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Sample records for reduction reaction orr

  1. Practical aspects of the oxygen reduction reaction (ORR)

    SciTech Connect

    Uribe, F.A.; Springer, T.E.; Wilson, M.S.; Zawodzinski, T.A. Jr.; Gottesfeld, S.

    1995-12-31

    The oxygen reduction reaction (ORR) is quite sensitive to the details of the three phase interface at which the reaction occurs. We describe here studies of the ORR at a well-defined recast Nafion/Pt microelectrode interface, emphasizing the effects of temperature and humidification on the reaction rate. We compare our results to those obtained in thin film composite electrodes used in polymer electrolyte fuel cells.

  2. Oxygen reduction reaction (ORR) on mixed oxy-nitride non-noble catalyst: Ab-initio simulation, elaboration and characterization

    NASA Astrophysics Data System (ADS)

    Seifitokaldani, Ali

    In this project, titanium oxy-nitride (TiOxN y) has been studied as a new non-noble electrocatalyst for the oxygen reduction reaction (ORR). A comprehensive comparison between four different sol-gel methods was carried out to evaluate the physicochemical and electrochemical properties of the produced electro-catalysts. Among them, a new urea-based sol-gel method (simply called U method) is introduced to prepare TiOxNy at a fairly low temperature and duration, with higher electro-catalytic activity for the ORR. The prepared electro-catalysts with different N/O ratios showed different properties from a less conductive behavior in oxygen-rich (low N/O ratio) materials to more conductive electro-catalyst behavior in nitrogen-rich (high N/O ratio) oxy-nitrides, respectively. Generally, electro-catalysts prepared by the U method had more titanium nitride in their structures than the electro-catalysts prepared by the other methods. Nevertheless, heat treatment had a key role in this phase transferring from having high oxide structure to high nitride structure. According to the elemental analysis done by energy dispersive spectroscopy (EDS), nitrogen percentage in the bulk material increased from 9 to 24 percent by increasing the temperature from 700 to 1100 °C, while the oxygen percentage was decreasing inversely. In addition, based on the X-ray diffraction (XRD) data, in the case of U method, the TiN characteristic peaks were obvious, even at lower temperatures. Increasing the temperature also made the peaks much sharper indicating the growth of the crystallite size. The calculated crystallite size showed the crystallite size of samples prepared by U method (20 to 40 nm) was almost in the same range of the TiN crystallite size, but the crystallite size of the samples prepared by the other sol-gel methods (40 to 60 nm) was in the same range of the TiO2 crystallite size. Scanning electron microscopy (SEM) and B.E.T. surface area analyzer were used to evaluate the particle

  3. Mesoporous Pt-Co oxygen reduction reaction (ORR) catalysts for low temperature proton exchange membrane fuel cell synthesized by alternating sputtering

    NASA Astrophysics Data System (ADS)

    Sievers, Gustav; Mueller, Steffen; Quade, Antje; Steffen, Florian; Jakubith, Sven; Kruth, Angela; Brueser, Volker

    2014-12-01

    Mesoporous catalysts with enhanced oxygen reduction reaction (ORR) activity for PEM fuel cells are synthesized by alternating sputtering of Pt and Co onto gas diffusion layers with microporous layers. Co is acting as a template for synthesis of a porous Pt nanostructure. For such proposed Pt-Co catalysts the kinetic current in the ORR was found to be increased by a factor of up to 16 and the mass specific current in PEM single cells by a factor of up to 7. Co was found to be deposited at the grain boundary of the Pt layer and dissolves under acidic conditions resulting in a mesoporous Pt catalyst which is advantageous for gas diffusion catalysts. Microstructural and compositional parameters were optimised in order to obtain a high kinetic current and lower onset potential for the ORR. The most favourable Co layer thickness was determined to be 2 nm. The optimal Pt-Co catalyst can be synthesized by continuously varying the Pt layer thickness. The highest Pt mass activity was found at a layer thickness of 30.5 nm. Catalysts were characterised by SEM, EDX, electrochemical half cell and PEM single cell tests.

  4. Cobalt-polypyrrole-carbon black (Co-PPY-CB) Electrocatalysts for the Oxygen Reduction Reaction (ORR) in Fuel Cells: Composition and Kinetic Activity

    SciTech Connect

    D Nguyen-Thanh; A Frenkel; J Wang; S OBrien; D Akins

    2011-12-31

    Electrocatalysts consisting of polypyrrole (PPY) and Co deposited on carbon black (CB) at several compositions were prepared and tested for the oxygen reduction reaction (ORR) in a HClO4 buffer (pH = 1) using a rotating ring-disk electrode (RRDE). It was determined that the most favorable catalyst composition (prior to calcination) had a CB:PPY weight ratio of 2 and a pyrrole:Co (i.e., PY:Co) molar ratio of 4. This catalyst had an onset potential of 0.785 V (vs. RHE) and a mass activity of ca. 1 A/g{sub cata} at the fuel cell relevant voltage of 0.65 V. Furthermore, it was found that the number of electrons exchanged during the ORR with the catalyst was ca. 3.5 and resulted in 28% yield of H{sub 2}O{sub 2} at 0.65 V, which hints to an indirect 4e{sup -} reduction of O{sub 2} to H{sub 2}O, with H{sub 2}O{sub 2} as an intermdiate. From energy dispersive spectroscopy (EDS) and extended X-ray absorption fine structure (EXAFS) analysis, it is proposed that a PY:Co ratio of 4 favors the formation, prior to calcination, in the catalyst precursor of Co-N complexes in which Co is coordinated to 3 or 4 N atoms, resulting in strong Co-N interactions that limit the formation upon calcination of low ORR activity Co nanoparticles. These Co-N complexes give rise upon calcination to CoN{sub x-2} sites in which the coordination of Co could favor the adsorption on them of O{sub 2}, which would make those sites particularly active and selective. At the same mass acitivity of 1 A/g{sub cata}, the voltage yielded by the catalyst was 200 mV lower than that for a state-of-the-art Pt (10 wt.%) catalyst, whoch H{sub 2}O{sub 2} output at 0.85 V was 39% and involves the exchange of 3.2 e{sup -}, overall making our material an attractive substitute to noble metal ORR electrocatalysts.

  5. Iron-embedded boron nitride nanosheet as a promising electrocatalyst for the oxygen reduction reaction (ORR): A density functional theory (DFT) study

    NASA Astrophysics Data System (ADS)

    Feng, Li-yan; Liu, Yue-jie; Zhao, Jing-xiang

    2015-08-01

    We performed comprehensive density functional theory (DFT) calculations to explore the possibility of the Fe-embedded hexagonal boron nitride (h-BN) sheet as a novel electrocatalyst for ORR. Our results show that Fe atom can strongly bind with defective BN sheet and thus ensure its high stability. Moreover, O2 molecule is found to be strongly chemisorbed on Fe-embedded BN sheet with the adsorption energy of -1.76 eV, which can server as precursors for ORR, followed by its hydrogenation into OOH species rather than direct breakage of the O-O bond. Further, the HOOH species in the process of OOH reduction is shown to be unstable and dissociates into two OH group, suggesting that ORR catalyzed by Fe-embedded BN sheet is a direct four-electron pathway. Finally, on the basis of the calculations on the free energy change and activate energy of each step in ORR, we expect that Fe-embedded BN sheet exhibits good catalytic activity for ORR. Our results provide an useful guidance for the design and fabrication of novel and nonprecious BN sheet-based electrocatalyst for ORR as the alternative of expensive Pt catalysts.

  6. Use of H2S to Probe the Active Sites in FeNC Catalysts for the Oxygen Reduction Reaction (ORR) in Acidic Media

    SciTech Connect

    Singh, Deepika; Mamtani, Kuldeep; Bruening, Christopher R.; Miller, Jeffrey T.; Ozkan, Umit S.

    2014-10-01

    H2S has been used as a probe molecule both in an “in situ” poisoning experiment and in intermediate-temperature heat-treatment steps during and after the preparation of FeNC catalysts in an attempt to analyze its effect on their ORR activity. The heat treatments were employed either on the ball-milled precursor of FeNC or after the Ar-NH3 high temperature heat treatments. ORR activity of the H2S-treated catalysts was seen to be significantly lower than the sulfur-free catalysts, whether the sulfur exposure was during a half-cell testing, or as an intermediate-temperature exposure to H2S. The incorporation of sulfur species and interaction of Fe with sulfur were confirmed by characterization using XPS, EXAFS, TPO, and TPD. This study provides crucial evidence regarding differences in active sites in FeNC versus nitrogen-containing carbon nanostructured (CNx) catalysts.

  7. Cobaltite oxide nanosheets anchored graphene nanocomposite as an efficient oxygen reduction reaction (ORR) catalyst for the application of lithium-air batteries

    NASA Astrophysics Data System (ADS)

    Gnana kumar, G.; Christy, Maria; Jang, Hosaeng; Nahm, Kee Suk

    2015-08-01

    The graphene/cubic cobaltite oxide nanosheets (rGO/Co3O4) with a face centered cubic crystalline structure are synthesized and are exploited as effective cathode catalysts in high performance Lithium-air batteries. The morphological images enunciate that 220 nm average diameter of Co3O4 nanosheets are effectively anchored over the graphene sheets and the diameter of individual nanoparticles that construct the cubic nanosheets is 5 nm. The growth and composite formation mechanisms of prepared nanostructures are identified from Raman and FT-IR spectroscopic techniques. rGO/Co3O4 composite exhibits a lower voltage, high discharge capacity of 4150 mAh g-1 and displays superior cyclability without any capacity losses, signifying the excellent rechargeability of the fabricated electrodes. The post mortem analysis of electrodes specify the existence of lithium peroxide (Li2O2), lithium oxide (Li2O) and lithium carbonate (Li2CO3) discharge products, revealing the involved electrochemical reaction of Lithium-air batteries. The excellent electrochemical properties of rGO/Co3O4 composite is due to the combination of rapid electrokinetics of electron transport and high electrocatalytic activity toward oxygen reduction reaction given via the synergetic effects of rGO and cubic Co3O4 nanosheets. These findings provide fundamental knowledge on understanding the influence of morphological and structural properties of graphene based nanostructures toward Lithium-air battery performances.

  8. Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 1

    NASA Astrophysics Data System (ADS)

    Pech-Pech, I. E.; Gervasio, Dominic F.; Godínez-Garcia, A.; Solorza-Feria, O.; Pérez-Robles, J. F.

    2015-02-01

    Silver (Ag) nanoparticles enriched with platinum (Pt) and palladium (Pd) on their surfaces (Ag@Pt0.1Pd0.1) are supported on Vulcan XC-72 carbon (C) to form a new catalyst (Ag@Pt0.1Pd0.1/C) for the oxygen reduction reaction (ORR) in acid electrolytes. This catalyst is prepared in one pot by reducing Ag and then Pt and Pd metal salts with sodium borohydride in the presence of trisodium citrate then adding XC-72 while applying intense ultrasound. The metallic Ag@Pt0.1Pd0.1 nanoparticles contain 2 weight percent of Pt, are spherical and have an average size less than 10 nm as determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). At the ORR potentials, Ag nanoparticles on carbon (Ag/C) rapidly lose Ag by dissolution and show no more catalytic activity for the ORR than the carbon support, whereas Ag@Pt0.1Pd0.1/C is a stable catalyst and exhibits 1.4 and 1.6 fold greater specific activity, also 3.6 and 2.8 fold greater mass activity for ORR in 0.5 M H2SO4 solution than comparable Pt/C and Pt0.5Pd0.5/C catalysts with the same Pt loading as determined for thin-films of these catalysts on a rotating-disk electrode (TF-RDE). Using silver nanoparticles increases Pt utilization and therefore decreases Pt-loading and cost of a catalyst for a proton exchange membrane fuel cell (PEMFC) electrode.

  9. Comparison of the oxygen reduction reaction between NaOH and KOH solutions on a Pt electrode: the electrolyte-dependent effect.

    PubMed

    Jin, Wei; Du, Hao; Zheng, Shili; Xu, Hongbin; Zhang, Yi

    2010-05-20

    The oxygen reduction reaction (ORR) on a polycrystalline Pt surface was studied using cyclic voltammetry techniques, and the influence of reaction media on the ORR is examined by comparing the ORR in NaOH and KOH solutions with concentration ranging from 0.5 to 14 M at 298 K. The results show that, in NaOH and KOH solutions, the ORR, a quasi-reversible diffusion-controlled reaction, is largely dependent on the electrolyte conditions, and KOH solutions are superior to NaOH solutions for the ORR process in both thermodynamic and kinetic consideration. As the alkaline concentration increases, the ORR performance frustrates, and the protonation of superoxide is suppressed; thus, the ORR shifts from a 2e reduction pathway to a 1e reduction pathway in both solutions. PMID:20411967

  10. Beneficial compressive strain for oxygen reduction reaction on Pt (111) surface

    SciTech Connect

    Kattel, Shyam; Wang, Guofeng

    2014-09-28

    We investigated the influence of compressive surface strain on the progression of oxygen reduction reaction (ORR) on Pt(111) surface using the density functional theory (DFT) calculation method. Specifically, we calculated the binding energies of all the chemical species possibly involved in ORR and the reaction energies (heat of reaction and activation energy) of all the possible ORR elementary reactions on the Pt(111) surfaces with −2% and −3% strain. Our DFT results indicate that all the ORR species bind more weakly on the compressively strained surfaces than on an unstrained surface owing to strain-induced d-electron band broadening. Our DFT calculations further predict that both OOH dissociation and HOOH dissociation pathways could be active for ORR on the Pt(111) surface with compressive strain between −2% and −3%. Moreover, the activation energies of the ORR rate-determining steps on the compressively strained Pt(111) surfaces were found to be lower than that on the unstrained Pt(111) surface. It was thus inferred that a −2% to −3% surface strain could lead to enhanced ORR activity on the Pt(111) catalysts. Consequently, our study suggests that tuning surface strain is an effective way to improve the performance of Pt-based electrocatalysts for ORR.

  11. Bio-inspired multinuclear copper complexes covalently immobilized on reduced graphene oxide as efficient electrocatalysts for the oxygen reduction reaction.

    PubMed

    Xi, Yue-Ting; Wei, Ping-Jie; Wang, Ru-Chun; Liu, Jin-Gang

    2015-05-01

    Inspired by the multicopper active site of laccase, which efficiently catalyzes the oxygen reduction reaction (ORR), herein we report a novel bio-inspired ORR catalyst composed of a multinuclear copper complex that was immobilized on the surface of reduced graphene oxide (rGO) via the covalently grafted triazole-dipyridine (TADPy) dinucleating ligand. This rGO-TADPyCu catalyst exhibited high ORR activity and superior long-term stability compared to Pt/C in alkaline media. PMID:25825826

  12. Iron phthalocyanine and nitrogen-doped graphene composite as a novel non-precious catalyst for the oxygen reduction reaction.

    PubMed

    Zhang, Chenzhen; Hao, Rui; Yin, Han; Liu, Fei; Hou, Yanglong

    2012-12-01

    We develop a facile method for the synthesis of an iron phthalocyanine (FePc) and nitrogen-doped graphene (NG) composite as a novel and efficient non-precious catalyst in the oxygen reduction reaction (ORR). The resulting product exhibits superior ORR catalytic activity, excellent tolerance to methanol crossover, and comparable stability to commercial Pt/C, which leads to the invention of a new non-precious catalyst for ORR in fuel cells. PMID:23086132

  13. Covalent grafting of carbon nanotubes with a biomimetic heme model compound to enhance oxygen reduction reactions.

    PubMed

    Wei, Ping-Jie; Yu, Guo-Qiang; Naruta, Yoshinori; Liu, Jin-Gang

    2014-06-23

    The oxygen reduction reaction (ORR) is one of the most important reactions in both life processes and energy conversion systems. The replacement of noble-metal Pt-based ORR electrocatalysts by nonprecious-metal catalysts is crucial for the large-scale commercialization of automotive fuel cells. Inspired by the mechanisms of dioxygen activation by metalloenzymes, herein we report a structurally well-defined, bio-inspired ORR catalyst that consists of a biomimetic model compound-an axial imidazole-coordinated porphyrin-covalently attached to multiwalled carbon nanotubes. Without pyrolysis, this bio-inspired electrocatalyst demonstrates superior ORR activity and stability compared to those of the state-of-the-art Pt/C catalyst in both acidic and alkaline solutions, thus making it a promising alternative as an ORR electrocatalyst for application in fuel-cell technology. PMID:24842193

  14. Tuning the catalytic activity of graphene nanosheets for oxygen reduction reaction via size and thickness reduction.

    PubMed

    Benson, John; Xu, Qian; Wang, Peng; Shen, Yuting; Sun, Litao; Wang, Tanyuan; Li, Meixian; Papakonstantinou, Pagona

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (<2.5±0.2 at. %), few layer graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts. PMID:25334050

  15. Activated carbon becomes active for oxygen reduction and hydrogen evolution reactions.

    PubMed

    Yan, Xuecheng; Jia, Yi; Odedairo, Taiwo; Zhao, Xiaojun; Jin, Zhao; Zhu, Zhonghua; Yao, Xiangdong

    2016-06-21

    We utilized a facile method for creating unique defects in the activated carbon (AC), which makes it highly active for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). The ORR activity of the defective AC (D-AC) is comparable to the commercial Pt/C in alkaline medium, and the D-AC also exhibits excellent HER activity in acidic solution. PMID:27277286

  16. Oxygen reduction and evolution reactions of air electrodes using a perovskite oxide as an electrocatalyst

    NASA Astrophysics Data System (ADS)

    Nishio, Koji; Molla, Sergio; Okugaki, Tomohiko; Nakanishi, Shinji; Nitta, Iwao; Kotani, Yukinari

    2015-03-01

    The oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) of air electrodes consisting of La0.5Sr0.5CoO3 and/or carbon in the electrocatalyst layer are studied by using two types of gas diffusion electrodes. Cyclic voltammetry and square wave voltammetry studies reveal very low ORR activity of carbon-free perovskite and remarkably enhanced ORR of perovskite-carbon composites. The ORR current density at -0.5 V vs. Hg/HgO is higher than 200 mA cm-2 in a wide range of perovskite-carbon composition, suggesting good peroxide reducing capability of the perovskite. The ORR mechanisms of perovskite-carbon composites are consistent with the 2+2-electron mechanisms. The ORR and OER properties of perovskite-carbon composite electrodes are significantly influenced by the carbon species. The electrode exhibits a higher ORR current density, but inferior cycling performances when a carbon material with a higher specific surface area is used, and vice versa. Under a current density of 20 mA cm-2 and ORR and OER durations of 30 min, a gas diffusion type electrode consists of La0.5Sr0.5CoO3 and a low surface area carbon are capable of more than 150 cycles.

