Browsing by Author "Erkartal, Mustafa"

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Anhydrous proton conducting poly(vinyl alcohol) (PVA)/ poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS)/1,2,4-triazole composite membrane
(Elsevier Ltd, 2016) Erkartal, Mustafa; Aslan, Ayse; Erkilic, Ufuk; Dadi, Seyma; Yazaydin, Ozgur; Usta, Hakan; Sen, Unal; 0000-0002-9772-128X; 0000-0003-1849-9180; 0000-0001-8562-723X; 0000-0002-0618-1979; 0000-0003-3736-5049; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Erkartal, Mustafa; Erkılıç, Ufuk; Dadı, Şeyma; Usta, Hakan; Şen, Ünal
The design and fabrication of anhydrous proton exchange membranes are critically important for high temperature proton exchange membrane fuel cell (HT-PEMFC) operating between 100 and 200 °C. Herein, we demonstrate a novel proton conducting membrane consisting of poly(vinyl alcohol) (PVA), poly (2-acrylamido-2-methylpropane sulfonic acid) (PAMPS) and 1,2,4-triazole, which was fabricated by physical blending, casting and solvent evaporation techniques. The in-situ chemical cross-linking was performed by glutaraldehyde (GA) to improve the water management of the membranes. The molecular structure of the membranes and intermolecular interactions between the constituents were confirmed by Fourier-transform infrared spectroscopy (FT-IR). The surface and cross-section morphologies of the membranes were observed by scanning electron microscopy (SEM). The thermal stability performance of the membranes was studied with thermogravimetric analysis (TGA). In order to determine the physico-chemical properties of the membranes, water uptake (WU), dimensional change and ion exchange capacity (IEC) tests were carried out. The proton conductivities of composite membranes increase with the temperature and the temperature dependencies exhibit an Arrhenius behavior. Proton conductivity measurements revealed an optimum ratio between PAMPS and 1,2,4-triazole content to achieve higher proton conductivity. In anhydrous state at 150 °C, the highest proton conductivity measured was 0.002 S/cm for PVA:PAMPS:1,2,4-triazole (1:1:1) composition. Overall, our investigation showed that 1,2,4-triazole is a promising proton carrier reagent above 100 °C when it is embedded into appropriate host polymers.
Basalt Fiber Reinforced Polymers: A Recent Approach to Electromagnetic Interference (EMI) Shielding
(WILEY Online Library, 2025) Fareez, Umar Naseef Mohamed; Loudiy, Aymen; Erkartal, Mustafa; Yilmaz, Cagatay; 0000-0001-9763-6598; 0000-0002-9772-128X; 0000-0002-8063-151X; AGÜ, Mühendislik Fakültesi, Makine Mühendisliği Bölümü; Fareez, Umar Naseef Mohamed; Loudiy, Aymen; Yilmaz, Cagatay
Electromagnetic wave (EMW) radiation pollution is getting more severe as result of the advancement of electronic technology. Researching shielding materials with superior EMI (electromagnetic interference) shielding characteristics is therefore crucial. Basalt fibers (BFs) have been an emerging candidate in the fiber-reinforced polymer (FRP) category due to their favorable mechanical and chemical properties, along with being favorites in sustainability and having low production costs. Therefore, due to the rising need for cheaper and efficient alternatives in the EMI shielding industry, the EMI shielding is covered in terms of BF composite materials and their properties in this review, starting with the EMI shielding mechanism and followed by how BF composites affect the EMI properties. This review then covers the post-treatments of BF composites and, finally, the factors of the composites that affect the EMI properties. Moreover, the EMI shielding applications in which BFRPs are used are comprehensively discussed as well. This review aspires to bridge an understanding between EMI shielding as a material property and the BF composites that are developed to aid in the EMI shielding application.
