.4 nm. The water vapor permeabilityof the bilayer dressing was obtained as 4021 to 4609 g/m(2)day, as it is in the ideal range for wound repair. The release ofthe CQ extract over 4 days reached 78-80% cumulative release.The release media were found to be antibacterial against Gram-negativeand Gram-positive bacteria. In vitro studies showedthat both CQ extract and POSS incorporation induced cell proliferationas well as wound healing activity and collagen deposition. As a result,CQ-loaded bilayer CHI-POSS nanocomposites were found as a potentialcandidate for wound healing applications.Article Citation - WoS: 10Citation - Scopus: 12Novel Hybrid Adsorption-Electrodialysis (aded) System for Removal of Boron From Geothermal Brine(American Chemical Society, 2022) Altınbaş, Bekir Fırat; Orak, Ceren; Ökten, Hatice Eser; Yüksel, AslıA novel hybrid adsorption-electrodialysis (AdED) system to remove environmentally harmful boron from geothermal brine was designed and effective operating parameters such as pH, voltage, and flow rate were studied. A cellulose-based adsorbent was synthesized from glycidyl methacrylate (GMA) grafted cellulose and modified with a boron selective n-methyl-d-glucamine (NMDG) group and characterized with SEM-EDX, FT-IR, and TGA analyses. Batch adsorption studies revealed that cellulose-based adsorbent showed a remarkable boron removal capacity (19.29 mg/g), a wide stable operating pH range (2-10), and an adsorption process that followed the Freundlich isotherm (R2= 0.95) and pseudo-second-order kinetics (R2= 0.99). In the hybrid AdED system, the optimum operating parameters for boron removal were found to be a pH of 10, a voltage of 10 V, a flow rate of 100 mL/min, and an adsorbent dosage of 4 g/L. The presence of the adsorbent in the hybrid system increased boron removal from real geothermal brine (containing 199 ppm boron) from 7.2% to 73.3%. The results indicate that the designed AdED system performs better than bare electrodialysis for boron removal from ion-rich real geothermal brine while utilizing environmentally friendly cellulose-based adsorbent.Article Citation - WoS: 11Citation - Scopus: 12Box-Behnken Design for Hydrogen Evolution From Sugar Industry Wastewater Using Solar-Driven Hybrid Catalysts(American Chemical Society, 2022) Orak, Ceren; Yüksel, AslıHydrogen is a clean and green fuel and can be produced from renewable sources via photocatalysis. Solar-driven hybrid catalysts were synthesized and characterized (scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, and UV-vis diffuse reflectance spectroscopy (DSR)), and the results implied that graphene-supported LaRuO3is a more promising photocatalyst to produce hydrogen and was used to produce hydrogen from sugar industry wastewater. To investigate the main and interaction effects of reaction parameters (pH, catalyst amount, and [H2O2]0) on the evolved hydrogen amount, the Box-Behnken experimental design model was used. The highest hydrogen evolution obtained was 6773 μmol/gcatfrom sugar industry wastewater at pH 3, 0.15 g/L GLRO, and 15 mM H2O2. Based on the Pareto chart for the evolved hydrogen amount using GLRO, among the main effects, the only effective parameter was the catalyst amount for the photocatalytic hydrogen evolution from sugar industry wastewater. In addition, the squares of pH and two-way interaction of pH and [H2O2]0were also statistically efficient over the evolved hydrogen amount.Article Citation - WoS: 7Citation - Scopus: 7Cross-Linked Phosphorylated Cellulose as a Potential Sorbent for Lithium Extraction From Water: Dynamic Column Studies and Modeling(American Chemical Society, 2022) Recepoğlu, Yaşar Kemal; Yüksel, AslıPhosphorylated functional cellulose was cross-linked with epichlorohydrin at different ratios because it is a very hydrophilic substance that instantly swells to form a hydrogel when it comes into contact with water. It was aimed to utilize a continuously packed bed column to recover lithium from water under varying operating conditions such as flow rate and bed height. The characterization results confirmed cross-linking based on morphology, structure, surface area, and thermal stability differences. Lithium recovery was more efficient with a low flow rate, but the dynamic sorption process was independent of bed height. The total capacities