  17. Enhanced electrocatalytic activity of nitrogen-doped olympicene/graphene hybrids for the oxygen reduction reaction.

    PubMed

    Hou, Xiuli; Zhang, Peng; Li, Shuang; Liu, Wei

    2016-08-17

    Developing inexpensive and non-precious metal electrocatalysts for the oxygen reduction reaction (ORR) is among the major goals in fuel cells. Herein, by using density-functional theory calculations, we show that N-doped olympicene/graphene hybrids exhibit unexpectedly high ORR catalytic activity-even comparable to that of the Pt(111) surface. Both graphitic-type and pyridine-type N-doped olympicene/graphene hybrids are highly active for the ORR and have good CO tolerance. The formation of the second H2O molecule is the rate-determining step for the ORR with the graphitic-type hybrid, whereas on the pyridine-type hybrid, it is the formation of OOH. Note that N-doped olympicene/graphene hybrid materials combine the high reactivity of olympicene and the high electrical conductivity of graphene, which allows them to be potentially used as low-cost and non-precious-metal ORR catalysts. PMID:27499058

  18. Novel nanowire-structured polypyrrole-cobalt composite as efficient catalyst for oxygen reduction reaction.

    PubMed

    Yuan, Xianxia; Li, Lin; Ma, Zhong; Yu, Xuebin; Wen, Xiufang; Ma, Zi-Feng; Zhang, Lei; Wilkinson, David P; Zhang, Jiujun

    2016-01-01

    A novel nanowire-structured polypyrrole-cobalt composite, PPy-CTAB-Co, is successfully synthesized with a surfactant of cetyltrimethylammounium bromide (CTAB). As an electro-catalyst towards oxygen reduction reaction (ORR) in alkaline media, this PPy-CTAB-Co demonstrates a superior ORR performance when compared to that of granular PPy-Co catalyst and also a much better durability than the commercial 20 wt% Pt/C catalyst. Physiochemical characterization indicates that the enhanced ORR performance of the nanowire PPy-CTAB-Co can be attributed to the high quantity of Co-pyridinic-N groups as ORR active sites and its large specific surface area which allows to expose more active sites for facilitating oxygen reduction reaction. It is expected this PPy-CTAB-Co would be a good candidate for alkaline fuel cell cathode catalyst. PMID:26860889

  19. Novel nanowire-structured polypyrrole-cobalt composite as efficient catalyst for oxygen reduction reaction

    PubMed Central

    Yuan, Xianxia; Li, Lin; Ma, Zhong; Yu, Xuebin; Wen, Xiufang; Ma, Zi-Feng; Zhang, Lei; Wilkinson, David P.; Zhang, Jiujun

    2016-01-01

    A novel nanowire-structured polypyrrole-cobalt composite, PPy-CTAB-Co, is successfully synthesized with a surfactant of cetyltrimethylammounium bromide (CTAB). As an electro-catalyst towards oxygen reduction reaction (ORR) in alkaline media, this PPy-CTAB-Co demonstrates a superior ORR performance when compared to that of granular PPy-Co catalyst and also a much better durability than the commercial 20 wt% Pt/C catalyst. Physiochemical characterization indicates that the enhanced ORR performance of the nanowire PPy-CTAB-Co can be attributed to the high quantity of Co-pyridinic-N groups as ORR active sites and its large specific surface area which allows to expose more active sites for facilitating oxygen reduction reaction. It is expected this PPy-CTAB-Co would be a good candidate for alkaline fuel cell cathode catalyst. PMID:26860889

  20. Novel nanowire-structured polypyrrole-cobalt composite as efficient catalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yuan, Xianxia; Li, Lin; Ma, Zhong; Yu, Xuebin; Wen, Xiufang; Ma, Zi-Feng; Zhang, Lei; Wilkinson, David P.; Zhang, Jiujun

    2016-02-01

    A novel nanowire-structured polypyrrole-cobalt composite, PPy-CTAB-Co, is successfully synthesized with a surfactant of cetyltrimethylammounium bromide (CTAB). As an electro-catalyst towards oxygen reduction reaction (ORR) in alkaline media, this PPy-CTAB-Co demonstrates a superior ORR performance when compared to that of granular PPy-Co catalyst and also a much better durability than the commercial 20 wt% Pt/C catalyst. Physiochemical characterization indicates that the enhanced ORR performance of the nanowire PPy-CTAB-Co can be attributed to the high quantity of Co-pyridinic-N groups as ORR active sites and its large specific surface area which allows to expose more active sites for facilitating oxygen reduction reaction. It is expected this PPy-CTAB-Co would be a good candidate for alkaline fuel cell cathode catalyst.

  1. First principles based mean field model for oxygen reduction reaction.

    PubMed

    Jinnouchi, Ryosuke; Kodama, Kensaku; Hatanaka, Tatsuya; Morimoto, Yu

    2011-12-21

    A first principles-based mean field model was developed for the oxygen reduction reaction (ORR) taking account of the coverage- and material-dependent reversible potentials of the elementary steps. This model was applied to the simulation of single crystal surfaces of Pt, Pt alloy and Pt core-shell catalysts under Ar and O(2) atmospheres. The results are consistent with those shown by past experimental and theoretical studies on surface coverages under Ar atmosphere, the shape of the current-voltage curve for the ORR on Pt(111) and the material-dependence of the ORR activity. This model suggests that the oxygen associative pathway including HO(2)(ads) formation is the main pathway on Pt(111), and that the rate determining step (RDS) is the removal step of O(ads) on Pt(111). This RDS is accelerated on several highly active Pt alloys and core-shell surfaces, and this acceleration decreases the reaction intermediate O(ads). The increase in the partial pressure of O(2)(g) increases the surface coverage with O(ads) and OH(ads), and this coverage increase reduces the apparent reaction order with respect to the partial pressure to less than unity. This model shows details on how the reaction pathway, RDS, surface coverages, Tafel slope, reaction order and material-dependent activity are interrelated. PMID:22064886

  2. Combinatorial search for oxygen reduction reaction electrocatalysts: A review

    NASA Astrophysics Data System (ADS)

    Jeon, Min Ku; Lee, Chang Hwa; Park, Geun Il; Kang, Kweon Ho

    2012-10-01

    Oxygen reduction reaction (ORR) is one of the most interesting research issues in the academia and industries due to its importance in polymer electrolyte membrane fuel cells. Development of new ORR catalysts with low cost and high activity is under intensive research, but it is a time-consuming process because of wide range of alloys to be explored. Combinatorial synthesis and high-throughput screening techniques were suggested as new experimental approaches to accelerate the ORR electrocatalyst research. The combinatorial method is focused on the synthesis of concentrated arrays and quick evaluation of the arrays via various screening techniques. In this report, the combinatorial approaches for the ORR catalyst research were reviewed based on the screening methods. Four screening techniques of optical screening, scanning electrochemical microscopy, multielectrode half cell, and multielectrode full cell were introduced as the representative ones. Other approaches were also briefly introduced. Merits and limitations of each method were discussed and representative research results of each method were shown in detail.

  3. The Pt(111)/electrolyte interface under oxygen reduction reaction conditions: an electrochemical impedance spectroscopy study.

    PubMed

    Bondarenko, Alexander S; Stephens, Ifan E L; Hansen, Heine A; Pérez-Alonso, Francisco J; Tripkovic, Vladimir; Johansson, Tobias P; Rossmeisl, Jan; Nørskov, Jens K; Chorkendorff, Ib

    2011-03-01

    The Pt(111)/electrolyte interface has been characterized during the oxygen reduction reaction (ORR) in 0.1 M HClO(4) using electrochemical impedance spectroscopy. The surface was studied within the potential region where adsorption of OH* and O* species occur without significant place exchange between the adsorbate and Pt surface atoms (0.45-1.15 V vs RHE). An equivalent electric circuit is proposed to model the Pt(111)/electrolyte interface under ORR conditions within the selected potential window. This equivalent circuit reflects three processes with different time constants, which occur simultaneously during the ORR at Pt(111). Density functional theory (DFT) calculations were used to correlate and interpret the results of the measurements. The calculations indicate that the coadsorption of ClO(4)* and Cl* with OH* is unlikely. Our analysis suggests that the two-dimensional (2D) structures formed in O(2)-free solution are also formed under ORR conditions. PMID:21244087

  4. Layered SiC Sheets: A Potential Catalyst for Oxygen Reduction Reaction

    PubMed Central

    Zhang, P.; Xiao, B. B.; Hou, X. L.; Zhu, Y. F.; Jiang, Q.

    2014-01-01

    The large-scale practical application of fuel cells cannot come true if the high-priced Pt-based electrocatalysts for oxygen reduction reaction (ORR) cannot be replaced by other efficient, low-cost, and stable electrodes. Here, based on density functional theory (DFT), we exploited the potentials of layered SiC sheets as a novel catalyst for ORR. From our DFT results, it can be predicted that layered SiC sheets exhibit excellent ORR catalytic activity without CO poisoning, while the CO poisoning is the major drawback in conventional Pt-based catalysts. Furthermore, the layered SiC sheets in alkaline media has better catalytic activity than Pt(111) surface and have potential as a metal-free catalyst for ORR in fuel cells. PMID:24448069

  5. Combinatorial density functional theory-based screening of surface alloys for the oxygen reduction reaction.

    SciTech Connect

    Greeley, J.; Norskov, J.; Center for Nanoscale Materials; Technical Univ. of Denmark

    2009-03-26

    A density functional theory (DFT) -based, combinatorial search for improved oxygen reduction reaction (ORR) catalysts is presented. A descriptor-based approach to estimate the ORR activity of binary surface alloys, wherein alloying occurs only in the surface layer, is described, and rigorous, potential-dependent computational tests of the stability of these alloys in aqueous, acidic environments are presented. These activity and stability criteria are applied to a database of DFT calculations on nearly 750 binary transition metal surface alloys; of these, many are predicted to be active for the ORR but, with few exceptions, they are found to be thermodynamically unstable in the acidic environments typical of low-temperature fuel cells. The results suggest that, absent other thermodynamic or kinetic mechanisms to stabilize the alloys, surface alloys are unlikely to serve as useful ORR catalysts over extended periods of operation.

  6. Heterocarbon nanosheets incorporating iron phthalocyanine for oxygen reduction reaction in both alkaline and acidic media.

    PubMed

    Hyun, Koangyong; Ueno, Tomonaga; Panomsuwan, Gasidit; Li, Oi Lun; Saito, Nagahiro

    2016-04-28

    Heterocarbon nanosheets incorporating iron phthalocyanine (FP-NCNs-SP) have been successfully synthesized by a facile one-pot solution plasma process at high repetition frequency. It was found that the Fe-N4 catalytic active sites could be preserved on the FP-NCNs-SP without degradation. The FP-NCNs-SP also possessed large surface area, good conductivity and high degree of graphitization. Electrochemical evaluations demonstrated that NCNs-SP had excellent electrocatalytic activity and selectivity toward oxygen reduction reaction (ORR) in alkaline medium through a direct four-electron pathway. Although the significant improvement in ORR activity was clearly observed in acidic medium, it was much poorer than in alkaline medium. We believe that the results presented in this work will shed light on the advanced synthesis and design of ORR electrocatalysts at room temperature with an abundance of catalytically active sites and high ORR performance. PMID:27055883

  7. Synergy among transition element, nitrogen, and carbon for oxygen reduction reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Li, Zhou Peng; Liu, Zi Xuan; Zhu, Kun Ning; Li, Zhuo; Liu, Bin Hong

    2012-12-01

    A series of M-doped polypyrrole (PPy)-modified BP2000 catalysts (M = Mn, Fe, Co, Ni, and Cu) are synthesized using the hydrothermal method. The synergy among a transition element, nitrogen, and carbon for oxygen reduction reaction (ORR) in alkaline medium is discussed based on the physical characterization and electrochemical analyses of the Co-doped PPy-modified BP2000. PPy is found to adhere carbon black particles together to form a porous 3D network during the PPy modification on BP2000. PPy reconfiguration occurs during the hydrothermal treatment process. The individual interactions between BP and PPy, BP and Co, and Co and PPy exhibit insignificant effects on the enhancement of ORR. The cooperative interaction among Co, N, and C plays a very important role in the enhancement of ORR. The doping effect of transition-metal salt on ORR enhancement depends on the nature of the transition element and the corresponding anion.

  8. Layered SiC Sheets: A Potential Catalyst for Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Zhang, P.; Xiao, B. B.; Hou, X. L.; Zhu, Y. F.; Jiang, Q.

    2014-01-01

    The large-scale practical application of fuel cells cannot come true if the high-priced Pt-based electrocatalysts for oxygen reduction reaction (ORR) cannot be replaced by other efficient, low-cost, and stable electrodes. Here, based on density functional theory (DFT), we exploited the potentials of layered SiC sheets as a novel catalyst for ORR. From our DFT results, it can be predicted that layered SiC sheets exhibit excellent ORR catalytic activity without CO poisoning, while the CO poisoning is the major drawback in conventional Pt-based catalysts. Furthermore, the layered SiC sheets in alkaline media has better catalytic activity than Pt(111) surface and have potential as a metal-free catalyst for ORR in fuel cells.

  9. Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 2

    NASA Astrophysics Data System (ADS)

    Pech-Pech, I. E.; Gervasio, Dominic F.; Pérez-Robles, J. F.

    2015-02-01

    In the first part of this work, the feasibility of developing a catalyst with high activity for the oxygen electroreduction reaction (ORR) in acid media and with low Pt loading was demonstrated by over coating a silver (Ag) nanoparticle with a shell of platinum (Pt) and palladium (Pd) [7]. The results show that best activity is not directly related to a higher PtPd loading on the surface of the Ag. The best catalyst in a series of this type of catalyst is found with Ag@Pt0.3Pd0.3/C which gives a specific activity for oxygen reduction, jk (in units of mA cm-2 of real area), of 0.07 mA cm-2 at 0.85 V vs. NHE, as compared to 0.04 mA cm-2 when with a commercial Pt on carbon catalyst (Pt20/C) is used in an identical electrode except for the catalyst. The mass activity, jm (in units of mA μg-1 of Pt), for Ag@Pt0.3Pd0.3/C is 0.04 mA μg-1 of Pt at 0.85 V vs. NHE, whereas that for the Pt20/C gives 0.02 mA μg-1 of Pt, showing Ag@Pt0.3Pd0.3/C is a lower-cost catalyst, because using a Ag core and Pd with Pt in the shell gives the highest catalytic activity using less Pt.

  10. Recent Advances in Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol; Chenitz, Regis

    2016-03-23

    The recent advances in electrocatalysis for oxygen reduction reaction (ORR) for proton exchange membrane fuel cells (PEMFCs) are thoroughly reviewed. This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core-shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts, and metal-free catalysts. The recent development of ORR electrocatalysts with novel structures and compositions is highlighted. The understandings of the correlation between the activity and the shape, size, composition, and synthesis method are summarized. For the carbon-based materials, their performance and stability in fuel cells and comparisons with those of platinum are documented. The research directions as well as perspectives on the further development of more active and less expensive electrocatalysts are provided. PMID:26886420

  11. Bioinspired synthesis of nitrogen/sulfur co-doped graphene as an efficient electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Huanhuan; Liu, Xiangqian; He, Guangli; Zhang, Xiaoxing; Bao, Shujuan; Hu, Weihua

    2015-04-01

    Efficient electrocatalyst of oxygen reduction reaction (ORR) is crucial for a variety of renewable energy applications and heteroatom-doped carbon materials have demonstrated promising catalytic performance towards ORR. In this paper we report a bioinspired method to synthesize nitrogen/sulfur (N/S) co-doped graphene as an efficient ORR electrocatalyst via self-polymerization of polydopamine (PDA) thin layer on graphene oxide sheets, followed by reacting with cysteine and finally thermal annealing in Argon (Ar) atmosphere. As-prepared N/S co-doped graphene exhibits significantly enhanced ORR catalytic activity in alkaline solution compared with pristine graphene or N-doped graphene. It also displays long-term operation stability and strong tolerance to methanol poison effect, indicating it a promising ORR electrocatalyst.