Boosting the Ceramics with In Situ MOF- Derived Nanocarbons
(AMER CHEMICAL SOC, 2023) Duden, Enes Ibrahim; Bayrak, Kubra Gurcan; Balkan, Mert; Cakan, Niyaz; Demiroglu, Arsen; Ayas, Erhan; Caglar, Mujdat; Turan, Servet; Islamoglu, Timur; Farha, Omar K; Erkartal, Mustafa; Şen, Ünal; 0000-0002-9772-128X; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Erkartal, Mustafa
Metal-organic framework (MOF)-derived nano-carbons have emerged as promising materials for energy and environmental applications owing to their high surface area, structural and chemical tunability, and hierarchical porosity. Although various carbon-based materials such as graphene and carbon nanotubes have been extensively used as secondary sintering additives to develop advanced ceramics with improved mechanical, thermal, and electrical properties, the potential of MOF-derived nanocarbon-based materials has not been ex-plored. Here, we report the first use of MOF-derived nanocarbons as a reinforcement phase in ceramic composites. To this end, Al2O3 and zeolitic imidazolate framework (ZIF-8) are used as the ceramic matrix and nanocarbon source, respectively. The ceramic composites are produced by densifying Al2O3 and ZIF-8 powder mixtures using spark plasma sintering (SPS) at 1550 degrees C and uniaxial pressure of 50 MPa. The fracture toughness of the composite increases up to 67% in comparison to an alumina monolith as ZIF-derived nanocarbons form interlayers to assist the dissipation of energy during the crack propagation and inhibit grain growth. The room-temperature electrical conductivity of the sintered samples drastically increases with the in situ formed nanocarbon-based fillers, reaching as high as 1410 S/m for 10 wt % ZIF-8 content. These results constitute an excellent initial step toward boosting the mechanical and electrical properties of ceramic matrix composites with in situ MOF-derived nanocarbons.
Boronic Acid Moiety as Functional Defect in UiO-66 and Its Effect on Hydrogen Uptake Capacity and Selective CO2 Adsorption: A Comparative Study
(AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 USA, 2018) Erkartal, Mustafa; Sen, Unal; 0000-0003-3736-5049; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü
Herein, we use linker fragmentation approach to introduce boronic acid moieties as functional defects into Zr-based metal organic frameworks (MOFs, UiO-66). Our findings show that the amount of permanently incorporated boronic acid containing ligand is directly dependent on the synthesis method. The accessible boronic acid moieties in the pore surfaces significantly improve the hydrogen uptake values, which are 3.10 and 3.44 wt % at 21 bar, 77 K for dimethylformamide (DMF)/H2O and DMF/HCI synthesis methods, respectively. Also, CO2 selectivity of the resulting MOFs over N-2 and CH4 significantly increases due to the quadrupolar interaction between active surfaces and CO2 molecules. To the best of our knowledge, both hydrogen storage and selectivity of CO2 for UiO-66 are the highest reported values in the literature to date. Furthermore, another striking result that emerged from the high-pressure hydrogen uptake isotherms is the direct correlation between the defects and hysteric adsorption behavior, which may result in the shift from rigidity to flexibility of the framework due to the uncoordinated sites.
Enhancing the Properties of Yttria-Stabilized Zirconia Composites with Zeolitic Imidazolate Framework-Derived Nanocarbons
(AMER CHEMICAL SOC, 2023) Cakan, Niyaz; Issa, Abduselam Abubeker; Alsalman, Hamza; Aliyev, Emin; Duden, Enes Ibrahim; Gurcan Bayrak, Kubra; Caglar, Mujdat; Turan, Servet; Erkartal, Mustafa; Sen, Unal; 0000-0002-9772-128X; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Erkartal, Mustafa
Ceramic matrix composites (CMCs) reinforced with nanocarbon have attracted significant interest due to their potential to enhance mechanical, thermal, and electrical properties. Although the investigation of carbon-based materials such as graphene and carbon nanotubes as additives for advanced ceramics has been widespread, the utilization of metal-organic framework (MOF)-derived nanocarbons in CMCs remains largely unexplored. We extended our previous proof-of-concept investigations by demonstrating the effectiveness of a different type of MOF-derived carbon as a reinforcing phase in an alternative ceramic matrix. We employed spark plasma sintering (SPS) to consolidate yttria-stabilized zirconia (YSZ) and zeolitic imidazolate framework (ZIF-67) powder blends at 1300 degrees C and a uniaxial pressure of 50 MPa. YSZ serves as the ceramic matrix, whereas ZIF-67 serves as the nanocarbon source. The composite exhibits a highly significant improvement in fracture toughness with an increase of up to 13% compared to that of the YSZ monolith. The formation of ZIF-derived nanocarbon interlayers is responsible for the observed enhancement in ductility, which can be attributed to their ability to facilitate energy dissipation during crack propagation and inhibit grain growth. Furthermore, the room-temperature electrical conductivity of the sintered samples demonstrates a substantial improvement, primarily due to the in situ formation of nanocarbon-based fillers, reaching an impressive 27 S/m with 10 wt % ZIF-67 content. Based on the results, it can be inferred that the incorporation of in situ MOF-derived nanocarbons into CMCs leads to a substantial improvement in both the mechanical and electrical properties.
