Browsing by Subject "Oxygen reduction reaction"

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Open Access
Atomic layer deposition of Pd nanoparticles on N-Doped electrospun carbon nanofibers: optimization of ORR activity of Pd-Based nanocatalysts by tuning their nanoparticle size and loading
(Wiley-VCHVerlagGmbH& Co. KGaA,Weinheim, 2019) Khalily, Mohammad Aref; Patil, Bhushan; Yılmaz, Eda; Uyar, Tamer
Optimization of size, loading and chemical composition of catalytic nanoparticles is a crucial step to achieve cost‐effective and efficient (electro) catalysts. This report elaborates optimization of palladium (Pd) nanoparticle size and loading on the electrospun based N‐doped carbon nanofibers (nCNF) towards oxygen reduction reaction (ORR) for the energy devices like fuel cell, metal air batteries. Electrospinning was utilized to produce one‐dimensional (1D) polyacrylonitrile nanofibers followed by a two‐step carbonization process obtaining well‐defined conductive nCNF having diameters in the range of 200–350 nm. As‐synthesized nCNF was decorated with discrete Pd nanoparticles ranging from 2.6±0.4 nm to 4.7±0.5 nm via thermal atomic layer deposition (ALD) technique. We found that nCNF deposited Pd nanoparticles having 3.9±0.6 nm size (Pd20/nCNF) showed the best ORR activity with the smallest Tafel slope of 58 mV dec−1 along with four electrons involved in the ORR. In addition, high value at half wave potential (E1/2=806 mV vs. RHE) and exchange current densities (i0=6.998 mA cm−2) at Pd20/nCNF makes it efficient catalyst among other Pd decorated nCNF. Moreover, we found that electrocatalyst with lower loading/density of Pd nanoparticles showed enhanced ORR activity.
Open Access
Carbon supported nano-sized Pt-Pd and Pt-Co electrocatalysts for proton exchange membrane fuel cells
(2009) Kadirgan, F.; Kannan, A. M.; Atilan, T.; Beyhan, S.; Ozenler, S. S.; Süzer, Şefik; Yörür, A.
Nano-sized Pt-Pd/C and Pt-Co/C electrocatalysts have been synthesized and characterized by an alcohol-reduction process using ethylene glycol as the solvent and Vulcan XC-72R as the supporting material. While the Pt-Pd/C electrodes were compared with Pt/C (20 wt.% E-TEK) in terms of electrocatalytic activity towards oxidation of H2, CO and H2-CO mixtures, the Pt-Co/C electrodes were evaluated towards oxygen reduction reaction (ORR) and compared with Pt/C (20 wt.% E-TEK) and Pt-Co/C (20 wt.% E-TEK) and Pt/C (46 wt.% TKK) in a single cell. In addition, the Pt-Pd/C and Pt-Co/C electrocatalyst samples were characterized by XRD, XPS, TEM and electroanalytical methods. The TEM images of the carbon supported platinum alloy electrocatalysts show homogenous catalyst distribution with a particle size of about 3-4 nm. It was found that while the Pt-Pd/C electrocatalyst has superior CO tolerance compared to commercial catalyst, Pt-Co/C synthesized by polyol method has shown better activity and stability up to 60 °C compared to commercial catalysts. Single cell tests using the alloy catalysts coated on Nafion-212 membranes with H2 and O2 gases showed that the fuel cell performance in the activation and the ohmic regions are almost similar comparing conventional electrodes to Pt-Pd anode electrodes. However, conventional electrodes give a better performance in the ohmic region comparing to Pt-Co cathode. It is worth mentioning that these catalysts are less expensive compared to the commercial catalysts if only the platinum contents were considered.