  12. Palladium and gold nanotubes as oxygen reduction reaction and alcohol oxidation reaction catalysts in base.

    PubMed

    Alia, Shaun M; Duong, Kathlynne; Liu, Toby; Jensen, Kurt; Yan, Yushan

    2014-06-01

    Palladium (PdNTs) and gold nanotubes (AuNTs) were synthesized by the galvanic displacement of silver nanowires. PdNTs and AuNTs have wall thicknesses of 6 nm, outer diameters of 60 nm, and lengths of 5-10 and 5-20 μm, respectively. Rotating disk electrode experiments showed that the PdNTs and AuNTs have higher area normalized activities for the oxygen reduction reaction (ORR) than conventional nanoparticle catalysts. The PdNTs produced an ORR area activity that was 3.4, 2.2, and 3.7 times greater than that on carbon-supported palladium nanoparticles (Pd/C), bulk polycrystalline palladium, and carbon-supported platinum nanoparticles (Pt/C), respectively. The AuNTs produced an ORR area activity that was 2.3, 9.0, and 2.0 times greater than that on carbon-supported gold nanoparticles (Au/C), bulk polycrystalline gold, and Pt/C, respectively. The PdNTs also had lower onset potentials than Pd/C and Pt/C for the oxidation of methanol (0.236 V), ethanol (0.215 V), and ethylene glycol (0.251 V). In comparison to Pt/C, the PdNTs and AuNTs further demonstrated improved alcohol tolerance during the ORR. PMID:24757078

  13. Screening of catalytic oxygen reduction reaction activity of metal-doped graphene by density functional theory

    NASA Astrophysics Data System (ADS)

    Chen, Xin; Chen, Shuangjing; Wang, Jinyu

    2016-08-01

    Graphene doping is a promising direction for developing effective oxygen reduction reaction (ORR) catalysts. In this paper, we computationally investigated the ORR performance of 10 kinds of metal-doped graphene (M-G) catalysts, namely, Al-, Si-, Mn-, Fe-, Co-, Ni-, Pd-, Ag-, Pt-, and Au-G. The results shown that the binding energies of the metal atoms incorporated into the graphene vacancy are higher than their bulk cohesive energies, indicating the formed M-G catalysts are even more stable than the corresponding bulk metal surfaces, and thus avoid the metals dissolution in the reaction environment. We demonstrated that the linear relation among the binding energies of the ORR intermediates that found on metal-based materials does not hold for the M-G catalysts, therefore a single binding energy of intermediate alone is not sufficient to evaluate the ORR activity of an arbitrary catalyst. By analysis of the detailed ORR processes, we predicted that the Au-, Co-, and Ag-G materials can be used as the ORR catalysts.

  14. The Mechanisms of Oxygen Reduction and Evolution Reactions in Nonaqueous Lithium-Oxygen Batteries

    SciTech Connect

    Cao, Ruiguo; Walter, Eric D.; Xu, Wu; Nasybulin, Eduard N.; Bhattacharya, Priyanka; Bowden, Mark E.; Engelhard, Mark H.; Zhang, Jiguang

    2014-09-01

    The oxygen reduction/evolution reaction (ORR/OER) mechanisms in nonaqueous Li-O2 batteries have been investigated by using electron paramagnetic resonance spectroscopy in this work. We identified the superoxide radical anion (O2•-) as an intermediate in the ORR process using 5,5-dimethyl-pyrroline N-oxide as a spin trap, while no O2•- in OER was detected during the charge process. These findings provide insightful understanding on the fundamental oxygen reaction mechanisms in rechargeable nonaqueous Li-O2 batteries.

  15. Some reflections on the understanding of the oxygen reduction reaction at Pt(111)

    PubMed Central

    Gómez-Marín, Ana M; Rizo, Ruben

    2013-01-01

    Summary The oxygen reduction reaction (ORR) is a pivotal process in electrochemistry. Unfortunately, after decades of intensive research, a fundamental knowledge about its reaction mechanism is still lacking. In this paper, a global and critical view on the most important experimental and theoretical results regarding the ORR on Pt(111) and its vicinal surfaces, in both acidic and alkaline media, is taken. Phenomena such as the ORR surface structure sensitivity and the lack of a reduction current at high potentials are discussed in the light of the surface oxidation and disordering processes and the possible relevance of the hydrogen peroxide reduction and oxidation reactions in the ORR mechanism. The necessity to build precise and realistic reaction models, which are deducted from reliable experimental results that need to be carefully taken under strict working conditions is shown. Therefore, progress in the understanding of this important reaction on a molecular level, and the choice of the right approach for the design of the electrocatalysts for fuel-cell cathodes is only possible through a cooperative approach between theory and experiments. PMID:24455454

  16. Some reflections on the understanding of the oxygen reduction reaction at Pt(111).

    PubMed

    Gómez-Marín, Ana M; Rizo, Ruben; Feliu, Juan M

    2013-12-27

    The oxygen reduction reaction (ORR) is a pivotal process in electrochemistry. Unfortunately, after decades of intensive research, a fundamental knowledge about its reaction mechanism is still lacking. In this paper, a global and critical view on the most important experimental and theoretical results regarding the ORR on Pt(111) and its vicinal surfaces, in both acidic and alkaline media, is taken. Phenomena such as the ORR surface structure sensitivity and the lack of a reduction current at high potentials are discussed in the light of the surface oxidation and disordering processes and the possible relevance of the hydrogen peroxide reduction and oxidation reactions in the ORR mechanism. The necessity to build precise and realistic reaction models, which are deducted from reliable experimental results that need to be carefully taken under strict working conditions is shown. Therefore, progress in the understanding of this important reaction on a molecular level, and the choice of the right approach for the design of the electrocatalysts for fuel-cell cathodes is only possible through a cooperative approach between theory and experiments. PMID:24455454

  17. Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

    SciTech Connect

    Ham, Hyung Chul; Hwang, Gyeong S.; Manogaran, Dhivya; Lee, Kang Hee; Jin, Seon-ah; You, Dae Jong; Pak, Chanho; Kwon, Kyungjung

    2013-11-28

    Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd{sub 3}Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd{sub 3}Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts.

  18. Reduction of chemical reaction models

    NASA Technical Reports Server (NTRS)

    Frenklach, Michael

    1991-01-01

    An attempt is made to reconcile the different terminologies pertaining to reduction of chemical reaction models. The approaches considered include global modeling, response modeling, detailed reduction, chemical lumping, and statistical lumping. The advantages and drawbacks of each of these methods are pointed out.

  19. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    SciTech Connect

    Nandan, Ravi Nanda, Karuna Kar

    2015-06-24

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min{sup −1}. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  20. Structure-activity relationship in high-performance iron-based electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Song, Ping; Wang, Ying; Pan, Jing; Xu, Weilin; Zhuang, Lin

    2015-12-01

    A sustainable Iron (Fe), Nitrogen (N) co-doped high performance Fe-Nx/C electrocatalyst for oxygen reduction reaction (ORR) is synthesized simply based on nitric acid oxidation of cheap carbon black. The obtained optimal nonprecious metal electrocatalyst shows high ORR performance in both alkaline and acidic conditions and possesses appreciable performance/price ratio due to its low cost. Furthermore, the structure-activity relationship of different active sites on Fe-Nx/C is revealed systematically: Fe-N4/2-C > Fe4-N-C > N-C >> Fe4-C ≥ C, from both experimental and theoretical points of view.

  1. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Nandan, Ravi; Nanda, Karuna Kar

    2015-06-01

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min-1. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  2. Electrochemical activation of commercial polyacrylonitrile-based carbon fiber for the oxygen reduction reaction.

    PubMed

    Xu, Haibo; Xia, Guangsen; Liu, Haining; Xia, Shuwei; Lu, Yonghong

    2015-03-28

    Nitrogen (N)-doped carbon and its non-noble metal composite replacing platinum-based oxygen reduction reaction (ORR) electrocatalysts still have some fundamental problems that remain. Here the micron-sized commercial polyacrylonitrile-based carbon fiber (PAN-CF) electrode was modified using an electrochemical method, converting its inherent pyridinic-N into 2-pyridone (or 2-hydroxyl pyridine) functional group existing in three-dimensional active layers with remarkable ORR catalytic activity and stability. The carbon atom adjacent to the nitrogen and oxygen atoms is prone to act as an active site to efficiently catalyze a two-electron ORR process. However, after coordinating pyridone to the Cu(2+) ion, together with the electrochemical reaction, the chemical redox between Cu(+) and ORR intermediates synergistically tends towards a four-electron pathway in alkaline solution. In different medium, the complexation and dissociation can induce the charge transfer and reconstruction among proton, metal ion and pyridone functionalities, eventually leading to the changes of ORR performance. PMID:25712410

  3. Carbonization of self-assembled nanoporous hemin with a significantly enhanced activity for the oxygen reduction reaction.

    PubMed

    Xie, Yan; Tang, Chizhou; Hao, Zhiqiang; Lv, Yang; Yang, Ruixia; Wei, Xuming; Deng, Weiqiao; Wang, Anjie; Yi, Baolian; Song, Yujiang

    2014-01-01

    The scarcity and high cost of Pt-based electrocatalysts for the oxygen reduction reaction (ORR) hinder the practical application of proton exchange membrane fuel cells (PEMFCs). It is critical to replace platinum with non-noble metal electrocatalysts (NNMEs). Carbonized metalloporphyrins represent an important class of NNMEs, but most metalloporphyrins are costly and the corresponding NNMEs do not possess a high ORR activity. Herein, we report that the self-assembly of inexpensive hemin leads to porous nanomaterials in water under ambient conditions and subsequent heat-treatment of the unprecedented nanoporous hemin results in a magnetic NNME with a much enhanced ORR activity compared with directly carbonized hemin without self-assembly. The improvement of the ORR activity likely originates from the exposure of more ORR active sites, caused by the surface area increase of the nanoporous hemin after carbonization over that of micro-scale pristine hemin crystals. Moreover, the ORR activity of heat-treated nanoporous hemin is actually comparable to that of commercial Pt/C in alkaline solution. Additionally, the carbonized nanoporous hemin is much better than commercial Pt/C in terms of durability and tolerance to methanol. This study opens up a new avenue to the production of inexpensive metalloporphyrin-based NNMEs with a high ORR performance by using a self-assembly method in combination with traditional pyrolysis. PMID:25406677

  4. Oxygen reduction reaction in a droplet on graphite: direct evidence that the edge is more active than the basal plane.

    PubMed

    Shen, Anli; Zou, Yuqin; Wang, Qiang; Dryfe, Robert A W; Huang, Xiaobing; Dou, Shuo; Dai, Liming; Wang, Shuangyin

    2014-09-26

    Carbon-based metal-free electrocatalysts for the oxygen reduction reaction (ORR) in alkaline medium have been extensively investigated with the aim of replacing the commercially available, but precious platinum-based catalysts. For the proper design of carbon-based metal-free electrocatalysts for the ORR, it would be interesting to identify the active sites of the electrocatalyst. The ORR was now studied with an air-saturated electrolyte solution droplet (diameter ca. 15 μm), which was deposited at a specified position either on the edge or on the basal plane of highly oriented pyrolytic graphite. Electrochemical measurements suggest that the edge carbon atoms are more active than the basal-plane ones for the ORR. This provides a direct way to identify the active sites of carbon materials for the ORR. Ball-milled graphite and carbon nanotubes with more exposed edges were also prepared and showed significantly enhanced ORR activity. DFT calculations elucidated the mechanism by which the charged edge carbon atoms result in the higher ORR activity. PMID:25124986

  5. Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation

    NASA Astrophysics Data System (ADS)

    Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.; Kocha, Shyam S.

    2016-09-01

    The impact of Nafion on the oxygen reduction reaction (ORR) activity is studied for Pt/C and Pt-alloy/C catalysts using thin-film rotating disk electrode (TF-RDE) methods in 0.1 M HClO4. Ultrathin uniform catalyst layers and standardized activity measurement protocols are employed to obtain accurate and reproducible ORR activity. Nafion lowers the ORR activity which plateaus with increasing loading on Pt catalysts. Pt particle size is found not to have significant influence on the extent of the SA decrease upon Nafion incorporation. Catalysts using high surface area carbon (HSC) support exhibit attenuated activity loss resulting from lower ionomer coverage on catalyst particles located within the deep pores. The impact of metallic composition on the activity loss due to Nafion incorporation is also discussed.

  6. Catalytic activity trends of oxygen reduction reaction for nonaqueous Li-air batteries.

    PubMed

    Lu, Yi-Chun; Gasteiger, Hubert A; Shao-Horn, Yang

    2011-11-30

    We report the intrinsic oxygen reduction reaction (ORR) activity of polycrystalline palladium, platinum, ruthenium, gold, and glassy carbon surfaces in 0.1 M LiClO(4) 1,2-dimethoxyethane via rotating disk electrode measurements. The nonaqueous Li(+)-ORR activity of these surfaces primarily correlates to oxygen adsorption energy, forming a "volcano-type" trend. The activity trend found on the polycrystalline surfaces was in good agreement with the trend in the discharge voltage of Li-O(2) cells catalyzed by nanoparticle catalysts. Our findings provide insights into Li(+)-ORR mechanisms in nonaqueous media and design of efficient air electrodes for Li-air battery applications. PMID:22044022

  7. Nitrogen doped carbon nanotubes with encapsulated ferric carbide as excellent electrocatalyst for oxygen reduction reaction in acid and alkaline media

    NASA Astrophysics Data System (ADS)

    Zhong, Guoyu; Wang, Hongjuan; Yu, Hao; Peng, Feng

    2015-07-01

    Nitrogen doped carbon nanotubes (NCNTs) with encapsulated Fe3C nanoparticles (Fe3C@NCNTs) are synthesized by a simple direct pyrolysis of melamine and ferric chloride. The characterization results reveal that Fe3C is mainly encapsulated in the interior of NCNTs and N species is mainly distributed on the outside surface of NCNTs. Iron and iron carbide catalyze the growth of NCNTs and are wrapped by carbon to form Fe3C@NCNTs. The as-prepared Fe3C@NCNTs catalyst exhibits superior oxygen reduction reaction (ORR) activity, excellent methanol tolerance and long-term stability in both acid and alkaline media. It is proven that the doped N is the main active site for ORR and the inner Fe3C with outside carbon form the synergetic active site to enhance ORR activity. The ORR mechanism of direct four electron transfer pathway is proved in acid and alkaline media.

  8. Structural Origin of the Activity in Mn3O4-Graphene Oxide Hybrid Electrocatalysts for the Oxygen Reduction Reaction.

    PubMed

    Wu, Kuang-Hsu; Zeng, Qingcong; Zhang, Bingsen; Leng, Xue; Su, Dang-Sheng; Gentle, Ian R; Wang, Da-Wei

    2015-10-12

    Non-precious metal oxide/carbon hybrid electrocatalysts are of increasing importance for the oxygen reduction reaction (ORR). A synergistic effect is commonly used to explain the superior ORR activity exerted by metal oxide/nanocarbon hybrids, and this effect is attributed to covalently coupled interfaces between the two materials. However, the origin of the high activity, the structure, and the electrocatalytic nature of the interface remain unclear. By combining X-ray photoelectron spectroscopy with synchrotron far-infrared spectroscopy, we resolved the interface structure between spinel manganese oxide nanocrystals and graphene oxide nanoribbons, and the role of this interface in the promoted ORR. Moreover, we demonstrated the excellent ORR activity by a functional synergism of the hybrid constituents through a series of comparative electrochemical experiments. PMID:26448527

  9. Surface Structure Dependent Electrocatalytic Activity of Co3O4 Anchored on Graphene Sheets toward Oxygen Reduction Reaction

    PubMed Central

    Xiao, Junwu; Kuang, Qin; Yang, Shihe; Xiao, Fei; Wang, Shuai; Guo, Lin

    2013-01-01

    Catalytic activity is primarily a surface phenomenon, however, little is known about Co3O4 nanocrystals in terms of the relationship between the oxygen reduction reaction (ORR) catalytic activity and surface structure, especially when dispersed on a highly conducting support to improve the electrical conductivity and so to enhance the catalytic activity. Herein, we report a controllable synthesis of Co3O4 nanorods (NR), nanocubes (NC) and nano-octahedrons (OC) with the different exposed nanocrystalline surfaces ({110}, {100}, and {111}), uniformly anchored on graphene sheets, which has allowed us to investigate the effects of the surface structure on the ORR activity. Results show that the catalytically active sites for ORR should be the surface Co2+ ions, whereas the surface Co3+ ions catalyze CO oxidation, and the catalytic ability is closely related to the density of the catalytically active sites. These results underscore the importance of morphological control in the design of highly efficient ORR catalysts. PMID:23892418

  10. Evaluation of the catalytic activity of Pd-Ag alloys on ethanol oxidation and oxygen reduction reactions in alkaline medium

    NASA Astrophysics Data System (ADS)

    Oliveira, M. C.; Rego, R.; Fernandes, L. S.; Tavares, P. B.

    2011-08-01

    Pd-Ag alloys containing different amounts of Ag (8, 21 and 34 at.%) were prepared in order to evaluate their catalytic activity towards the ethanol oxidation (EOR) and oxygen reduction (ORR) reactions. A sequential electroless deposition of Ag and Pd on a stainless steel disc, followed by annealing at 650 °C under Ar stream, was used as the alloy electrode deposition process. From half-cell measurements in a 1.0 M NaOH electrolyte at ≅20 °C, it was found that alloying Pd with Ag leads to an increases of the ORR and EOR kinetics, relative to Pd. Among the alloys under study, the 21 at.% Ag content alloy presents the highest catalytic activity for the EOR and the lowest Ag content alloy (8 at.% Ag) shows the highest ORR activity. Moreover, it was found that the selectivity of Pd-Ag alloys towards ORR is sustained when ethanol is present in the electrolyte.