Extreme flexibility and unusual piezomechanical properties of zinc-alkyl-based metal-organic frameworks: A first principles study
(ELSEVIER, 2023) Erkartal, Mustafa; 0000-0002-9772-128X; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Erkartal, Mustafa
The behavior of three Zn-alkyl-based MOFs, ZnGA (Zn-Glutarate), ZnAA (Zn-Adipate), and ZAG-4 (Zinc Alky Gate), under hydrostatic compression has been investigated using first-principles DFT simulation, which has proven its reliability in previous studies. Due to the lack of the high pressure experimental data for ZnGA and ZnAA, the reliability of the simulation parameters was tested by taking ZAG-4, whose structural flexibility has been previously reported experimentally and computationally, as a benchmark. All three structures were found to exhibit elastic deformation under pressure up to 15 GPa, due to the flexibility of the alkyl chains that allow the structures to move without disrupting the metal-ligand coordination. Interestingly, the structures exhibit different mechanical properties, with ZAG-4 showing negative linear compressibility (NLC), ZnGA showing positive linear compressibility (PLC), and ZnAA showing zero linear compressibility (ZLC). The NLC in ZAG-4 is attributed to the proton transfer between phosphonate oxygen and water in the structure as previously reported, while the ZLC in ZnAA is due to a dumbbell-like structural motif formed by substructures displaying both NLC and PLC.
From 2-methylimidazole to 1,2,3-triazole: a topological transformation of ZIF-8 and ZIF-67 by post-synthetic modification
(ROYAL SOC CHEMISTRYTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND, 2017) Erkartal, Mustafa; Erkilic, Ufuk; Tam, Benjamin; Yazaydin, Ozgur; Hupp, Joseph T.; Farha, Omar K.; Sen, Unal; 0000-0002-0618-1979; 0000-0003-1849-9180; 0000-0002-9772-128X; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Erkartal, Mustafa; Erkilic, Ufuk; Usta, Hakan
Bridging ligand replacement in zeolitic imidazolate frameworks, ZIF-8 and ZIF-67, by 1,2,3-triazole was investigated. A complete substitution of 2-methylimidazole by 1,2,3-triazole resulted in a topological transformation of the parent framework from a sodalite (SOD) network to a diamond (DIA) network.
Giant Negative Linear Compressibility, Isosymmetric Phase Transition, and Breathing Effect in a 3D Covalent Organic Framework
(AMER CHEMICAL SOC, 2023) Erkartal, Mustafa; 0000-0002-9772-128X; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Erkartal, Mustafa
A set of remarkable piezo-mechanical properties, including isosymmetric phase transition, negative linear compressibility (NLC), and a breathing effect in a three-dimensional covalent organic framework (NPN-3), was uncovered using density functional theory. The pressure-induced first-order phase transition observed between 0.9 and 1 GPa is isosymmetric and irreversible. NPN-3 shows giant NLC along the c-axis (K-c = 42.04 TPa-1) prior to the phase transition. The high-density NPN-3-hd obtained as a result of the phase transition shows an exciting phase transition from a closed pore to an open pore under hydrostatic tensile pressure, similar to the breathing effect. These extraordinary piezo-mechanical attributes within NPN-3 can be attributed to the diamondoid (dia) topology, which is commonly found within flexible MOFs and COFs. Additionally, the remarkable adaptability of the tetraphenyl adamantane monomer to distinct conformations under pressure can be seen in these properties. These findings underscore the potential utility of COFs as materials for piezo-mechanical sensors and serve as a source of inspiration for further exploration into the intricate mechanical behaviors of COFs.