at the three flow rates with 1.5 cm bed height were 33.56, 30.15, and 25.54 mg g-1, and the total saturation times at the three different bed heights with 0.5 mL min-1 flow rate were 659, 1001, and 1007 min, respectively. Only 15.75 mL of 5% H2SO4 solution was required to desorb approximately 100% of Li from the saturated sorbent.Article Citation - WoS: 31Citation - Scopus: 35Electrochemical Degradation of Methylene Blue by a Flexible Graphite Electrode: Techno-Economic Evaluation(American Chemical Society, 2022) Gören, Ayşegül Yağmur; Recepoğlu, Yaşar Kemal; Edebali, Özge; Şahin, Çağrı; Genişoğlu, Mesut; Ökten, Hatice EserIn this study, electrochemical removal of methylene blue (MB) from water using commercially available and low-cost flexible graphite was investigated. The operating conditions such as initial dye concentration, initial solution pH, electrolyte dose, electrical potential, and operating time were investigated. The Box-Behnken experimental design (BBD) was used to optimize the system's performance with the minimum number of tests possible, as well as to examine the independent variables' impact on the removal efficiency, energy consumption, operating cost, and effluent MB concentration. The electrical potential and electrolyte dosage both improved the MB removal efficiency, since increased electrical potential facilitated production of oxidizing agents and increase in electrolyte dosage translated into an increase in electrical current transfer. As expected, MB removal efficiency increased with longer operational periods. The combined effects of operating time-electrical potential and electrical potential-electrolyte concentration improved the MB removal efficiency. The maximum removal efficiency (99.9%) and lowest operating cost (0.012 $/m3) were obtained for initial pH 4, initial MB concentration 26.5 mg/L, electrolyte concentration 0.6 g/L, electrical potential 3 V, and operating time 30 min. The reaction kinetics was maximum for pH 5, and as the pH increased the reaction rates decreased. Consequent techno-economic assessment showed that electrochemical removal of MB using low-cost and versatile flexible graphite had a competitive advantage.Article Citation - WoS: 12Citation - Scopus: 12Biofouling-Resistant Ultrafiltration Membranes Via Codeposition of Dopamine and Cetyltrimethylammonium Bromide With Retained Size Selectivity and Water Flux(American Chemical Society, 2022) Cihanoğlu, Aydın; Schiffman, Jessica D.; Alsoy Altınkaya, SacideBiofouling is a serious problem in ultrafiltration (UF) membrane applications. Modifying the surface of membranes with low molecular weight, commercially available antibacterial chemistries is an excellent strategy to mitigate biofouling. Herein, we report a new strategy to impart antibacterial and anti-biofouling behavior without changing the support membrane’s size selectivity and pure water permeance (PWP). To this end, a strong antibacterial agent, cetyltrimethylammonium bromide (CTAB), was codeposited with dopamine onto commercial polyethersulfone (PES) UF membranes in the presence of nitrogen (N2) gas backflow. The PWP and pore size of the support membrane did not change with codeposition, confirming the benefit of N2 backflow in mitigating the solution intrusion phenomenon. X-ray photoelectron spectroscopy (XPS), surface ζ potentials, and contact angle measurements confirmed the successful codeposition of polydopamine (PDA) and CTAB onto the membrane. Among three different CTAB concentrations systematically investigated, the membrane functionalized with CTAB at the critical micelle concentration (CMC) provided the best anti-biofouling activity against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria and retained its surface ζ potential after being stored in 1 M NaCl (pH = 6.8) for 3 months. Our results demonstrate the potential of using a facile, one-step approach to modify commercial UF membranes without compromising their pore size or flux, while simultaneously endowing antibacterial activity.Article Citation - WoS: 12Citation - Scopus: 13Selected Persistent Organic Pollutants in Ambient Air in Turkey: Regional Sources and Controlling Factors(American Chemical Society, 2021) Güngörmüş, Elif; Sofuoğlu, Aysun; Çelik, Halil; Gedik, Kadir; Mulder, Marie D.; Lammel, Gerhard; Sofuoğlu, Sait