  11. 3,4-Ethylenedioxythiophene functionalized graphene with palladium nanoparticles for enhanced electrocatalytic oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Choe, Ju Eun; Ahmed, Mohammad Shamsuddin; Jeon, Seungwon

    2015-05-01

    Poly(3,4-ethylenedioxythiophene) functionalized graphene with palladium nanoparticles (denoted as Pd/PEDOT/rGO) has been synthesized for electrochemical oxygen reduction reaction (ORR) in alkaline solution. The structural features of catalyst are characterized by scanning electron microscopy, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The TEM images suggest a well dispersed PdNPs onto PEDOT/rGO film. The ORR activity of Pd/PEDOT/rGO has been investigated via cyclic voltammetry (CV), rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) techniques in 0.1 M KOH aqueous solution. Comparative CV analysis suggests a general approach of intermolecular charge-transfer in between graphene sheet and PdNPs via PEDOT which leads to the better PdNPs dispersion and subsequently superior ORR kinetics. The results from ORR measurements show that Pd/PEDOT/rGO has remarkable electrocatalytic activity and stability compared to Pd/rGO and state-of-the-art Pt/C. The Koutecky-Levich and Tafel analysis suggest that the proposed main path in the ORR mechanism has direct four-electron transfer process with faster transfer kinetic rate on the Pd/PEDOT/rGO.

  12. Effect of mass transfer on the oxygen reduction reaction catalyzed by platinum dendrimer encapsulated nanoparticles

    PubMed Central

    Dumitrescu, Ioana; Crooks, Richard M.

    2012-01-01

    Here we report on the effect of the mass transfer rate (kt) on the oxygen reduction reaction (ORR) catalyzed by Pt dendrimer-encapsulated nanoparticles (DENs) comprised of 147 and 55 atoms (Pt147 and Pt55). The experiments were carried out using a dual-electrode microelectrochemical device, which enables the study of the ORR under high kt conditions with simultaneous detection of H2O2. At low kt (0.02 to 0.12 cm s-1) the effective number of electrons involved in ORR, neff, is 3.7 for Pt147 and 3.4 for Pt55. As kt is increased, the mass-transfer-limited current for the ORR becomes significantly lower than the value predicted by the Levich equation for a 4-electron process regardless of catalyst size. However, the percentage of H2O2 detected remains constant, such that neff barely changes over the entire kt range explored (0.02 cm s-1). This suggests that mass transfer does not affect neff, which has implications for the mechanism of the ORR on Pt nanoparticles. Interestingly, there is a significant difference in neff for the two sizes of Pt DENs (neff = 3.7 and 3.5 for Pt147 and Pt55, respectively) that cannot be assigned to mass transfer effects and that we therefore attribute to a particle size effect. PMID:22665772

  13. Theoretical predictions for hexagonal BN based nanomaterials as electrocatalysts for the oxygen reduction reaction.

    PubMed

    Lyalin, Andrey; Nakayama, Akira; Uosaki, Kohei; Taketsugu, Tetsuya

    2013-02-28

    The catalytic activity for the oxygen reduction reaction (ORR) of both the pristine and defect-possessing hexagonal boron nitride (h-BN) monolayer and H-terminated nanoribbon have been studied theoretically using density functional theory. It is demonstrated that an inert h-BN monolayer can be functionalized and become catalytically active by nitrogen doping. It is shown that the energetics of adsorption of O(2), O, OH, OOH, and H(2)O on N atom impurities in the h-BN monolayer (N(B)@h-BN) is quite similar to that known for a Pt(111) surface. The specific mechanism of destructive and cooperative adsorption of ORR intermediates on the surface point defects is discussed. It is demonstrated that accounting for entropy and zero-point energy (ZPE) corrections results in destabilization of the ORR intermediates adsorbed on N(B)@h-BN, while solvent effects lead to their stabilization. Therefore, entropy, ZPE and solvent effects partly cancel each other and have to be taken into account simultaneously. Analysis of the free energy changes along the ORR pathway allows us to suggest that a N-doped h-BN monolayer can demonstrate catalytic properties for the ORR under the condition that electron transport to the catalytically active center is provided. PMID:23338859

  14. Carbonized nanoscale metal-organic frameworks as high performance electrocatalyst for oxygen reduction reaction.

    PubMed

    Zhao, Shenlong; Yin, Huajie; Du, Lei; He, Liangcan; Zhao, Kun; Chang, Lin; Yin, Geping; Zhao, Huijun; Liu, Shaoqin; Tang, Zhiyong

    2014-12-23

    The oxygen reduction reaction (ORR) is one of the key steps in clean and efficient energy conversion techniques such as in fuel cells and metal-air batteries; however, several disadvantages of current ORRs including the kinetically sluggish process and expensive catalysts hinder mass production of these devices. Herein, we develop carbonized nanoparticles, which are derived from monodisperse nanoscale metal organic frameworks (MIL-88B-NH3), as the high performance ORR catalysts. The onset potential and the half-wave potential for the ORR at these carbonized nanoparticles is up to 1.03 and 0.92 V (vs RHE) in 0.1 M KOH solution, respectively, which represents the best ORR activity of all the non-noble metal catalysts reported so far. Furthermore, when used as the cathode of the alkaline direct fuel cell, the power density obtained with the carbonized nanoparticles reaches 22.7 mW/cm2, 1.7 times higher than the commercial Pt/C catalysts. PMID:25426850

  15. Oxygen reduction reaction on Cu-doped Ag cluster for fuel-cell cathode.

    PubMed

    Ma, Wenqiang; Chen, Fuyi; Zhang, Nan; Wu, Xiaoqiang

    2014-10-01

    The development of fuel cells as clean-energy technologies is largely limited by the prohibitive cost of the noble-metal catalysts needed for catalyzing the oxygen reduction reaction (ORR) in fuel cells. A fundamental understanding of catalyst design principle that links material structures to the catalytic activity can accelerate the search for highly active and abundant bimetallic catalysts to replace platinum. Here, we present a first-principles study of ORR on Ag12Cu cluster in alkaline environment. The adsorptions of O2, OOH, and OH on Cu-doped Ag13 are stronger than on Ag13. The d-band centers of adsorption sites show the Cu-doping makes d-electrons transferred to higher energy state, and improves O2 dissociation. ORR processes on Ag12Cu and Ag13 indicate Cu-doping can strongly promote ORR, and ORR process can be better preformed on Ag12Cu than on Ag13. For four-electron transfer, the effective reversible potential is 0.401 V/RHE on Ag12Cu in alkaline medium. PMID:25227449

  16. Ultrathin Icosahedral Pt-Enriched Nanocage with Excellent Oxygen Reduction Reaction Activity.

    PubMed

    He, Dong Sheng; He, Daping; Wang, Jing; Lin, Yue; Yin, Peiqun; Hong, Xun; Wu, Yuen; Li, Yadong

    2016-02-10

    Cost-efficient utilization of Pt in the oxygen reduction reaction (ORR) is of great importance for the potential industrial scale demand of proton-exchange membrane fuel cells. Designing a hollow structure of a Pt catalyst offers a great opportunity to enhance the electrocatalytic performance and maximize the use of precious Pt. Herein we report a routine to synthesize ultrathin icosahedral Pt-enriched nanocages. In detail, the Pt atoms were conformally deposited on the surface of Pd icosahedral seeds, followed by selective removal of the Pd core by a concentrated HNO3 solution. The icosahedral Pt-enriched nanocage that is a few atomic layers thick includes the merits of abundant twin defects, an ultrahigh surface/volume ratio, and an ORR-favored Pt{111} facet, all of which have been demonstrated to be promoting factors for ORR. With a 10 times higher specific activity and 7 times higher mass activity, this catalyst shows more extraordinary ORR activity than the commercial Pt/C. The ORR activity of icosahedral Pt-enriched nanocages outperforms the cubic and octahedral nanocages reported in the literature, demonstrating the superiority of the icosahedral nanocage structure. PMID:26808073

  17. Oxygen reduction reaction on stepped platinum surfaces in alkaline media.

    PubMed

    Rizo, Ruben; Herrero, Enrique; Feliu, Juan M

    2013-10-01

    The oxygen reduction reaction (ORR) in 0.1 M NaOH on platinum single crystal electrodes has been studied using hanging meniscus rotating disk electrode configuration. Basal planes and stepped surfaces with (111) and (100) terraces have been employed. The results indicate that the Pt(111) electrode has the highest electrocatalytic activity among all the studied surfaces. The addition of steps on this electrode surface significantly diminishes the reactivity of the surface towards the ORR. In fact, the reactivity of the steps on the surfaces with wide terraces can be considered negligible with respect to that measured for the terrace. On the other hand, Pt(100) and Pt(110) electrodes have much lower activity than the Pt(111) electrode. These results have been compared with those obtained in acid media to understand the effect of the pH and the adsorbed OH on the mechanism. It is proposed that the surface covered by adsorbed OH is active for the reduction of the oxygen molecules. PMID:23936903

  18. Creation of Ge-Nx-Cy Configures in Carbon Nanotubes: Origin of Enhanced Electrocatalytic Performance for Oxygen Reduction Reaction.

    PubMed

    She, Xilin; Li, Qianqian; Ma, Na; Sun, Jin; Jing, Dengwei; Chen, Chengmeng; Yang, Lijun; Yang, Dongjiang

    2016-04-27

    High-performance nitrogen and germanium codoped carbon nanotubes (N-Ge-CNTs) were synthesized as oxygen reduction reaction (ORR) catalysts by one-step sintering of carboxyethyl germanium sesquioxide and multiwalled CNTs in NH3 atmosphere. The ORR electrocatalytic activity evaluation was performed by using limited current density, selective reaction pathway, onset potential, H2O2 yields, and kinetic current density. In comparison with Ge or N solely doped CNTs, the codoped samples display more excellent ORR catalytic performance. It was observed that the codoped GeN3C, GeN4, and GeN4 + NC3 microstructures in N-Ge-CNTs are crucial to improving ORR catalytic performance, such as ideal 4 electron pathway (3.95) and positive onset potential (-0.08 V). The high ORR performance is attributed to the synergistic effect of N and Ge doping, which is capable of activating the π electrons of sp(2) hybridized orbital around carbon nantotubes. The ORR catalytic synergistic effect has also been verified by calculating the work function on the basis of density functional theory (DFT). PMID:27077893

  19. Easy conversion of protein-rich enoki mushroom biomass to a nitrogen-doped carbon nanomaterial as a promising metal-free catalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Guo, Chaozhong; Liao, Wenli; Li, Zhongbin; Sun, Lingtao; Chen, Changguo

    2015-09-01

    The search for low-cost, highly active, and stable catalysts to replace the Pt-based catalysts for oxygen reduction reaction (ORR) has recently become a topic of interest. Herein, we report a new strategy to design a nitrogen-doped carbon nanomaterial for use as a metal-free ORR catalyst based on facile pyrolysis of protein-rich enoki mushroom (Flammulina velutipes) biomass at 900 °C with carbon nanotubes as a conductive agent and inserting matrix. We found that various forms of nitrogen (nitrile, pyrrolic and graphitic) were incorporated into the carbon molecular skeleton of the product, which exhibited more excellent ORR electrocatalytic activity and better durability in alkaline medium than those in acidic medium. Remarkably, the ORR half-wave potential measured on our material was around 0.81 V in alkaline medium, slightly lower than that on the commercial 20 wt% Pt/C catalyst (0.86 V). Meanwhile, the ORR followed the desired 4-electron transfer mechanism involving the direct reduction pathway. The ORR performance was also markedly better than or at least comparable to the leading results in the literature based on biomass-derived carbon-based catalysts. Besides, we significantly proposed that the graphitic-nitrogen species that is most responsible for the ORR activity can function as the electrocatalytically active center for ORR, and the pyrrolic-nitrogen species can act as an effective promoter for ORR only. The results suggested a promising route based on economical and sustainable fungi biomass towards the large-scale production of valuable carbon nanomaterials as highly active and stable metal-free catalysts for ORR under alkaline conditions.The search for low-cost, highly active, and stable catalysts to replace the Pt-based catalysts for oxygen reduction reaction (ORR) has recently become a topic of interest. Herein, we report a new strategy to design a nitrogen-doped carbon nanomaterial for use as a metal-free ORR catalyst based on facile pyrolysis of

  20. Hydrothermal synthesis of vanadium nitride and modulation of its catalytic performance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Huang, Taizhong; Mao, Shun; Zhou, Guihua; Wen, Zhenhai; Huang, Xingkang; Ci, Suqin; Chen, Junhong

    2014-07-01

    A creative hydrothermal synthesis method followed by calcination for vanadium nitride (VN) is reported. The oxygen reduction reaction (ORR) study of the catalyst shows that VN possesses a comparable catalytic performance to commercial Pt/C catalyst. The ORR catalytic activity study of vanadium nitride, vanadium carbonitride, and vanadium carbide reveals that tuning anions offers a promising route for the activity enhancement of the non-precious metal catalysts.A creative hydrothermal synthesis method followed by calcination for vanadium nitride (VN) is reported. The oxygen reduction reaction (ORR) study of the catalyst shows that VN possesses a comparable catalytic performance to commercial Pt/C catalyst. The ORR catalytic activity study of vanadium nitride, vanadium carbonitride, and vanadium carbide reveals that tuning anions offers a promising route for the activity enhancement of the non-precious metal catalysts. Electronic supplementary information (ESI) available: Experimental methods; SEM characterization of the catalysts; Tafel test of Pt/C catalyst; BET and cyclic performance tests of VN. See DOI: 10.1039/c4nr02646b

  1. Boron- and Nitrogen-Substituted Graphene Nanoribbons as Efficient Catalysts for Oxygen Reduction Reaction

    DOE PAGESBeta

    Gong, Yongji; Fei, Huilong; Zou, Xiaolong; Zhou, Wu; Yang, Shubin; Ye, Gonglan; Liu, Zheng; Peng, Zhiwei; Lou, Jun; Vajtai, Robert; et al

    2015-02-02

    Here, we show that nanoribbons of boron- and nitrogen-substituted graphene can be used as efficient electrocatalysts for the oxygen reduction reaction (ORR). Optimally doped graphene nanoribbons made into three-dimensional porous constructs exhibit the highest onset and half-wave potentials among the reported metal-free catalysts for this reaction and show superior performance compared to commercial Pt/C catalyst. Moreover, this catalyst possesses high kinetic current density and four-electron transfer pathway with low hydrogen peroxide yield during the reaction. Finally, first-principles calculations suggest that such excellent electrocatalytic properties originate from the abundant edges of boron- and nitrogen-codoped graphene nanoribbons, which significantly reduce the energymore » barriers of the rate-determining steps of the ORR reaction.« less

  2. Boron- and Nitrogen-Substituted Graphene Nanoribbons as Efficient Catalysts for Oxygen Reduction Reaction

    SciTech Connect

    Gong, Yongji; Fei, Huilong; Zou, Xiaolong; Zhou, Wu; Yang, Shubin; Ye, Gonglan; Liu, Zheng; Peng, Zhiwei; Lou, Jun; Vajtai, Robert; Yakobson, Boris I.; Tour, James M.; Ajayan, Pulickel M.

    2015-02-02

    Here, we show that nanoribbons of boron- and nitrogen-substituted graphene can be used as efficient electrocatalysts for the oxygen reduction reaction (ORR). Optimally doped graphene nanoribbons made into three-dimensional porous constructs exhibit the highest onset and half-wave potentials among the reported metal-free catalysts for this reaction and show superior performance compared to commercial Pt/C catalyst. Moreover, this catalyst possesses high kinetic current density and four-electron transfer pathway with low hydrogen peroxide yield during the reaction. Finally, first-principles calculations suggest that such excellent electrocatalytic properties originate from the abundant edges of boron- and nitrogen-codoped graphene nanoribbons, which significantly reduce the energy barriers of the rate-determining steps of the ORR reaction.

  3. New insights into the effects of alloying Pt with Ni on oxygen reduction reaction mechanisms in acid medium: a first-principles study.