An in-depth investigation of Mg-Zn-Ca metallic glasses: A first principles study
(Elsevier, 2018) Erkartal, Mustafa; Durandurdu, Murat; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü;
The atomic structures, glass forming evolutions, mechanical properties and high pressure behavior of Mg75Zn20Ca5 and Mg60Zn35Ca5 bulk metallic glasses, which are promising candidates for biomedical implants, have been examined by using ab initio molecular dynamics simulations. The pair-distribution function and coordination number analyses show that increasing Zn content in the alloy results in a decrease in several bond distances and an increase in the total coordination number of each species due to the atomic size difference between Mg and Zn atoms. According to the Voronoi tessellation, bond pair and bond angle distribution analyzes, the fivefold geometrical arrangements (pentagonal-bipyramid) are the most predominant in the first coordination shell, indicating the stability of the amorphous states and their dense atomic packing. The most striking result emerged from the calculations of mechanical properties is that an increase of Zn (?30%) content in the alloy yields embrittlement in the alloys. Under uniaxial compressions, both compositions undergo structural failure between 6 and 8?GPa. Under hydrostatic pressure, a diminishing in fcc/hcp ordering and an enlargement of the ideal icosahedral ordering may indicate a more disordered structure. In our view, these results represent a good step toward understanding the atomic structures Mg-Zn-Ca bulk metallic glasses.
Mesoscale Morphologies of Nafion-Based Blend Membranes by Dissipative Particle Dynamics
(MDPIST ALBAN-ANLAGE 66, CH-4052 BASEL, SWITZERLAND, 2021) Sen, Unal; Ozdemir, Mehmet; Erkartal, Mustafa; Kaya, Alaattin Metin; Manda, Abdullah A.; Oveisi, Ali Reza; Ali Aboudzadeh, M.; Tokumasu, Takashi; 0000-0002-1940-8749; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Kaya, Alaattin Metin
Polymer electrolyte membrane (PEM) composed of polymer or polymer blend is a vital element in PEM fuel cell that allows proton transport and serves as a barrier between fuel and oxygen. Understanding the microscopic phase behavior in polymer blends is very crucial to design alternative cost-effective proton-conducting materials. In this study, the mesoscale morphologies of Nafion/poly(1-vinyl-1,2,4-triazole) (Nafion-PVTri) and Nafion/poly(vinyl phosphonic acid) (Nafion-PVPA) blend membranes were studied by dissipative particle dynamics (DPD) simulation technique. Simulation results indicate that both blend membranes can form a phase-separated microstructure due to the different hydrophobic and hydrophilic character of different polymer chains and different segments in the same polymer chain. There is a strong, attractive interaction between the phosphonic acid and sulfonic acid groups and a very strong repulsive interaction between the fluorinated and phosphonic acid groups in the Nafion-PVPA blend membrane. By increasing the PVPA content in the blend membrane, the PVPA clusters' size gradually increases and forms a continuous phase. On the other hand, repulsive interaction between fluorinated and triazole units in the Nafion-PVTri blend is not very strong compared to the Nafion-PVPA blend, which results in different phase behavior in Nafion-PVTri blend membrane. This relatively lower repulsive interaction causes Nafion-PVTri blend membrane to have non-continuous phases regardless of the composition.