Open Access
Investigating the effect of catalysts in sodium-oxygen batteries
(2017-11) Tovini, Mohammad Fathi
The unique electrochemical and chemical features of sodium oxygen (Na-O2) batteries distinguish them from the lithium-oxygen (Li-O2) batteries. NaO2, which is the main discharge product, is unstable in the cell environment and its dissolution in the electrolyte triggers side products formation and charging potential increment. In the rst part of this thesis, RuO2 nanoparticles (NPs) dispersed on carbon nanotubes (CNTs) are used as a catalyst for Na-O2 batteries to elucidate the e ect of catalyst on this complex electrochemical system. RuO2/CNT contributes to the formation of a poorly crystalline and coating like NaO2 structure during oxygen reduction reaction (ORR) which is drastically di erent from the conventional micron sized cubic NaO2 crystals deposited on CNT. Our ndings demonstrate a competition among NaO2 and side products decompositions for RuO2/CNT during oxygen evolution reaction (OER). We believe that this is due to the lower stability of coating like NaO2 because of its non-crystalline nature and high electrode/electrolyte contact area. Although RuO2/CNT catalyzes the decomposition of side products at a lower potential (3.66 V) compared to CNT (4.03 V), it cannot actively contribute to the main electrochemical reaction of the cell during OER (NaO2→ Na+ + O2 + e{ ) due to the fast chemical decomposition of lm NaO2 to side products. Even though the long term e ect of RuO2 catalyst during cycling and resting tests seems to be positive in terms of lower overpotential, no bene ts of catalyst is observed for stability and e ciency of the cell for the rst cycles. Therefore, tuning the morphology and crystallinity of NaO2 by catalyst is detrimental for Na-O2 cell performance and it should be taken into account for the future applications. In the second part of this thesis, a 3D RuO2/Mn2O3/carbon nano ber (CNF) composite has been prepared as a bi-functional electrocatalyst towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in Na-O2 batteries. RuO2/Mn2O3/CNF exhibited higher speci c capacity (9352 mAh.gcarbon -1) than CNF (1395 mAh.gcarbon -1), Mn2O3/CNF (3108 mAh.gcarbon -1) and RuO2/CNF (4859 mAh.gcarbon -1), which is believed to be due to its higher active surface area than its counterparts and its unique morphology. Taking the bene t of RuO2 and Mn2O3 synergistic e ect, the decomposition of inevitable side products at the end of charge occurs at 3.838 V vs. Na/Na+ by using RuO2/Mn2O3/CNF, which is 388 mV more cathodic compared with CNF.
Open Access
Metal-free N-doped ultrafine carbon fibers from electrospun Polymers of Intrinsic microporosity (PIM-1) based fibers for oxygen reduction reaction
(Elsevier, 2020) Patil, Bhushan; Satılmış, Bekir; Uyar, Tamer
Synthesis of nitrogen-doped carbon fibers (CF) has been proved to be one of the most promising oxygen reduction reaction (ORR) catalysts which can replace the state-of-art Pt catalyst for non-noble metal-free light-weight devices. Polymers of Intrinsic Microporosity (PIM-1) is soluble in common organic solvents and can be tailored by functionalization owing to nitrile groups in the backbone. PIM-1 was functionalized to amide (hydrolyzed PIM-1), amine and amidoxime groups. The modified PIM-1s were electrospun into ultrafine fibers and pyrolyzed to obtain CF. The present article investigates the influence of different functional groups on the properties of PIM-1 based CF and their nitrogen-doping. Particularly, their ORR performance has been evaluated. Interestingly, CF from hydrolyzed PIM-1 have the highest pore volume with small pore size among the CF based on PIM-1, amine and amidoxime PIM-1. The amount of nitrogen-doping in these CF shows the trend according to the functional groups as PIM-1 > amine > amidoxime > amide. Among all these PIM-1 based CF; CF from hydrolyzed PIM-1 has the highest percentage of pyridinic and graphitic nitrogen, furthermore, electrocatalysis revealed that ORR processed through four-electron with the onset potential 985 mV vs. reversible hydrogen electrode (RHE) which is comparable with the standard Pt/C catalysts.