    PubMed

    Ou, Li-Hui

    2015-11-01

    The effects of alloying Pt with transition metal Ni on oxygen reduction reaction (ORR) mechanisms was investigated based on a systematic density functional theory (DFT) calculation explored in the present work. New insights into the ORR mechanisms were reported at the atomic level on Pt-segregated Pt3Ni(111). Only one molecular chemisorption state with the end-on OOH configuration was identified through geometry optimization and minimum energy path (MEP) analysis; top-bridge-top configuration as observed on pure Pt(111) was not identified on Pt-segregated Pt3Ni(111), indicating that alloying Pt with Ni influences the intermediates of ORR, and leads to only the dissociation mechanism of chemisorption state OOH species being involved in acid medium on Pt-segregated Pt3Ni(111). By contrast, the dissociation mechanisms of chemisorbed O2 molecule with top-bridge-top configuration and OOH species both were involved on pure Pt(111). The rds of the entire four-electron ORR was changed after Pt alloying with Ni. The rds of the entire ORR is the proton and electron transfer to O2 to form OOH on Pt-segregated Pt3Ni(111), whereas it is the reaction of O atom protonation to form OH species on pure Pt(111), indicating that sublayer Ni strongly influences the rds of ORR. The comparison of the ORR mechanisms explained that Pt3Ni alloy enhanced the ORR electrocatalytic activity more than pure Pt. The effect of electrode potential on ORR pathway on the pure Pt and Pt3Ni alloy was considered to obtain further insights into the electrochemical reduction of O2. Results showed that the proton and electron transfer becomes difficult at high potential. The ORR can easily proceed when the electrode potential lowers. For pure Pt- and Pt-based alloys, this phenomenon may imply the origin of the overpotential. PMID:26450348

  4. Surface profile control of FeNiPt/Pt core/shell nanowires for oxygen reduction reaction

    SciTech Connect

    Zhu, Huiyuan; Zhang, Sen; Su, Dong; Jiang, Guangming; Sun, Shouheng

    2015-03-18

    The ever-increasing energy demand requires renewable energy schemes with low environmental impacts. Electrochemical energy conversion devices, such as fuel cells, combine fuel oxidization and oxygen reduction reactions and have been studied extensively for renewable energy applications. However, their energy conversion efficiency is often limited by kinetically sluggish chemical conversion reactions, especially oxygen reduction reaction (ORR). [1-5] To date, extensive efforts have been put into developing efficient ORR catalysts with controls on catalyst sizes, compositions, shapes and structures. [6-12] Recently, Pt-based catalysts with core/shell and one-dimensional nanowire (NW) morphologies were found to be promising to further enhance ORR catalysis. With the core/shell structure, the ORR catalysis of a nanoparticle (NP) catalyst can be tuned by both electronic and geometric effects at the core/shell interface. [10,13,14] With the NW structure, the catalyst interaction with the conductive support can be enhanced to facilitate electron transfer between the support and the NW catalyst and to promote ORR. [11,15,16]

  5. Surface profile control of FeNiPt/Pt core/shell nanowires for oxygen reduction reaction

    DOE PAGESBeta

    Zhu, Huiyuan; Zhang, Sen; Su, Dong; Jiang, Guangming; Sun, Shouheng

    2015-03-18

    The ever-increasing energy demand requires renewable energy schemes with low environmental impacts. Electrochemical energy conversion devices, such as fuel cells, combine fuel oxidization and oxygen reduction reactions and have been studied extensively for renewable energy applications. However, their energy conversion efficiency is often limited by kinetically sluggish chemical conversion reactions, especially oxygen reduction reaction (ORR). [1-5] To date, extensive efforts have been put into developing efficient ORR catalysts with controls on catalyst sizes, compositions, shapes and structures. [6-12] Recently, Pt-based catalysts with core/shell and one-dimensional nanowire (NW) morphologies were found to be promising to further enhance ORR catalysis. With themore » core/shell structure, the ORR catalysis of a nanoparticle (NP) catalyst can be tuned by both electronic and geometric effects at the core/shell interface. [10,13,14] With the NW structure, the catalyst interaction with the conductive support can be enhanced to facilitate electron transfer between the support and the NW catalyst and to promote ORR. [11,15,16]« less

  6. Utilizing in Situ Electrochemical SHINERS for Oxygen Reduction Reaction Studies in Aprotic Electrolytes.

    PubMed

    Galloway, Thomas A; Hardwick, Laurence J

    2016-06-01

    Spectroscopic detection of reaction intermediates upon a variety of electrode surfaces is of major interest within physical chemistry. A notable technique in the study of the electrochemical interface has been surface-enhanced Raman spectroscopy (SERS). The drawback of SERS is that it is limited to roughened gold and silver substrates. Herein we report that shell-isolated nanoparticles for enhanced Raman spectroscopy (SHINERS) can overcome the limitations of SERS and has followed the oxygen reduction reaction (ORR), within a nonaqueous electrolyte, on glassy carbon, gold, palladium, and platinum disk electrodes. The work presented demonstrates SHINERS for spectroelectrochemical studies for applied and fundamental electrochemistry in aprotic electrolytes, especially for the understanding and development of future metal-oxygen battery applications. In particular, we highlight that with the addition of Li(+), both the electrode surface and solvent influence the ORR mechanism, which opens up the possibility of tailoring surfaces to produce desired reaction pathways. PMID:27195529

  7. Covalent hybridization of thiolated graphene sheet and platinum nanoparticles for electrocatalytic oxygen reduction reaction.

    PubMed

    Ahmed, Mohammad Shamsuddin; Kim, Daekun; Han, Hyoung Soon; Jeong, Haesang; Jeon, Seungwon

    2012-11-01

    A covalently bonded thiolated graphene sheet-supported platinum electrocatalyst (GOS-Pt) has synthesized for electrochemical oxygen reduction reaction (ORR) in neutral media. The catalyst's structural features are characterized by transmission electron microscopy (TEM), energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). Its activity towards the ORR has investigated by using cyclic voltammetry (CV), rotating disk electrode (RDE), and rotating ring disk electrode (RRDE) in 0.1 mol l(-1) phosphate buffer solution (PBS) at pH 7, which is also used to assess the catalyst's kinetic parameters. On a glassy carbon electrode (GCE), the catalyst shows a significant catalytic activity, with its electrocatalysis of O2 reduction occurring via four-electron transfer reduction to H2O with minimal generation of H2O2. PMID:23421215

  8. Oxygen reduction reaction activity on Pt{111} surface alloys.

    PubMed

    Attard, Gary A; Brew, Ashley; Ye, Jin-Yu; Morgan, David; Sun, Shi-Gang

    2014-07-21

    PtM overlayers (where M=Fe, Co or Ni) supported on Pt{111} are prepared via thermal annealing in either a nitrogen/water or hydrogen ambient of dilute aqueous droplets containing M(Z+) cations directly attached to the electrode. Two different PtM phases are detected depending on the nature of the post-annealing cooling environment. The first of these consists of small (<20 nm), closely packed microcrystals comprised of a central metallic core and a shell (several monolayers thick) of mixed metal oxides/hydroxides. The second type of PtM phase is prepared by cooling in a stream of hydrogen gas. Although this second phase also consists of numerous microcrystals covering the Pt{111} electrode surface, these are both flatter than before and moreover are entirely metallic in character. A positive shift in the onset of PtM oxide formation correlates with increased activity towards the oxygen reduction reaction (ORR), which we ascribe to the greater availability of platinum metallic sites under ORR conditions. PMID:24986646

  9. O2 and H2O2 transformation steps for the oxygen reduction reaction catalyzed by graphitic nitrogen-doped carbon nanotubes in acidic electrolyte from first principles calculations.

    PubMed

    Li, Yuhang; Zhong, Guoyu; Yu, Hao; Wang, Hongjuan; Peng, Feng

    2015-09-14

    It is highly challenging but extremely desirable to develop carbon catalysts with high oxygen reduction reaction (ORR) activity and stability in acidic medium for commercial application. In this paper, based on density functional theory (DFT) calculations with long range interaction correction and solvation effects, the elementary transformations of all the probable intermediates in the ORR and the hydrogen peroxide reduction reaction (HPRR) over graphitic nitrogen-doped carbon nanotubes (NCNTs) in acidic medium were evaluated, and it was found that all the rate determining steps are related to the bonding hydroxyl group because of the strong interaction between the hydroxyl group and carbon. Thus, it is hard for the direct four-electron ORR and the two-electron HPRR to proceed. Together with hydrogen peroxide disproportionation (HPD), a mixed mechanism for the ORR in acidic electrolyte was proposed, where the two-electron and three-electron ORRs and HPD dominate the electrode reaction. The experimental result for the ORR catalyzed by NCNTs in acidic electrolyte also well illustrated the rationality of the theoretical calculations. This study not only gives new insights into the effect of graphitic nitrogen doping on the ORR catalyzed by carbon, but also provides a guide to design carbon catalysts with high ORR activity in acidic electrolyte. PMID:26234475

  10. Solid-state chemistry-enabled scalable production of octahedral Pt-Ni alloy electrocatalyst for oxygen reduction reaction.

    PubMed

    Zhang, Changlin; Hwang, Sang Youp; Trout, Alexis; Peng, Zhenmeng

    2014-06-01

    Although octahedral Pt-Ni alloy nanoparticles possess an excelling property in oxygen reduction reaction (ORR) and are of great potential as an electrocatalyst for polymer electrolyte membrane fuel cells (PEMFCs), mass production of the materials at low cost remains a big challenge. By combining the advantages of both solid-state chemistry and wet synthetic chemistry, we developed one scalable, surfactant-free, and cost-effective method for producing octahedral Pt-Ni alloy nanoparticles on carbon support. The octahedral Pt-Ni samples were prepared with different compositions and studied for the ORR property. They exhibit a much improved reaction activity compared to the commercial catalyst. The experiments demonstrate an innovative strategy for preparing shaped metal nanoparticles and make significant progress in the ORR catalyst research. PMID:24827592

  11. DFT Study of Oxygen Reduction Reaction on N-substituted Carbon Electrodes. Adsorption

    NASA Astrophysics Data System (ADS)

    Kobayashi, Hisayoshi; Tomoya, Nakzono; Miyazaki, Soichi; Miura, Toshiko; Takeuchi, Nobuyuki; Yamabe, Tokio

    2011-05-01

    Carbon alloys attract attention as metal-free cathode catalysts. Mechanisms of oxygen reduction reactions are investigated using the DFT calculations and molecular models such as N-substituted coronene, circum pyrene, and corannulene. The overall oxygen reduction reaction (ORR) is decomposed into five elementary reactions. Adsorption of O2 is important as the first step of reduction, and it depends strongly on the spin density on C atoms, introduced by the N atom. Secondly the peripheral C atoms have an advantage due to the rehybridization freedom to the sp3 configuration. Based on the reversible electrode potential (REP) for each elementary reaction, the overpotential is expected for the first reduction of O2 to OOH and the final reduction of OH to H2O. These features indicate that N-substituted carbon electrode resembles Pt electrode compared to other less active metals, such as Au.

  12. Catalytic activities enhanced by abundant structural defects and balanced N distribution of N-doped graphene in oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Bai, Xiaogong; Shi, Yantao; Guo, Jiahao; Gao, Liguo; Wang, Kai; Du, Yi; Ma, Tingli

    2016-02-01

    N-doped graphene (NG) is a promising candidate for oxygen reduction reaction (ORR) in the cathode of fuel cells. However, the catalytic activity of NG is lower than that of commercial Pt/C in alkaline and acidic media. In this study, NG samples were obtained using urea as N source. The structural defects and N distribution in the samples were adjusted by regulating the pyrolysis temperature. The new NG type exhibited remarkable catalytic activities for ORR in both alkaline and acidic media.

  13. Trend in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium

    SciTech Connect

    Dathar, Gopi Krishna Phani; Shelton Jr, William Allison; Xu, Ye

    2012-01-01

    Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O{sub 2} on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes for nonaqueous Li-air batteries.

  14. Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction.

    PubMed

    Liang, Yongye; Li, Yanguang; Wang, Hailiang; Zhou, Jigang; Wang, Jian; Regier, Tom; Dai, Hongjie

    2011-10-01

    Catalysts for oxygen reduction and evolution reactions are at the heart of key renewable-energy technologies including fuel cells and water splitting. Despite tremendous efforts, developing oxygen electrode catalysts with high activity at low cost remains a great challenge. Here, we report a hybrid material consisting of Co₃O₄ nanocrystals grown on reduced graphene oxide as a high-performance bi-functional catalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Although Co₃O₄ or graphene oxide alone has little catalytic activity, their hybrid exhibits an unexpected, surprisingly high ORR activity that is further enhanced by nitrogen doping of graphene. The Co₃O₄/N-doped graphene hybrid exhibits similar catalytic activity but superior stability to Pt in alkaline solutions. The same hybrid is also highly active for OER, making it a high-performance non-precious metal-based bi-catalyst for both ORR and OER. The unusual catalytic activity arises from synergetic chemical coupling effects between Co₃O₄ and graphene. PMID:21822263

  15. N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells

    PubMed Central

    Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

    2015-01-01

    The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells. PMID:26601132

  16. Graphene-based transition metal oxide nanocomposites for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Sun, Meng; Liu, Huijuan; Liu, Yang; Qu, Jiuhui; Li, Jinghong

    2015-01-01

    The development of low cost, durable and efficient nanocatalysts to substitute expensive and rare noble metals (e.g. Pt, Au and Pd) in overcoming the sluggish kinetic process of the oxygen reduction reaction (ORR) is essential to satisfy the demand for sustainable energy conversion and storage in the future. Graphene based transition metal oxide nanocomposites have extensively been proven to be a type of promising highly efficient and economic nanocatalyst for optimizing the ORR to solve the world-wide energy crisis. Synthesized nanocomposites exhibit synergetic advantages and avoid the respective disadvantages. In this feature article, we concentrate on the recent leading works of different categories of introduced transition metal oxides on graphene: from the commonly-used classes (FeOx, MnOx, and CoOx) to some rare and heat-studied issues (TiOx, NiCoOx and Co-MnOx). Moreover, the morphologies of the supported oxides on graphene with various dimensional nanostructures, such as one dimensional nanocrystals, two dimensional nanosheets/nanoplates and some special multidimensional frameworks are further reviewed. The strategies used to synthesize and characterize these well-designed nanocomposites and their superior properties for the ORR compared to the traditional catalysts are carefully summarized. This work aims to highlight the meaning of the multiphase establishment of graphene-based transition metal oxide nanocomposites and its structural-dependent ORR performance and mechanisms.

  17. Graphene-based transition metal oxide nanocomposites for the oxygen reduction reaction.

    PubMed

    Sun, Meng; Liu, Huijuan; Liu, Yang; Qu, Jiuhui; Li, Jinghong

    2015-01-28

    The development of low cost, durable and efficient nanocatalysts to substitute expensive and rare noble metals (e.g. Pt, Au and Pd) in overcoming the sluggish kinetic process of the oxygen reduction reaction (ORR) is essential to satisfy the demand for sustainable energy conversion and storage in the future. Graphene based transition metal oxide nanocomposites have extensively been proven to be a type of promising highly efficient and economic nanocatalyst for optimizing the ORR to solve the world-wide energy crisis. Synthesized nanocomposites exhibit synergetic advantages and avoid the respective disadvantages. In this feature article, we concentrate on the recent leading works of different categories of introduced transition metal oxides on graphene: from the commonly-used classes (FeOx, MnOx, and CoOx) to some rare and heat-studied issues (TiOx, NiCoOx and Co-MnOx). Moreover, the morphologies of the supported oxides on graphene with various dimensional nanostructures, such as one dimensional nanocrystals, two dimensional nanosheets/nanoplates and some special multidimensional frameworks are further reviewed. The strategies used to synthesize and characterize these well-designed nanocomposites and their superior properties for the ORR compared to the traditional catalysts are carefully summarized. This work aims to highlight the meaning of the multiphase establishment of graphene-based transition metal oxide nanocomposites and its structural-dependent ORR performance and mechanisms. PMID:25502117

  18. Oxygen reduction reaction catalyzed by platinum nanonetwork prepared by template free one step synthesis for polymer electrolyte membrane fuel cells

    SciTech Connect

    Narayanamoorthy, B.; Kumar, B.V.V.S. Pavan; Eswaramoorthy, M.; Balaji, S.

    2014-07-01

    Highlights: • Supportless Pt nanonetwork (Pt NN) synthesized by novel template free one step method as per our earlier reported procedure. • Electrocatalytic activity of Pt NN studied taking oxygen reduction reaction in acid medium. • Kinetic and thermodynamic parameters were deduced under hydrodynamic conditions. • ORR mechanistic pathway was proposed based on kinetic rate constants. • ADT analysis found enhanced stability (5000 cycles) for Pt NN than Pt NN/VC and reported Pt/C. - Abstract: The reduction reaction of molecular oxygen (ORR) was investigated using supportless Pt nanonetwork (Pt NN) electrocatalyst in sulfuric acid medium. Pt NN was prepared by template free borohydride reduction. The transmission electron microscope images revealed a network like nano-architecture having an average cluster size of 30 nm. The electrochemical characterization of supportless and Vulcan carbon supported Pt NN (Pt NN/VC) was carried out using rotating disc and ring disc electrodes at various temperatures. Kinetic and thermodynamic parameters were estimated under hydrodynamic conditions and compared with Pt NN/VC and reported Pt/C catalysts. The accelerated durability test revealed that supportless Pt NN is quite stable for 5000 potential cycles with 22% reduction in electrochemical surface area (ECSA). While the initial limiting current density has in fact increased by 11.6%, whereas Pt NN/VC suffered nearly 55% loss in ECSA and 13% loss in limiting current density confirming an enhanced stability of supportless Pt NN morphology for ORR compared to conventional Pt/C ORR catalysts in acid medium.