Poly(lauryl methacrylate)-Grafted Amino-Functionalized Zirconium-Terephthalate Metal-Organic Framework: Efficient Adsorbent for Extraction of Polycyclic Aromatic Hydrocarbons from Water Samples
(AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 USA, 2020) Tabatabaii, Maryam; Khajeh, Mostafa; Oveisi, Ali Reza; Erkartal, Mustafa; Sen, Unal; 0000-0002-0075-211X; 0000-0002-7097-2898; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü
In this study, a novel porous hybrid material, poly(lauryl methacrylate) polymer-grafted UiO-66-NH2 (UiO = University of Oslo), was synthesized for efficient extraction of polycyclic aromatic hydrocarbons (PAHs) from aqueous samples. The polymer end-tethered covalently to the MOF's surface was synthesized by surface-initiated atom transfer radical polymerization, revealing a distinct type of morphology. The adsorbent was characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, powder X-ray diffraction, N-2 adsorption-desorption analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The analyses were carried out by gas chromatography-mass spectrometry. Parameters including the type and volume of the eluent, the amount of the adsorbent, and adsorption and desorption times were investigated and optimized. Under optimal conditions, the limit of detection, intraday precision, and interday precision were in the range of 3-8 ng L-1, 1.4-3.1, and 4.1-6.5%, respectively. The procedure was used for analysis of PAHs from natural water samples.
Pressure-Induced Amorphization of MOF-5: A First Principles Study
(Wiley Online Library, 2018) Erkartal, Mustafa; Durandurdu, Murat; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü;
Amorphous metal-organic frameworks (MOFs) and the amorphization of crystalline MOFs under mechanical stimuli are attracting considerable interest in last few years. However, we still have limited knowledge on their atomic arrangement and the physical origin of crystalline-to-amorphous phase transitions under mechanical stimuli. In this study, ab initio simulations within a generalized gradient approximation are carried out to investigate the high-pressure behavior of MOF-5. Similar to the previous experimental findings, a pressure-induced amorphization is observed at 2 GPa through the simulations. The phase transformation is an irreversible first order transition and accompanied by around 68% volume collapse. Remarkably, the transition arises from local distortions and, contrary to previous suggestions, does not involve any bond breaking and formation. Additionally, a drastic band gap closure is perceived for the amorphous state. This study has gone some way towards enhancing our understanding of pressure-induced amorphization in MOFs.
Pressure-Induced Amorphization of MOF-5: A First Principles Study
(WILEY-V C H VERLAG GMBH, POSTFACH 101161, 69451 WEINHEIM, GERMANY, 2018) Erkartal, Mustafa; Durandurdu, Murat; 0000-0001-5636-3183; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü
Amorphous metal-organic frameworks (MOFs) and the amorphization of crystalline MOFs under mechanical stimuli are attracting considerable interest in last few years. However, we still have limited knowledge on their atomic arrangement and the physical origin of crystalline-to-amorphous phase transitions under mechanical stimuli. In this study, ab initio simulations within a generalized gradient approximation are carried out to investigate the high-pressure behavior of MOF-5. Similar to the previous experimental findings, a pressure-induced amorphization is observed at 2 GPa through the simulations. The phase transformation is an irreversible first order transition and accompanied by around 68% volume collapse. Remarkably, the transition arises from local distortions and, contrary to previous suggestions, does not involve any bond breaking and formation. Additionally, a drastic band gap closure is perceived for the amorphous state. This study has gone some way towards enhancing our understanding of pressure-induced amorphization in MOFs
Pressure-induced amorphization, mechanical and electronic properties of zeolitic imidazolate framework (ZIF-8)
(ELSEVIER SCIENCE SA, PO BOX 564, 1001 LAUSANNE, SWITZERLAND, 2020) Erkartal, Mustafa; Durandurdu, Murat; 0000-0002-9772-128X; 0000-0001-5636-3183; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü
Ab initio molecular dynamics (AIMD) simulations are carried out to probe the high-pressure behavior of ZIF-8 over wide pressure-range. Under compression, the enormous distortions in the ZnN4 tetrahedral units lead to a crystal-to-amorphous phase transition at around 3 GPa. During the amorphization process, the Zn-N coordination is retained. No other phase change but a possible fracture of the system is proposed above 10 GPa. Depending on released pressures, amorphous states with different densities are recovered. Yet when the applied pressure is released just before the amorphization, the rotations of imidazolate linkers (swing effect) cause an isostructural crystal-to-crystal phase transition, in agreement with experiments. In the tensile regime, no phase transition is perceived up to -2.75 GPa at which point the structural failure is observed. The crystal-amorphous phase transitions are also discovered at around 4 GPa under uniaxial compressions. The amorphous structures formed under uniaxial stress are about 20% denser than the one formed under the hydrostatic pressure. The average Young's modulus and Poisson's ratio of ZIF-8 are estimated to be around 5.6 GPa and 0.4, respectively. Interestingly, the tensile strength of ZIF-8 is found to be about 50% greater than its compressive strength. This paper shows that the experimentally observed phase transitions can be successfully reproduced with a clear explanation about the transition mechanism(s) at the atomistic level and all mechanical properties can be accurately calculated for a given ZIF structure by using AIMD simulations.