Open Access
Modification of the Fe,Co–N/C catalysts for oxygen reduction reaction by a chemical post-treatment with oxidizing agents
(Elsevier Ltd, 2023-11-17) Lastovina, Tatiana; Bugaev, A.; Fedorenko, A.; Nikolskiy, A.; Kozakov, A.; Anokhin, A.; Yohannes, W.; Budnyk, Andriy
The transition-metals carbon catalysts belong to intensively studied alternatives to the Pt-based catalysts promoting the oxygen reduction reaction (ORR) in electrochemical fuel cells (FCs). Commonly studied Fe,Co–N–C composites are usually obtained through pyrolysis and used as such or after a chemical post-treatment with an oxidizing agent. This treatment is applied to remove inactive metal species, thus, promoting the electrochemical activity. The impact of an oxidizing agent is poorly addressed in the literature, while its nature may negatively affect the catalyst's performance. Herein we report the first comparative study on the effect of post-treatment with the most common oxidizing agents such as HCl, HNO3, H2SO4 and H2O2, on the structural and electrochemical properties of the Fe,Co–N–C catalyst. The catalyst is made by pyrolysis of the Co,Zn-ZIF metal-organic framework enriched with iron and nitrogen. Its structure was observed withstanding the action of mineral acids but suffers from hydrogen peroxide. The treatment with either nitric or chloric acid may improve the electrochemical performance up to 4%, while other agents decrease that by 6% and slow down the ORR rate. These findings are useful for the careful design of post-treatment procedures for carbon catalysts.
Open Access
Nanohybrid structured RuO2/Mn2O3/CNF as a catalyst for Na-O2 batteries
(Institute of Physics Publishing, 2018) Tovini, M. F.; Patil, B.; Koz, C.; Uyar, Tamer; Yılmaz, E.
A 3D RuO2/Mn2O3/carbon nanofiber (CNF) composite has been prepared in this study by a facile two step microwave synthesis, as a bi-functional electrocatalyst towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). RuO2 nanoparticles with the mean size of 1.57 nm are uniformly distributed on Mn2O3 nano-rods grown on electrospun CNFs. The electrocatalytic activity of the composites are investigated towards ORR/OER under alkaline condition. The ternary RuO2/Mn2O3/CNF composite showed superior ORR activity in terms of onset potential (0.95 V versus RHE) and Tafel slope (121 mV dec-1) compared to its RuO2/CNF and Mn2O3/CNF counterparts. In the case of OER, the RuO2/Mn2O3/CNF exhibited 0.34 V over-potential value measured at 10 mA cm-2 and 52 mV dec-1 Tafel slope which are lower than those of the other synthesized samples and as compared to state of the art RuO2 and IrO x type materials. RuO2/Mn2O3/CNF also exhibited higher specific capacity (9352 mAh ) than CNF (1395 mAh ), Mn2O3/CNF (3108 mAh ) and RuO2/CNF (4859 mAh g carbon -1) as the cathode material in Na-O2 battery, which indicates the validity of the results in non-aqueous medium. Taking the benefit of RuO2 and Mn2O3 synergistic effect, the decomposition of inevitable side products at the end of charge occurs at 3.838 V versus Na/Na+ by using RuO2/Mn2O3/CNF, which is 388 mV more cathodic compared with CNF.
Open Access
One-step codoping of reduced graphene oxide using boric and nitric acid mixture and its use in metal-free electrocatalyst
(Elsevier, 2015) Tien H.N.; Kocabas, C.; Hur, S.H.
In this study, the preparation of a highly efficient metal-free electrocatalyst, boron and nitrogen codoped reduced graphene oxide (BN-rGO), with an excellent durability is reported. The BN-rGO were prepared in one step using boric and nitric acid mixture, exhibiting highly improved oxygen reduction reaction (ORR) activity than those of the pristine GO and single doped rGOs. The electrocatalyst also showed the excellent long-term durability and CO tolerance than those of the commercial Pt/C catalysts. © 2014 Elsevier B.V.All rights reserved.