  19. Density functional theory study of oxygen reduction reaction on Pt/Pd3Al(111) alloy electrocatalyst.

    PubMed

    Xiao, B B; Jiang, X B; Jiang, Q

    2016-05-25

    Developing efficient catalysts for the oxygen reduction reaction (ORR) to reduce cathode Pt loading without sacrificing the performance has been under intensive research. Herein, by using density functional theory calculations, the activity and stability of a Pt monolayer supported on Pd3Al(111) as the ORR catalyst have been systematically studied. The simulations demonstrate that due to alloying, the ORR intermediates bind weakly on Pt/Pd3Al(111) with optimal adsorption energy of O and OH. By considering the elemental ORR steps, the ORR mechanism is predicted to be an OOH dissociation mechanism. The rate determining step is OOH dissociation with a reaction barrier of 0.37 eV, lower than the corresponding value on Pt/Pt3Al(111) and Pt(111), indicating the superior activity of Pt/Pd3Al(111). Even considering the unfeasible H adsorption under high potential, the ORR mechanism on Pt/Pd3Al(111) would proceed via O2 hydration, OOH hydration, H2O formation, and H2O desorption, indicating a good ORR electrocatalyst. Furthermore, stability was evaluated by calculating the alloy formation energy and the electrochemical potential shift of surface Pt dissolution. The exceptionally negative alloy formation energy of Pd3Al and the positive dissolution potential shift of the surface Pt atoms show the enhanced durability of Pt/Pd3Al(111). The improved activity, in combination with its enhanced stability, makes the novel ternary alloy electrocatalyst very promising for development of new cathode catalysts for fuel cells. PMID:27167779

  20. Theoretical insights on the catalytic activity and mechanism for oxygen reduction reaction at Fe and P codoped graphene.

    PubMed

    He, Feng; Li, Kai; Xie, Guangyou; Wang, Ying; Jiao, Menggai; Tang, Hao; Wu, Zhijian

    2016-05-14

    The non-precious metal graphene catalyst doped with Fe-Px are recently proposed as a promising candidate in substituting Pt for catalyzing oxygen reduction reaction (ORR) in fuel cells. Systematic DFT calculations are performed to investigate the catalytic activity and the ORR mechanism on the Fe-Px (x = 1-4) system in acid medium in this work. Our results indicated that the configuration with one Fe and two P atoms codoped at zigzag edge site (Fe-P2-zig-G) is the most stable, in excellent agreement with the experimental observation that the ratio of Fe and P is nearly 1 : 2. The four-electron reduction mechanism for ORR on the Fe-P2-zig-G is via the competing OOH hydrogenation pathways (to form either OH + OH or O + H2O). The rate determining step is the O2 hydrogenation with an energy barrier of 0.43 eV, much smaller that of calculated 0.80 eV for pure Pt. In addition, the highest energy barrier of the studied ORR mechanism is the O2 dissociation with an energy barrier of 0.70 eV, a value also smaller than that of pure Pt. This demonstrated that the zigzag edge site of the Fe-P2 codoped graphene should be active for the ORR. PMID:27094325

  1. Ni- and Mn-Promoted Mesoporous Co3O4: A Stable Bifunctional Catalyst with Surface-Structure-Dependent Activity for Oxygen Reduction Reaction and Oxygen Evolution Reaction.

    PubMed

    Song, Wenqiao; Ren, Zheng; Chen, Sheng-Yu; Meng, Yongtao; Biswas, Sourav; Nandi, Partha; Elsen, Heather A; Gao, Pu-Xian; Suib, Steven L

    2016-08-17

    Efficient bifunctional catalysts for electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly desirable due to their wide applications in fuel cells and rechargeable metal air batteries. However, the development of nonprecious metal catalysts with comparable activities to noble metals is still challenging. Here we report a one-step wet-chemical synthesis of Ni-/Mn-promoted mesoporous cobalt oxides through an inverse micelle process. Various characterization techniques including powder X-ray diffraction (PXRD), N2 sorption, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) confirm the successful incorporation of Ni and Mn leading to the formation of Co-Ni(Mn)-O solid solutions with retained mesoporosity. Among these catalysts, cobalt oxide with 5% Ni doping demonstrates promising activities for both ORR and OER, with an overpotential of 399 mV for ORR (at -3 mA/cm(2)) and 381 mV (at 10 mA/cm(2)) for OER. Furthermore, it shows better durability than precious metals featuring little activity decay throughout 24 h continuous operation. Analyses of cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), Raman, and O2-temperature-programmed desorption (O2-TPD) reveal that redox activity of Co(3+) to Co(4+) is crucial for OER performance, while the population of surface oxygen vacancies and surface area determine ORR activities. The comprehensive investigation of the intrinsic active sites for ORR and OER by correlating different physicochemical properties to the electrochemical activities is believed to provide important insight toward the rational design of high-performance electrocatalysts for ORR and OER reactions. PMID:27458646

  2. In-plane graphene/boron-nitride heterostructures as an efficient metal-free electrocatalyst for the oxygen reduction reaction.

    PubMed

    Sun, Qiao; Sun, Caixia; Du, Aijun; Dou, Shixue; Li, Zhen

    2016-08-01

    Exploiting metal-free catalysts for the oxygen reduction reaction (ORR) and understanding their catalytic mechanisms are vital for the development of fuel cells (FCs). Our study has demonstrated that in-plane heterostructures of graphene and boron nitride (G/BN) can serve as an efficient metal-free catalyst for the ORR, in which the C-N interfaces of G/BN heterostructures act as reactive sites. The formation of water at the heterointerface is both energetically and kinetically favorable via a four-electron pathway. Moreover, the water formed can be easily released from the heterointerface, and the catalytically active sites can be regenerated for the next cycle. Since G/BN heterostructures with controlled domain sizes have been successfully synthesized in recent reports (e.g. Nat. Nanotechnol., 2013, 8, 119), our results highlight the great potential of such heterostructures as a promising metal-free catalyst for the ORR in FCs. PMID:27396486

  3. Linking structure to function: The search for active sites in non-platinum group metal oxygen reduction reaction catalysts

    DOE PAGESBeta

    Holby, Edward F.; Zelenay, Piotr

    2016-05-17

    Atomic-scale structures of oxygen reduction reaction (ORR) active sites in non-platinum group metal (non-PGM) catalysts, made from pyrolysis of carbon, nitrogen, and transition-metal (TM) precursors have been the subject of continuing discussion in the fuel cell electrocatalysis research community. We found that quantum chemical modeling is a path forward for understanding of these materials and how they catalyze the ORR. Here, we demonstrate through literature examples of how such modeling can be used to better understand non-PGM ORR active site relative stability and activity and how such efforts can also aid in the interpretation of experimental signatures produced by thesemore » materials.« less

  4. Current status, key challenges and its solutions in the design and development of graphene based ORR catalysts for the microbial fuel cell applications.

    PubMed

    Kannan, M V; Gnana Kumar, G

    2016-03-15

    Microbial fuel cells (MFC) are considered as the futuristic energy device that generates electricity from the catalytic degradation of biodegradable organic wastes using microbes, which exist in waste water. In MFCs, oxygen serves as a cathodic electron acceptor and oxygen reduction kinetics played a significant role in the determination of overall efficiency. A wide range of strategies have been developed for the preparation and substantial modification of oxygen reduction reaction (ORR) catalysts to improve the maximum volumetric power density of MFCs, in which the efforts on graphene based ORR catalysts are highly imperative. Although numerous research endeavors have been achieved in relation with the graphene based ORR catalysts applicable for MFCs, still their collective summary has not been developed, which hinders the acquirement of adequate knowledge on tuning the specific properties of said catalysts. The intension of this review is to outline the significant role of ORR catalysts, factors influencing the ORR activity, strategies behind the modifications of ORR catalysts and update the research efforts devoted on graphene based ORR catalysts. This review can be considered as a pertinent guide to understand the design and developmental strategies of competent graphene based ORR catalysts, which are not only applicable for MFCs but also for number of electrochemical applications. PMID:26606182

  5. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resulting in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.

  6. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    DOE PAGESBeta

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

  7. Promotion of oxygen reduction reaction durability of carbon-supported PtAu catalysts by surface segregation and TiO₂ addition.

    PubMed

    Liu, Chen-Wei; Chen, Hong-Shuo; Lai, Chien-Ming; Lin, Jiunn-Nan; Tsai, Li-Duan; Wang, Kuan-Wen

    2014-02-12

    Highly effective carbon supported-Pt75Au25 catalysts for oxygen reduction reaction (ORR) are prepared though titanium dioxide modification and post heat treatment. After accelerated durability test (ADT) of 1700 cycles, the ORR activity of PtAu/C catalysts modified by TiO2 and air heat treatment is 3 times higher than that of the commercial Pt/C. The enhancement of ORR activity is attributed to surface and structural alteration by air-induced Pt surface segregation and lower unfilled d states. On the contrary, for TiO2 modified and H2 treated PtAu/C catalysts, the deterioration of the ORR activity may be due to the loss of electrochemical surface area after ADT and the increase of d-band vacancy. PMID:24447040

  8. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    DOEpatents

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  9. In-plane graphene/boron-nitride heterostructures as an efficient metal-free electrocatalyst for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Sun, Qiao; Sun, Caixia; Du, Aijun; Dou, Shixue; Li, Zhen

    2016-07-01

    Exploiting metal-free catalysts for the oxygen reduction reaction (ORR) and understanding their catalytic mechanisms are vital for the development of fuel cells (FCs). Our study has demonstrated that in-plane heterostructures of graphene and boron nitride (G/BN) can serve as an efficient metal-free catalyst for the ORR, in which the C-N interfaces of G/BN heterostructures act as reactive sites. The formation of water at the heterointerface is both energetically and kinetically favorable via a four-electron pathway. Moreover, the water formed can be easily released from the heterointerface, and the catalytically active sites can be regenerated for the next cycle. Since G/BN heterostructures with controlled domain sizes have been successfully synthesized in recent reports (e.g. Nat. Nanotechnol., 2013, 8, 119), our results highlight the great potential of such heterostructures as a promising metal-free catalyst for the ORR in FCs.Exploiting metal-free catalysts for the oxygen reduction reaction (ORR) and understanding their catalytic mechanisms are vital for the development of fuel cells (FCs). Our study has demonstrated that in-plane heterostructures of graphene and boron nitride (G/BN) can serve as an efficient metal-free catalyst for the ORR, in which the C-N interfaces of G/BN heterostructures act as reactive sites. The formation of water at the heterointerface is both energetically and kinetically favorable via a four-electron pathway. Moreover, the water formed can be easily released from the heterointerface, and the catalytically active sites can be regenerated for the next cycle. Since G/BN heterostructures with controlled domain sizes have been successfully synthesized in recent reports (e.g. Nat. Nanotechnol., 2013, 8, 119), our results highlight the great potential of such heterostructures as a promising metal-free catalyst for the ORR in FCs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03288e

  10. Synthesis and x-ray characterization of cobalt phosphide (Co₂P) nanorods for the oxygen reduction reaction

    SciTech Connect

    Doan-Nguyen, Vicky V.T.; Su, Dong; Zhang, Sen; Trigg, Edward B.; Agarwal, Rahul; Li, Jing; Winey, Karen I.; Murray, Christopher B.

    2015-07-14

    Low temperature fuel cells are clean, effective alternative fuel conversion technology. Oxygen reduction reaction (ORR) at the fuel cell cathode has required Pt as the electrocatalyst for high activity and selectivity of the four-electron reaction pathway. Targeting a less expensive, earth abundant alternative, we have developed the synthesis of cobalt phosphide (Co₂P) nanorods for ORR. Characterization techniques that include total X-ray scattering and extended X-ray absorption fine structure revealed a deviation of the nanorods from bulk crystal structure with a contraction along the b orthorhombic lattice parameter. The carbon supported nanorods have comparable activity but are remarkably more stable than conventional Pt catalysts for the oxygen reduction reaction in alkaline environments.

  11. Synthesis and x-ray characterization of cobalt phosphide (Co₂P) nanorods for the oxygen reduction reaction

    DOE PAGESBeta

    Doan-Nguyen, Vicky V.T.; Su, Dong; Zhang, Sen; Trigg, Edward B.; Agarwal, Rahul; Li, Jing; Winey, Karen I.; Murray, Christopher B.

    2015-07-14

    Low temperature fuel cells are clean, effective alternative fuel conversion technology. Oxygen reduction reaction (ORR) at the fuel cell cathode has required Pt as the electrocatalyst for high activity and selectivity of the four-electron reaction pathway. Targeting a less expensive, earth abundant alternative, we have developed the synthesis of cobalt phosphide (Co₂P) nanorods for ORR. Characterization techniques that include total X-ray scattering and extended X-ray absorption fine structure revealed a deviation of the nanorods from bulk crystal structure with a contraction along the b orthorhombic lattice parameter. The carbon supported nanorods have comparable activity but are remarkably more stable thanmore » conventional Pt catalysts for the oxygen reduction reaction in alkaline environments.« less

  12. Effect of mass transfer on the oxygen reduction reaction catalyzed by platinum dendrimer encapsulated nanoparticles.

    PubMed

    Dumitrescu, Ioana; Crooks, Richard M

    2012-07-17

    Here we report on the effect of the mass transfer rate (k(t)) on the oxygen reduction reaction (ORR) catalyzed by Pt dendrimer-encapsulated nanoparticles (DENs) comprised of 147 and 55 atoms (Pt(147) and Pt(55)). The experiments were carried out using a dual-electrode microelectrochemical device, which enables the study of the ORR under high k(t) conditions with simultaneous detection of H(2)O(2). At low k(t) (0.02 to 0.12 cm s(-1)) the effective number of electrons involved in ORR, n(eff), is 3.7 for Pt(147) and 3.4 for Pt(55). As k(t) is increased, the mass-transfer-limited current for the ORR becomes significantly lower than the value predicted by the Levich equation for a 4-electron process regardless of catalyst size. However, the percentage of H(2)O(2) detected remains constant, such that n(eff) barely changes over the entire k(t) range explored (0.02 cm s(-1)). This suggests that mass transfer does not affect n(eff), which has implications for the mechanism of the ORR on Pt nanoparticles. Interestingly, there is a significant difference in n(eff) for the two sizes of Pt DENs (n(eff) = 3.7 and 3.5 for Pt(147) and Pt(55), respectively) that cannot be assigned to mass transfer effects and that we therefore attribute to a particle size effect. PMID:22665772

  13. Effects of halogen doping on nanocarbon catalysts synthesized by a solution plasma process for the oxygen reduction reaction.

    PubMed

    Ishizaki, Takahiro; Wada, Yuta; Chiba, Satoshi; Kumagai, Sou; Lee, Hoonseung; Serizawa, Ai; Li, Oi Lun; Panomsuwan, Gasidit

    2016-08-01

    Halogen-doped carbon nanoparticles (CNPs) were synthesized by a simple one-step solution plasma process at room temperature using a mixture of benzene (C6H6) and organics containing halogen atoms as the precursors (i.e., hexafluorobenzene (C6F6), hexachlorobenzene (C6Cl6), and hexabromobenzene (C6Br6)). The experimental results demonstrated that halogen doping, especially F and Cl, could lead to more efficient removal of residual hydrogen compared to carbon synthesized with pure benzene. This phenomenon was related to the different binding energies between hydrogen and halogens to form hydrogen halides. Their crystallinity and morphology did not change and remained the same as non-doped carbon. The electrochemical evaluation of oxygen reduction reaction (ORR) activity in an alkaline solution revealed that halogen doping did not play a significant role in shifting the onset potential for the ORR, while a slight enhancement in diffusion limited current density was observed at high overpotentials. Moreover, the electron transfer number involved in the ORR process determined from the Koutecky-Levich plot at -0.6 V was found to increase for halogen-doped carbons in the following order: F-CNPs > Br-CNPs > Cl-CNPs > CNPs. The improved ORR performance of F-CNPs could reasonably be attributed to the synergistic effects of specific bonding states between the halogen and carbon, structural defects and surface functional groups. Our results confirmed the validity of using halogen doping to improve the ORR catalytic activity of CNPs. PMID:27435811

  14. Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction

    PubMed Central

    2013-01-01

    A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

  15. Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction.

    PubMed

    Yuan, Xianxia; Hu, Xin-Xin; Ding, Xin-Long; Kong, Hai-Chuan; Sha, Hao-Dong; Lin, He; Wen, Wen; Shen, Guangxia; Guo, Zhi; Ma, Zi-Feng; Yang, Yong

    2013-01-01

    A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

  16. Theoretical investigations on SiC2 siligraphene as promising metal-free catalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Dong, Huilong; Lin, Bin; Gilmore, Keith; Hou, Tingjun; Lee, Shuit-Tong; Li, Youyong

    2015-12-01

    The design and discovery of high-performance metal-free catalytic materials for oxygen reduction reaction (ORR) electrocatalysis is vital for the development of fuel cells. By performing density functional theory (DFT) calculations, we investigate the potential applications of SiC2 siligraphene (g-SiC2) as metal-free ORR catalyst. The g-SiC2 exhibits higher adsorption affinity for the O2 molecule and other ORR intermediates than the traditional Pt (111), and shows good tolerance against CO poisoning. The detailed LH and ER mechanisms in catalyzing ORR by g-SiC2 are simulated and discussed, both in acidic and alkaline environment. We find that, in alkaline environment, the g-SiC2 presents a very low activation barrier (0.16 eV) for the rate determining step (RDS) and shows no overpotential at the equilibrium potential. Our theoretical simulations validate that the siligraphene with alternatively arranged Si and C atoms holds great potential as ORR catalyst in alkaline environment.