Proton conducting poly(vinyl alcohol) (PVA)/poly (2-acrylamido-2-methylpropane sulfonic acid) (PAMPS)/zeolitic imidazolate framework (ZIF) ternary composite membrane
(ELSEVIERRADARWEG 29, 1043 NX AMSTERDAM, NETHERLANDS, 2016) Erkartal, Mustafa; Usta, Hakan; Citir, Murat; Sen, Unal; 0000-0002-0618-1979; 0000-0002-6666-4980; 0000-0003-3736-5049; 0000-0002-9772-128X; AGÜ, Mühendislik Fakültesi, Makine Mühendisliği Bölümü; Erkartal, Mustafa; Usta, Hakan; Citir, Murat; Sen, Unal
The design, synthesis and characterization of novel proton exchange membranes (PEMs) are of significant scientific and technological importance for the realization of fuel cells, actuators, and sensors. Here, we demonstrate a novel ternary composite membrane consisting of poly(vinyl alcohol) (PVA), poly (2-acrylamido-2-methylpropane sulfonic acid) (PAMPS), zeolitic imidazolate framework-8 (ZIF-8), which is prepared by physical blending and casting methods. To enhance the water management of the membranes, in situ chemical cross-linking is carried out by glutaraldehyde (GA). During the characterization of the new membranes, FT-IR is used for intermolecular and inter-polymer interactions between different components of the membrane, SEM is used to identify morphology, XRD is used to prove the presence of ZIF-8 nanoparticles, and finally TGA is used for thermal stability. The proton conductivity of the membranes is found to increase with temperature and also with the increasing content of PAMPS. The highest proton conductivity under fully hydrated state at 80 degrees C is measured as 0.134 S cm(-1) for PVA: PAMPS: ZIF-8 (55:40:5) composition. In this study, it is clearly shown that ZIF-8 nanoparticles contribute to the proton conductivity by forming hydrogen bonds with the polymer network in the membrane. The water uptake (WU) and ion exchange capacity (IEC) values are 3.28 (gig) and 1.52 meq g(-1), respectively for the same membrane. To the best our knowledge, this study shows one of the first example of a MOFcontaining membrane with truly high proton conductivities, and both values of proton conductivity and electrochemical properties are comparable to those of well-studied membrane, Nation. (C) 2015 Elsevier B.V. All rights reserved.