CemilAs a result of its unique location, Turkey receives air masses from Europe, Russia, Middle East, and Africa, making it an important place in terms of long-range atmospheric transport (LRT) of contaminants. Atmospheric levels of 22 organochlorine pesticides (OCPs), 45 polychlorinated biphenyls (PCBs), and 14 polybrominated diphenyl ethers (PBDEs) were measured in two metropolitan cities, Istanbul and Izmir, on a weekly basis from May 2014 to May 2015. Dichlorodiphenyltrichloroethane (DDT) and its derivatives were dominant OCP species, followed by isomers of hexachlorocyclohexane (HCH) at both sites. The annual mean concentration of Sigma DDX (sum of o,p'-DDT, p,p'-DDT, o,p'-DDD, p,p'-DDD, o,p'-DDE, and p,p'-DDE) was 82 pg/m(3) for Istanbul and 89 pg/m(3) for Izmir, while these levels were about 46 pg/m(3) for Sigma HCHs (sum of alpha-, beta-, gamma-, and delta-HCH) at both of the sites. At both stations, tri- and tetra-PCBs and tetra- and penta-PBDEs were dominant congeners. The temperature dependence indicates that both LRT and local contaminated areas contribute to the elevated levels. A Lagrangian particle dispersion model (FLEXPART) showed a few potential source regions in northern Africa and Middle East, southern-southwestern and eastern Europe including Russia, as well as from local domestic metropolitan areas.Article Citation - WoS: 69Citation - Scopus: 77Design of Cobalt Fischer-Tropsch Catalysts for the Combined Production of Liquid Fuels and Olefin Chemicals From Hydrogen-Rich Syngas(American Chemical Society, 2021) Jeske, Kai; Kızılkaya, Ali Can; Lopez-Luque, Ivan; Pfaender, Norbert; Bartsch, Mathias; Concepcion, Patricia; Prieto, GonzaloAdjusting hydrocarbon product distributions in the Fischer-Tropsch (FT) synthesis is of notable significance in the context of so-called X-to-liquids (XTL) technologies. While cobalt catalysts are selective to long-chain paraffin precursors for synthetic jet- and diesel-fuels, lighter (C10-) alkane condensates are less valuable for fuel production. Alternatively, iron carbide-based catalysts are suitable for the coproduction of paraffinic waxes alongside liquid (and gaseous) olefin chemicals; however, their activity for the water-gas-shift reaction (WGSR) is notoriously detrimental when hydrogen-rich syngas feeds, for example, derived from (unconventional) natural gas, are to be converted. Herein the roles of pore architecture and oxide promoters of Lewis basic character on CoRu/Al2O3 FT catalysts are systematically addressed, targeting the development of catalysts with unusually high selectivity to liquid olefins. Both alkali and lanthanide oxides lead to a decrease in turnover frequency. The latter, particularly PrOx, prove effective to boost the selectivity to liquid (C5-10) olefins without undesired WGSR activity. In situ CO-FTIR spectroscopy suggests a dual promotion via both electronic modification of surface Co sites and the inhibition of Lewis acidity on the support, which has direct implications for double-bond isomerization reactivity and thus the regioisomery of liquid olefin products. Density functional theory calculations ascribe oxide promotion to an enhanced competitive adsorption of molecular CO versus hydrogen and olefins on oxide-decorated cobalt surfaces, dampening (secondary) olefin hydrogenation, and suggest an exacerbated metal surface carbophilicity to underlie the undesired induction of WGSR activity by strongly electron-donating alkali oxide promoters. Enhanced pore molecular transport within a multimodal meso-macroporous architecture in combination with PrOx as promoter, at an optimal surface loading of 1 Prat nm(-2), results in an unconventional product distribution, reconciling benefits intrinsic to Co- and Fe-based FT catalysts, respectively. A chain-growth probability of 0.75, and thus >70 C% selectivity to C5+ products, is achieved alongside lighter hydrocarbon (C5-10) condensates that are significantly enriched in added-value chemicals (67 C%), predominantly alpha-olefins but also linear alcohols, remarkably with essentially no CO2 side-production (<1%). Such unusual product distributions, integrating precursors for synthetic fuels and liquid platform chemicals, might be desired to diversify the scope and improve the economics of small-scale gas- and biomass-to-liquid processes.