  17. Highly Functional Bioinspired Fe/N/C Oxygen Reduction Reaction Catalysts: Structure-Regulating Oxygen Sorption.

    PubMed

    Yao, Yingfang; You, Yong; Zhang, Gaixia; Liu, Jianguo; Sun, Haoran; Zou, Zhigang; Sun, Shuhui

    2016-03-16

    Tuna is one of the most rapid and distant swimmers. Its unique gill structure with the porous lamellae promotes fast oxygen exchange that guarantees tuna's high metabolic and athletic demands. Inspired by this specific structure, we designed and fabricated microporous graphene nanoplatelets (GNPs)-based Fe/N/C electrocatalysts for oxygen reduction reaction (ORR). Careful control of GNP structure leads to the increment of microporosity, which influences the O2 adsorption positively and desorption oppositely, resulting in enhanced O2 diffusion, while experiencing reduced ORR kinetics. Working in the cathode of proton-exchange membrane fuel cells, the GNP catalysts require a compromise between adsorption/desorption for effective O2 exchange, and as a result, appropriate microporosity is needed. In this work, the highest power density, 521 mW·cm(-2), at zero back pressure is achieved. PMID:26902179

  18. Solution-processed PEDOT:PSS/graphene composites as the electrocatalyst for oxygen reduction reaction.

    PubMed

    Zhang, Miao; Yuan, Wenjing; Yao, Bowen; Li, Chun; Shi, Gaoquan

    2014-03-12

    Composites of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and reduced graphene oxide (rGO) have been prepared by solution mixing and applied as electrocatalysts for oxygen reduction reaction (ORR) after treatment with concentrated H2SO4. The blending of rGO induces the conformational change of PEDOT chains from benzoid to quionoid structure and charge transfer from rGO to PEDOT. H2SO4 post-treatment can remove part of insulating PSS from the surface of the PEDOT:PSS/rGO composite film, resulting in a significant conductivity enhancement of the composite. This synergistic effect makes the H2SO4-treated PEDOT:PSS/rGO composite a promising catalyst for ORR. It exhibits enhanced electrocatalytic activity, better tolerance to a methanol crossover effect and CO poisoning, and longer durability than those of the platinum/carbon catalyst. PMID:24456474

  19. Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction.

    PubMed

    Nie, Yao; Li, Li; Wei, Zidong

    2015-04-21

    Developing highly efficient catalysts for the oxygen reduction reaction (ORR) is key to the fabrication of commercially viable fuel cell devices and metal-air batteries for future energy applications. Herein, we review the most recent advances in the development of Pt-based and Pt-free materials in the field of fuel cell ORR catalysis. This review covers catalyst material selection, design, synthesis, and characterization, as well as the theoretical understanding of the catalysis process and mechanisms. The integration of these catalysts into fuel cell operations and the resulting performance/durability are also discussed. Finally, we provide insights into the remaining challenges and directions for future perspectives and research. PMID:25652755

  20. Dramatic increase in the oxygen reduction reaction for platinum cathodes from tuning the solvent dielectric constant.

    PubMed

    Fortunelli, Alessandro; Goddard, William A; Sha, Yao; Yu, Ted H; Sementa, Luca; Barcaro, Giovanni; Andreussi, Oliviero

    2014-06-23

    Hydrogen fuel cells (FC) are considered essential for a sustainable economy based on carbon-free energy sources, but a major impediment are the costs. First-principles quantum mechanics (density functional theory including solvation) is used to predict how the energies and barriers for the mechanistic steps of the oxygen reduction reaction (ORR) over the fcc(111) platinum surface depend on the dielectric constant of the solvent. The ORR kinetics can be strongly accelerated by decreasing the effective medium polarizability from the high value it has in water. Possible ways to realize this experimentally are suggested. The calculated volcano structure for the dependence of rate on solvent polarization is considered to be general, and should be observed in other electrochemical systems. PMID:24828005

  1. Electrocatalytic performances of N-doped graphene with anchored iridium species in oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Choi, Kwangrok; Lee, Seungjun; Shim, Yeonjun; Oh, Junghoon; Kim, Sujin; Park, Sungjin

    2015-09-01

    Development of new systems with high catalytic performances in the oxygen reduction reaction (ORR) for practical applications in fuel cells and metal-air batteries is a challenge. We develop a one-pot solution method for producing a novel hybrid material consisting of Ir species anchored on N-doped graphene. The hybrid is synthesized by reacting graphene oxide with IrCl3 · xH2O in dimethylformamide under reflux. Chemical and structural analyses confirm the attachment of Ir atoms to the N and O atoms of the N-doped graphene-based materials. The hybrid shows a good electrocatalytic performance for the ORR in alkaline media, with an onset potential of 0.88 V (versus the reversible hydrogen electrode), high long-term durability, and good tolerance for methanol poisoning.

  2. Nitrogen-doped Graphene-Supported Transition-metals Carbide Electrocatalysts for Oxygen Reduction Reaction

    PubMed Central

    Chen, Minghua; Liu, Jilei; Zhou, Weijiang; Lin, Jianyi; Shen, Zexiang

    2015-01-01

    A novel and facile two-step strategy has been designed to prepare high performance bi-transition-metals (Fe- and Mo-) carbide supported on nitrogen-doped graphene (FeMo-NG) as electrocatalysts for oxygen reduction reactions (ORR). The as-synthesized FeMo carbide -NG catalysts exhibit excellent electrocatalytic activities for ORR in alkaline solution, with high onset potential (−0.09 V vs. saturated KCl Ag/AgCl), nearly four electron transfer number (nearly 4) and high kinetic-limiting current density (up to 3.5 mA cm−2 at −0.8 V vs. Ag/AgCl). Furthermore, FeMo carbide -NG composites show good cycle stability and much better toxicity tolerance durability than the commercial Pt/C catalyst, paving their application in high-performance fuel cell and lithium-air batteries. PMID:25997590

  3. Nitrogen-doped Graphene-Supported Transition-metals Carbide Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Chen, Minghua; Liu, Jilei; Zhou, Weijiang; Lin, Jianyi; Shen, Zexiang

    2015-01-01

    A novel and facile two-step strategy has been designed to prepare high performance bi-transition-metals (Fe- and Mo-) carbide supported on nitrogen-doped graphene (FeMo-NG) as electrocatalysts for oxygen reduction reactions (ORR). The as-synthesized FeMo carbide -NG catalysts exhibit excellent electrocatalytic activities for ORR in alkaline solution, with high onset potential (-0.09 V vs. saturated KCl Ag/AgCl), nearly four electron transfer number (nearly 4) and high kinetic-limiting current density (up to 3.5 mA cm(-2) at -0.8 V vs. Ag/AgCl). Furthermore, FeMo carbide -NG composites show good cycle stability and much better toxicity tolerance durability than the commercial Pt/C catalyst, paving their application in high-performance fuel cell and lithium-air batteries. PMID:25997590

  4. Nitrogen-doped Graphene-Supported Transition-metals Carbide Electrocatalysts for Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Chen, Minghua; Liu, Jilei; Zhou, Weijiang; Lin, Jianyi; Shen, Zexiang

    2015-05-01

    A novel and facile two-step strategy has been designed to prepare high performance bi-transition-metals (Fe- and Mo-) carbide supported on nitrogen-doped graphene (FeMo-NG) as electrocatalysts for oxygen reduction reactions (ORR). The as-synthesized FeMo carbide -NG catalysts exhibit excellent electrocatalytic activities for ORR in alkaline solution, with high onset potential (-0.09 V vs. saturated KCl Ag/AgCl), nearly four electron transfer number (nearly 4) and high kinetic-limiting current density (up to 3.5 mA cm-2 at -0.8 V vs. Ag/AgCl). Furthermore, FeMo carbide -NG composites show good cycle stability and much better toxicity tolerance durability than the commercial Pt/C catalyst, paving their application in high-performance fuel cell and lithium-air batteries.

  5. A Discussion on the Activity Origin in Metal-Free Nitrogen-Doped Carbons For Oxygen Reduction Reaction and their Mechanisms.

    PubMed

    Wu, Kuang-Hsu; Wang, Da-Wei; Su, Dang-Sheng; Gentle, Ian R

    2015-09-01

    The origin of oxygen reduction reaction activity in metal-free N-doped carbons has been a stimulating, yet unsolved issue for the rational design of cost-effective electrocatalysts for fuel cells and metal-air batteries. At present, there are several inconsistent opinions on the materials chemistry and the mechanism of the oxygen reduction reaction (ORR) performed on this type of materials. This article provides a brief review of the current understanding of ORR processes and the history of electrocatalyst development. With special attention, the focus of the discussion is on the major contentions of the current opinions towards metal-free N-doped carbon chemistry and the arguments for the probable ORR mechanisms. By clarifying the fundamental aspects of each opinion, a converging consensus on N-doped carbon electrocatalysts can be established and thus facilitate the substantial development of large-capacity energy devices. PMID:26334773

  6. The Role of OOH Binding Site and Pt Surface Structure on ORR Activities

    PubMed Central

    Jia, Qingying; Caldwell, Keegan; Ziegelbauer, Joseph M.; Kongkanand, Anusorn; Wagner, Frederick T.; Mukerjee, Sanjeev; Ramaker, David E.

    2015-01-01

    We present experimentally observed molecular adsorbate coverages (e.g., O(H), OOH and HOOH) on real operating dealloyed bimetallic PtMx (M = Ni or Co) catalysts under oxygen reduction reaction (ORR) conditions obtained using X-ray absorption near edge spectroscopy (XANES). The results reveal a complex Sabatier catalysis behavior and indicate the active ORR mechanism changes with Pt–O bond weakening from the O2 dissociative mechanism, to the peroxyl mechanism, and finally to the hydrogen peroxide mechanism. An important rearrangement of the OOH binding site, an intermediate in the ORR, enables facile H addition to OOH and faster O–O bond breaking on 111 faces at optimal Pt–O bonding strength, such as that occurring in dealloyed PtM core-shell nanoparticles. This rearrangement is identified by previous DFT calculations and confirmed from in situ measured OOH adsorption coverages during the ORR. The importance of surface structural effects and 111 ordered faces is confirmed by the higher specific ORR rates on solid core vs porous multi-core nanoparticles. PMID:26190857

  7. Manageable N-doped graphene for high performance oxygen reduction reaction.

    PubMed

    Zhang, Yuewei; Ge, Jun; Wang, Lu; Wang, Donghong; Ding, Feng; Tao, Xiaoming; Chen, Wei

    2013-01-01

    Catalysts for oxygen reduction reaction (ORR) are at the heart of key green-energy fuel cell technology. N-doped graphene is a potential metal-free electrode with much better electrocatalytic activity, long-term stability, and tolerance to crossover effect than expensive platinum-based electrocatalysts. Here, we report a feasible direct-synthesis method in preparing N-graphene with manageable N contents in a large scale. The resultant N-graphene used as electrocatalysts exhibits similar catalytic activity but superior stability compared to commercial Pt/C for ORR in an alkaline solution. It was found that their electrocatalytic activities were demonstrated to depend largely on N-doping content. When nitrogen content reaches a high value at about 24-25%, ORR reaction exhibits a favorable formation of water via a four-electron pathway. Furthermore, the effect of pyrolysis temperature and precursor on the activity of N-graphene is systematically analyzed, and may shed some light on the principle of choosing appropriate way for preparing N-graphene. PMID:24067782

  8. Gold-doped graphene: A highly stable and active electrocatalysts for the oxygen reduction reaction

    SciTech Connect

    Stolbov, Sergey Alcántara Ortigoza, Marisol

    2015-04-21

    In addressing the growing need of renewable and sustainable energy resources, hydrogen-fuel-cells stand as one of the most promising routes to transform the current energy paradigm into one that integrally fulfills environmental sustainability. Nevertheless, accomplishing this technology at a large scale demands to surpass the efficiency and enhance the cost-effectiveness of platinum-based cathodes, which catalyze the oxygen reduction reaction (ORR). In this work, our first-principles calculations show that Au atoms incorporated into graphene di-vacancies form a highly stable and cost-effective electrocatalyst that is, at the same time, as or more (dependently of the dopant concentration) active toward ORR than the best-known Pt-based electrocatalysts. We reveal that partial passivation of defected-graphene by gold atoms reduces the reactivity of C dangling bonds and increases that of Au, thus optimizing them for catalyzing the ORR and yielding a system of high thermodynamic and electrochemical stabilities. We also demonstrate that the linear relation among the binding energies of the reaction intermediates assumed in computational high-throughput material screening does not hold, at least for this non-purely transition-metal material. We expect Au-doped graphene to finally overcome the cathode-related challenge hindering the realization of hydrogen-fuel cells as the leading means of powering transportation and portable devices.

  9. Manageable N-doped Graphene for High Performance Oxygen Reduction Reaction

    PubMed Central

    Zhang, Yuewei; Ge, Jun; Wang, Lu; Wang, Donghong; Ding, Feng; Tao, Xiaoming; Chen, Wei

    2013-01-01

    Catalysts for oxygen reduction reaction (ORR) are at the heart of key green-energy fuel cell technology. N-doped graphene is a potential metal-free electrode with much better electrocatalytic activity, long-term stability, and tolerance to crossover effect than expensive platinum-based electrocatalysts. Here, we report a feasible direct-synthesis method in preparing N-graphene with manageable N contents in a large scale. The resultant N-graphene used as electrocatalysts exhibits similar catalytic activity but superior stability compared to commercial Pt/C for ORR in an alkaline solution. It was found that their electrocatalytic activities were demonstrated to depend largely on N-doping content. When nitrogen content reaches a high value at about 24–25%, ORR reaction exhibits a favorable formation of water via a four-electron pathway. Furthermore, the effect of pyrolysis temperature and precursor on the activity of N-graphene is systematically analyzed, and may shed some light on the principle of choosing appropriate way for preparing N-graphene. PMID:24067782

  10. Supportless silver nanowires as oxygen reduction reaction catalysts for hydroxide-exchange membrane fuel cells.

    PubMed

    Alia, Shaun M; Duong, Kathlynne; Liu, Toby; Jensen, Kurt; Yan, Yushan

    2012-08-01

    Silver nanowires (AgNWs) and nanoparticles (AgNPs) have been synthesized to facilitate hydroxide-exchange membrane fuel cell development and commercialization. AgNWs and AgNPs with variable diameters (25-60 nm AgNWs, 2.4-30 nm AgNPs) have been studied with rotating-disk electrode experiments to examine the impact of size and morphology on the oxygen reduction reaction (ORR). Although a detrimental particle size effect is observed, AgNWs exceed the specific activity of bulk polycrystalline Ag. AgNWs with a diameter of 25 nm further exceed the ORR specific and mass activity of 2.4 nm AgNPs 5.3 times and by 16 %, respectively. Rotating ring-disk electrode testing demonstrates minimal peroxide formation on AgNWs; peroxide production increases with the use of AgNPs by as much as an order of magnitude and further increases with particle size reduction. Silver catalysts demonstrate alcohol tolerance for ORR, illustrating the benefit of silver and AgNWs as catalysts in hydroxide and alcohol hydroxide-based fuel cells. PMID:22887923

  11. Carboxylated, Fe-filled multiwalled carbon nanotubes as versatile catalysts for O2 reduction and H2 evolution reactions at physiological pH.

    PubMed

    Bracamonte, M Victoria; Melchionna, Michele; Stopin, Antoine; Giulani, Angela; Tavagnacco, Claudio; Garcia, Yann; Fornasiero, Paolo; Bonifazi, Davide; Prato, Maurizio

    2015-09-01

    The development of new electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) at physiological pH is critical for several fields, including fuel cells and biological applications. Herein, the assembly of an electrode based on carboxyl-functionalised hydrophilic multiwalled carbon nanotubes (MWCNTs) filled with Fe phases and their excellent performance as electrocatalysts for ORR and HER at physiological pH are reported. The encapsulated Fe dramatically enhances the catalytic activity, and the graphitic shells play a double role of efficiently mediating the electron transfer to O2 and H2 O reactants and providing a cocoon that prevents uncontrolled Fe oxidation or leaching. PMID:26179742

  12. Titanium Dioxide-Grafted Copper Complexes: High-Performance Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Media.

    PubMed

    Wang, Fei-Fei; Wei, Ping-Jie; Yu, Guo-Qiang; Liu, Jin-Gang

    2016-01-01

    The sluggish kinetics of the oxygen reduction reaction (ORR) at the cathodes of fuel cells significantly hampers fuel cell performance. Therefore, the development of high-performance, non-precious-metal catalysts as alternatives to noble metal Pt-based ORR electrocatalysts is highly desirable for the large-scale commercialization of fuel cells. TiO2 -grafted copper complexes deposited on multiwalled carbon nanotubes (CNTs) form stable and efficient electrocatalysts for the ORR. The optimized catalyst composite CNTs@TiO2 -ZA-[Cu(phen${{^{{\\rm NO}{_{2}}}}}$)(BTC)] shows surprisingly high selectivity for the 4 e(-) reduction of O2 to water (approximately 97 %) in alkaline solution with an onset potential of 0.988 V vs. RHE, and demonstrates superior stability and excellent tolerance for the methanol crossover effect in comparison to a commercial Pt/C catalyst. The copper complexes were grafted onto the surface of TiO2 through coordination of an imidazole-containing ligand, zoledronic acid (ZA), which binds to TiO2 through its bis-phosphoric acid anchoring group. Rational optimization of the copper catalyst's ORR performance was achieved by using an electron-deficient ligand, 5-nitro-1,10-phenanthroline (phen${{^{{\\rm NO}{_{2}}}}}$), and bridging benzene-1,3,5-tricarboxylate (BTC). This facile approach to the assembly of copper catalysts on TiO2 with rationally tuned ORR activity will have significant implications for the development of high-performance, non-precious-metal ORR catalysts. PMID:26602327

  13. EFFECT OF PRETREATMENT ON PT-CO/C CATHODE CATALYSTS FOR THE OXYGEN-REDUCTION REACTION

    SciTech Connect

    Fox, E.; Colon-Mercado, H.