Proton Conducting Self-Assembled Metal-Organic Framework/Polyelectrolyte Hollow Hybrid Nanostructures
(AMER CHEMICAL SOC1155 16TH ST, NW, WASHINGTON, DC 20036, 2016) Sen, Unal; Erkartal, Mustafa; Kung, Chung-Wei; Ramani, Vijay; Hupp, Joseph T; Farha, Omar K.; 0000-0003-3736-5049; 0000-0002-9772-128X; AGÜ, Mühendislik Fakültesi, Makine Mühendisliği Bölümü; Sen, Unal; Erkartal, Mustafa
Herein, a room temperature chemical process to synthesize functional, hollow nanostructures from zeolitic imidazolate framework-8 (ZIF-8) and poly(vinylphosphonic acid) (PVPA) is reported. Syntheses are initiated by physically blending the components a process that is accompanied first by encapsulation of ZIF-8 crystallites by PVPA and then by fragmentation of the crystallites. The fragmentation process is driven by partial displacement of the methyl-imidazolate ligands of Zn(II) in ZIF-8 by phosphonate groups on PVPA. Differences in rates of diffusion for the components of the reactive mixture yield a Kirkendall-like effect that is expressed as a hollow-particle morphology. The obtained hollow nanostructures feature hybrid shells containing PVPA, ZIF-8, and their cross-reacted products. The hybrid structures display substantial proton conductivities that increase with increasing temperature, even under the anhydrous conditions prevailing at temperatures above the boiling point of water. For example, at T = 413 K the proton conductivity of ZIF-8@PVPA reaches 3.2 (+/- 0.12) x 10(-3) S cm(-1), a value comparatively higher than that for PVPA (or ZIF-8) in isolation. The high value may reflect the availability in the hybrid structures of free (and partially free), amphoteric imidazole species, and their hydrogen-bonding interactions with phosphonate and/or phosphonic acid units. The persistence of ample conductivity at high temperature reflects the elimination of phosphonic acid group dehydration and dimerization-an effect that strikingly degrades the conductivity of pure PVPA under anhydrous conditions.
A Solution-Processable Liquid-Crystalline Semiconductor for Low-Temperature-Annealed Air-Stable N-Channel Field-Effect Transistors
(WILEY-V C H VERLAG GMBHPOSTFACH 101161, 69451 WEINHEIM, GERMANY, 2017) Ozdemir, Resul; Choi, Donghee; Ozdemir, Mehmet; Kim, Hyekyoung; Kostakoglu, Sinem Tuncel; Erkartal, Mustafa; Kim, Hyungsug; Kim, Choongik; Usta, Hakan; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Ozdemir, Resul; Ozdemir, Mehmet; Erkartal, Mustafa; Usta, Hakan
A new solution-processable and air-stable liquid-crystalline nchannel organic semiconductor (2,2'-(2,8-bis(5-(2-octyldodecyl) thiophen-2-yl) indeno[1,2-b] fluorene-6,12-diylidene) dimalononitrile, alpha,omega-2OD-TIFDMT) with donor-acceptor-donor (D-AD) pi conjugation has been designed, synthesized, and fully characterized. The new semiconductor exhibits a low LUMO energy (-4.19 eV) and a narrow optical bandgap (1.35 eV). The typical pseudo-focal-conic fan-shaped texture of a hexagonal columnar liquid-crystalline (LC) phase was observed over a wide temperature range. The spin-coated semiconductor thin films show the formation of large (approximate to 0.5-1 mu m) and highly crystalline platelike grains with edge-on molecular orientations. Low-temperature-annealed (50 degrees C) top-contact/bottom-gate OFETs have provided good electron obility values as high as 0.11 cm(2) (Vs)(-1) and high I-on/I-off ratios of 10(7) to 10(8) with excellent ambient stability. This indicates an enhancement of two orders of magnitude (100 V) when compared with the b-substituted parent semiconductor, beta-DD-TIFDMT (2,2'-(2,8-bis(3-dodecylthiophen- 2-yl) indeno[1,2-b] fluorene-6,12-diylidene) dimalononitrile). The current rational alkyl-chain engineering route offers great advantages for D-A-D pi-core coplanarity in addition to maintaining good solubility in organic solvents, and leads to favorable optoelectronic/physicochemical characteristics. These remarkable findings demonstrate that alpha,omega-2OD-TIFDMT is a promising semiconductor material for the development of n-channel OFETs on flexible plastic substrates and LC-state annealing of the columnar liquid crystals can lower the electron mobility for transistor-type charge transport.
Synthesis of benzotriazole functionalized ZIF-8 by postsynthetic modification for enhanced CH4 and CO2 uptakes
(ELSEVIER, 2022) Erkartal, Mustafa; Incekara, Kaan; Sen, Unal; 0000-0002-9772-128X; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Erkartal, Mustafa
In this work, a series of functionalized ZIF-8 were synthesized via incorporation of benzotriazole ligands into the framework with a post-synthetic method. The crystal structure and porosity were preserved for all functionalized samples. Although a relatively low percentage of ligand exchange (approximately 10–22%) was observed due to steric and kinetic effects, a remarkable improvement was found in CO2 and CH4 uptake capacities due to the incorporation of more polar N sites into the structure and the change in pore size of the frameworks. The resulting ZIF-8-S5 exhibited 45.17(CO2) and 15.08 (CH4) cm3 g− 1 at 273 K under 1.2 bar, which corresponds to an enhancement of 20 and 35% compared to pristine ZIF-8. Further, all functionalized samples showed the significant improvement of selective CO2 over N2.
Three-Dimensional Au-Coated Electrosprayed Nanostructured BODIPY Films on Aluminum Foil as Surface-Enhanced Raman Scattering Platforms and Their Catalytic Applications
(AMER CHEMICAL SOC1155 16TH ST, NW, WASHINGTON, DC 20036, 2017) Yilmaz, Mehme; Erkartal, Mustafa; Ozdemir, Mehmet; Sen, Unal; Usta, Hakan; Demirel, Gokhan; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Erkartal, Mustafa; Ozdemir, Mehmet; Usta, Hakan
The design and development of three-dimensional (3D) nanostructures with high surface-enhanced Raman scattering (SERS) performances have attracted considerable attention in the fields of chemistry, biology, and materials science. Nevertheless, electrospraying of organic smalt molecules on low-cost flexible substrates has never been studied to realize large-scale SERS-active platforms. Here, we report the facile, efficient, and low-cost fabrication of-Stable and reproducible Au-coated electrosprayed organic semiconductor films (Au@BDY-4TEBDY) on flexible regular aluminum foil at a large scale (5 cm X 5 cm) for practical SERS and catalytic applications. To this end, a well-designed-acceptor-donor-atceptor-type solution-processable molecular semiconductor, BDY-4T-BDY, developed by our group, is used because of its advantageous structural and electrical properties. The morphology of the electrosprayed organic film changes by solution concentration, and two different 3D morphologies with out-of-plane features are obtained. Highly uniform dendritic nanoribbons with sharp needle-like tips and vertically oriented nanoplates (similar to 50 nm thickness) are achieved when electrospraying solution concentrations of 240 and 253% w/v.(mgimL) are, respectively, used. When these electrosprayed organic films are coated with a nanoscopic thin (30 nm) Au layer, the resulting Au@BDY-4T-BDY platforms demonstrate remarkable SERS enhancement factors up to 1.7 X 10(6) with excellent Raman signal reproducibility (relative standard deviation <= 0.13) for methylene blue over the entire film. Finally, Au@BDY-4T-BDY films showed good catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol with rate constants of 1.3 X 10(-2) and 9.2 X 10(-3) min(-1). Our results suggest that electrospraying of rationally designed organic semiconductor molecules on flexible substrates holds great promise to enable low-cost, solution-processed, SERS-active platforms.
Unveiling the multifaceted properties of a 3d covalent-organic framework: Pressure-induced phase transition, negative linear compressibility and auxeticity
(ELSEVIER, 2023) Erkartal, Mustafa; 0000-0002-9772-128X; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Erkartal, Mustafa
High-pressure behavior and mechanical properties of a three-dimensional covalent-organic framework (NPN-1) were investigated by using different types of first principles molecular simulations. An irreversible pressureinduced first-order isosymmetric phase transition was predicted at 0.14 GPa. The subunit of NPN-1 retains its rigidity under pressure thanks to the strong covalent bonds. However, compression leads to significant tilting of the nitrophenyl groups. The mechanical properties of frameworks are highly anisotropic. Remarkably, both phases exhibit not only negative linear compressibility along the c-axis but also negative Poisson’s ratio in certain directions. Detailed structural analysis revealed that the origin of the phase transition and anomalous mechanical properties of both phases are the wine-rack motif and strut-hinge mechanism. To the best of our knowledge, this study is the first report of such behavior in COFs, opening up new avenues for the exploration of COFs as materials for many promising applications.