    2010-01-19

    Carbon supported Pt and Pt-Co electrocatalysts for the oxygen reduction reaction in low temperature fuel cells were prepared by the reduction of the metal salts with sodium borohydride and sodium formate. The effect of surface treatment with nitric acid on the carbon surface and Co on the surface of carbon prior to the deposition of Pt was studied. The catalysts where Pt was deposited on treated carbon the ORR reaction preceded more through the two electron pathway and favored peroxide production, while the fresh carbon catalysts proceeded more through the four electron pathway to complete the oxygen reduction reaction. NaCOOH reduced Pt/C catalysts showed higher activity that NaBH{sub 4} reduced Pt/C catalysts. It was determined that the Co addition has a higher impact on catalyst activity and active surface area when used with NaBH{sub 4} as reducing agent as compared to NaCOOH.

  14. Metal-Organic Framework Derived Hierarchically Porous Nitrogen-Doped Carbon Nanostructures as Novel Electrocatalyst for Oxygen Reduction Reaction

    SciTech Connect

    Fu, Shaofang; Zhu, Chengzhou; Zhou, Yazhou; Yang, Guohai; Jeon, Ju Won; Lemmon, John P.; Du, Dan; Nune, Satish K.; Lin, Yuehe

    2015-10-01

    The hierarchically porous nitrogen-doped carbon materials, derived from nitrogen-containing isoreticular metal-organic framework-3 (IRMOF-3) through direct carbonization, exhibited excellent electrocatalytic activity in alkaline solution for oxygen reduction reaction (ORR). This high activity is attributed to the 10 presence of high percentage of quaternary and pyridinic nitrogen, the high surface area as well as good conductivity. When IRMOF-3 was carbonized at 950 °C (CIRMOF-3-950), it showed four-electron reduction pathway for ORR and exhibited better stability (about 78.5% current density was maintained) than platinum/carbon (Pt/C) in the current durability test. In addition, CIRMOF-3-950 presented high selectivity to cathode reactions compared to commercial Pt/C.

  15. Design of Laccase-Metal Organic Framework-Based Bioelectrodes for Biocatalytic Oxygen Reduction Reaction.

    PubMed

    Patra, Snehangshu; Sene, Saad; Mousty, Christine; Serre, Christian; Chaussé, Annie; Legrand, Ludovic; Steunou, Nathalie

    2016-08-10

    Laccase in combination with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as a mediator is a well-known bioelectrocatalyst for the 4-electron oxygen reduction reactions (ORR). The present work deals with the first exploitation of mesoporous iron(III) trimesate-based metal organic frameworks (MOF) MIL-100(Fe) (MIL stands for materials from Institut Lavoisier) as a new and efficient immobilization matrix of laccase for the building up of biocathodes for ORR. First, the immobilization of ABTS in the pores of the MOF was studied by combining micro-Raman spectroscopy, X-ray powder diffraction (XRPD), and N2 porosimetry. The ABTS-MIL-100(Fe)-based modified electrode presents excellent properties in terms of charge transfer kinetics and ionic conductivity as well as a very stable and reproducible electrochemical response, showing that MIL-100(Fe) provides a suitable and stabilizing microenvironment for electroactive ABTS molecules. In a second step, laccase was further immobilized on the MIL-100(Fe)-ABTS matrix. The Lac-ABTS-MIL-100(Fe)-CIE bioelectrode presents a high electrocatalytic current density of oxygen reduction and a reproducible electrochemical response characterized by a high stability over a long period of time (3 weeks). These results constitute a significant advance in the field of laccase-based bioelectrocatalysts for ORR. According to our work, it appears that the high catalytic efficiency of Lac-ABTS-MIL-100(Fe) for ORR may result from a synergy of chemical and catalytic properties of MIL-100(Fe) and laccase. PMID:27447023

  16. Simultaneous synthesis of gold nanoparticle/graphene nanocomposite for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Govindhan, Maduraiveeran; Chen, Aicheng

    2015-01-01

    We report here on a novel and facile technique for the simultaneous synthesis of a highly active and stable gold (Au) nanoparticle/reduced graphene oxide (rGO) sheet nanocomposite as an efficient electrocatalyst to facilitate the oxygen reduction reaction (ORR). X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscope (SEM), energy-dispersive X-ray (EDX) spectroscopy and electrochemical methods were employed to characterize the Au and rGO nanocomposites formed on the electrode surface. The major advantage of the simultaneous synthetic method is the integration of the superb properties of both Au nanoparticles and graphene in a single-step with a 100% usage of the precursors. The Au/rGO nanocomposites exhibited pronounced electrocatalytic performance towards ORR with approximately three times higher than that of Au nanoparticles. The nanocomposites show the ORR onset peak potentials at 0.12 and -0.03 V (vs Ag/AgCl), with reduction peaks at -0.06 and -0.16 V (vs Ag/AgCl) in 0.1 M H2SO4 and KOH media, which is ∼120-190 mV more positive than that of Au nanoparticles and a commercial Pt/C catalyst. Moreover, the nanocomposites exhibit excellent methanol tolerance and high durability in comparison with the commercial Pt/C. The new method demonstrated in this study provides an efficient route for the generation of ultrafine and highly dense Au nanoparticles that are homogeneously dispersed on rGO sheets for ORR.

  17. Investigation of catalytic activity towards oxygen reduction reaction of Pt dispersed on boron doped graphene in acid medium.

    PubMed

    Pullamsetty, Ashok; Sundara, Ramaprabhu

    2016-10-01

    Boron doped graphene was prepared by a facile method and platinum (Pt) decoration over boron doped graphene was done in various chemical reduction methods such as sodium borohydride (NaBH4), polyol and modified polyol. X-ray diffraction analysis indicates that the synthesized catalyst particles are present in a nanocrystalline structure and transmission and scanning electron microscopy were employed to investigate the morphology and particle distribution. The electrochemical properties were investigated with the help of the rotating disk electrode (RDE) technique and cyclic voltammetry. The results show that the oxygen reduction reaction (ORR) takes place by a four-electron process. The kinetics of the ORR was evaluated using K-L and Tafel plots. The electrocatalyst obtained in modified polyol reduction method has shown the better catalytic activity compared to other two electrocatalysts. PMID:27393888

  18. Nitrogen-Doped Carbon Nanoparticle-Carbon Nanofiber Composite as an Efficient Metal-Free Cathode Catalyst for Oxygen Reduction Reaction.

    PubMed

    Panomsuwan, Gasidit; Saito, Nagahiro; Ishizaki, Takahiro

    2016-03-23

    Metal-free nitrogen-doped carbon materials are currently considered at the forefront of potential alternative cathode catalysts for the oxygen reduction reaction (ORR) in fuel cell technology. Despite numerous efforts in this area over the past decade, rational design and development of a new catalyst system based on nitrogen-doped carbon materials via an innovative approach still present intriguing challenges in ORR catalysis research. Herein, a new kind of nitrogen-doped carbon nanoparticle-carbon nanofiber (NCNP-CNF) composite with highly efficient and stable ORR catalytic activity has been developed via a new approach assisted by a solution plasma process. The integration of NCNPs and CNFs by the solution plasma process can lead to a unique morphological feature and modify physicochemical properties. The NCNP-CNF composite exhibits a significantly enhanced ORR activity through a dominant four-electron pathway in an alkaline solution. The enhancement in ORR activity of NCNP-CNF composite can be attributed to the synergistic effects of good electron transport from highly graphitized CNFs as well as abundance of exposed catalytic sites and meso/macroporosity from NCNPs. More importantly, NCNP-CNF composite reveals excellent long-term durability and high tolerance to methanol crossover compared with those of a commercial 20 wt % supported on Vulcan XC-72. We expect that NCNP-CNF composite prepared by this synthetic approach can be a promising metal-free cathode catalyst candidate for ORR in fuel cells and metal-air batteries. PMID:26908214

  19. Catalytic activity of transition metal-N4 moieties in graphene toward the oxygen reduction reaction: A DFT study

    NASA Astrophysics Data System (ADS)

    Orellana, Walter

    2013-03-01

    The search for non-precious metal cathode catalysts for the oxygen reduction reaction (ORR) that replace platinum in proton exchange membrane fuel cells is one of the main challenges toward the use of hydrogen as clean energy for transportation. Most current works on ORR catalysts focuses on N-coordinated iron in a carbon matrix. Although the nature of the active site is still a mystery, different carbon-supported Fe-Nx active sites have been proposed. In this work, The O2 dissociation after the interaction with the metal center of M-N4 moieties in graphene (with M = Mn, Fe, and Co) are addressed by density functional theory calculations. Both, saddle points and minimum energy paths for the ORR in the allowed spin channels have been identified. Our results show that the Mn-N4 center in graphene exhibits the lowest activation barrier in all spin channel, less than 1 eV, suggesting improved ORR activity, while for Fe-N4 and Co-N4 they range between 1.2 and 1.6 eV. Our calculations suggest that the O2 dissociation would proceed through different spin channel which would increase the reaction rate, particularly for Mn-O2 and Fe-O2 moieties. We also investigate energetically favorable routes to incorporate the M-N4 centers in graphene. Work supported by FONDECYT under Grant No. 1090489

  20. Graphene-based non-noble-metal Co/N/C catalyst for oxygen reduction reaction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Niu, Kexing; Yang, Baoping; Cui, Jinfeng; Jin, Jutao; Fu, Xiaogang; Zhao, Qiuping; Zhang, Junyan

    2013-12-01

    This study develops a promising catalyst for oxygen reduction reaction (ORR) via a simple two-step heat treatment of a mixture of cobalt(II) nitrate hexahydrate (Co(NO3)2·6H2O), polyethyleneimine (PEI), and graphene oxide (GO), firstly in argon atmosphere and then in ammonia atmosphere. X-ray photoemission spectroscopy (XPS) result reveals that the catalyst has pyridinic N-dominant (46% atomic concentration among all N components) on the surface. The kinetics measurement of the catalyst in 0.1 M KOH solution using a rotating disk electrode (RDE) reveals that the catalyst (Co/N/rGO(NH3)) has high activity. Furthermore, the number of electrons exchanged during the ORR with the catalyst is determined to be ˜3.9, suggesting that the ORR is dominated by a 4e- reduction of O2 to H2O. The catalyst has good stability, and its performance is superior to the commercial Pt/C(20%) catalyst in alkaline condition, making the material a promising substitute to noble metal ORR electrocatalyst on the cathode side of fuel cells.

  1. Nitrogen-doped carbon nanotubes as catalysts for the oxygen reduction reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Yang, Mei; Yang, Duangguang; Chen, Hongbiao; Gao, Yong; Li, Huaming

    2015-04-01

    A novel electrocatalyst for the oxygen reduction reaction (ORR) is fabricated by directly annealing oxidized carbon nanotubes and tripyrrolyl[1,3,5]triazine in nitrogen. The structural and chemical properties of the resultant N-doped carbon nanotubes (NCNTs) are systematically investigated. The electrocatalytic activity of the NCNTs towards ORR in O2-saturated 0.1 M KOH electrolyte is evaluated using rotating disk electrode voltammetry. The results demonstrate that the as-prepared NCNT-900 (annealed at 900 °C) exhibits excellent electrochemical performance towards ORR in alkaline medium with an onset potential of -0.038 V (vs Ag/AgCl), a high kinetic current density of 31.26 mA cm-2 at -0.25 V, a dominant four-electron transfer mechanism (n = 3.88 at -0.25 V), and excellent methanol tolerance and durability. The results obtained are significant for the development of N-doped carbon-based electrocatalysts for alkaline fuel cells.

  2. Cu,N-codoped Hierarchical Porous Carbons as Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Yu, Haiyan; Fisher, Adrian; Cheng, Daojian; Cao, Dapeng

    2016-08-24

    It remains a huge challenge to develop nonprecious electrocatalysts with high activity to substitute commercial Pt catalysts for oxygen reduction reactions (ORR). Here, the Cu,N-codoped hierarchical porous carbon (Cu-N-C) with a high content of pyridinic N was synthesized by carbonizing Cu-containing ZIF-8. Results indicate that Cu-N-C shows excellent ORR electrocatalyst properties. First of all, it nearly follows the four-electron route, and its electron transfer number reaches 3.92 at -0.4 V. Second, both the onset potential and limited current density of Cu-N-C are almost equal to those of a commercial Pt/C catalyst. Third, it exhibits a better half-wave potential (∼16 mV) than a commercial Pt/C catalyst. More importantly, the Cu-N-C displays better stability and methanol tolerance than the Pt/C catalyst. All of these good properties are attributed to hierarchical structure, high pyridinic N content, and the synergism of Cu and N dopants. The metal-N codoping strategy can significantly enhance the activity of electrocatalysts, and it will provide reference for the design of novel N-doped porous carbon ORR catalysts. PMID:27490846

  3. Multifunctional Co3S4/graphene composites for lithium ion batteries and oxygen reduction reaction.

    PubMed

    Mahmood, Nasir; Zhang, Chenzhen; Jiang, Jie; Liu, Fei; Hou, Yanglong

    2013-04-15

    Cobalt sulfide is a good candidate for both lithium ion batteries (LIBs) and cathodic oxygen reduction reaction (ORR), but low conductivity, poor cyclability, capacity fading, and structural changes hinder its applications. The incorporation of graphene into Co3S4 makes it a promising electrode by providing better electrochemical coupling, enhanced conductivity, fast mobility of ions and electrons, and a stabilized structure due to its elastic nature. With the objective of achieving high-performance composites, herein we report a facile hydrothermal process for growing Co3S4 nanotubes (NTs) on graphene (G) sheets. Electrochemical impedance spectroscopy (EIS) verified that graphene dramatically increases the conductivity of the composites to almost twice that of pristine Co3S4. Electrochemical measurements indicated that the as-synthesized Co3S4/G composites exhibit good cyclic stability and a high discharge capacity of 720 mA h g(-1) up to 100 cycles with 99.9% coulombic efficiency. Furthermore, the composites react with dissolved oxygen in the ORR by four- and two-electron mechanisms in both acidic and basic media with an onset potential close to that of commercial Pt/C. The stability of the composites is much higher than that of Pt/C, and exhibit high methanol tolerance. Thus, these properties endorse Co3 S4 /G composites as auspicious candidates for both LIBs and ORR. PMID:23447515

  4. FePt nanoparticles assembled on graphene as enhanced catalyst for oxygen reduction reaction.

    PubMed

    Guo, Shaojun; Sun, Shouheng

    2012-02-01

    Seven-nanometer FePt nanoparticles (NPs) were synthesized and assembled on graphene (G) by a solution-phase self-assembly method. These G/FePt NPs were a more active and durable catalyst for oxygen reduction reaction (ORR) in 0.1 M HClO(4) than the same NPs or commercial Pt NPs deposited on conventional carbon support. The G/FePt NPs annealed at 100 °C for 1 h under Ar + 5% H(2) exhibited specific ORR activities of 1.6 mA/cm(2) at 0.512 V and 0.616 mA/cm(2) at 0.557 V (vs Ag/AgCl). As a comparison, the commercial Pt NPs (2-3 nm) had specific activities of 0.271 and 0.07 mA/cm(2) at the same potentials. The G/FePt NPs were also much more stable in the ORR condition and showed nearly no activity change after 10 000 potential sweeps. The work demonstrates that G is indeed a promising support to improve NP activity and durability for practical catalytic applications. PMID:22279956

  5. Co-N Decorated Hierarchically Porous Graphene Aerogel for Efficient Oxygen Reduction Reaction in Acid.

    PubMed

    Fu, Xiaogang; Choi, Ja-Yeon; Zamani, Pouyan; Jiang, Gaopeng; Hoque, Md Ariful; Hassan, Fathy Mohamed; Chen, Zhongwei

    2016-03-01

    Nitrogen-functionalized graphene materials have been demonstrated as promising electrocatalyst for the oxygen reduction reaction (ORR), owning to their respectable activity and excellent stability in alkaline electrolyte. However, they exhibit unacceptable catalytic activity in acid medium. Here, a hierarchically porous Co-N functionalized graphene aerogel is prepared as an efficient catalyst for the ORR in acid electrolyte. In the preparation process, polyaniline (PANI) is introduced as a pore-forming agent to aid in the self-assembly of graphene species into a porous aerogel networks, and a nitrogen precursor to induce in situ nitrogen doping. Therefore, a Co-N decorated graphene aerogel framework with a large surface area (485 m(2) g(-1)) and an abundance of meso/macropores is effectively formed after heat treatment. Such highly desired structures can not only expose sufficient active sites for the ORR but also guarantee the fast mass transfer in the catalytic process, which provides significant catalytic activity with positive onset and half wave potentials, low hydrogen peroxide yield, high resistance to methanol crossover, and remarkable stability that is comparable to commercial Pt/C in acid medium. PMID:26937737

  6. Al13@Pt42 Core-Shell Cluster for Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Xiao, B. B.; Zhu, Y. F.; Lang, X. Y.; Wen, Z.; Jiang, Q.

    2014-06-01

    To increase Pt utilization for oxygen reduction reaction (ORR) in fuel cells, reducing particle sizes of Pt is a valid way. However, poisoning or surface oxidation limits the smallest size of Pt particles at 2.6 nm with a low utility of 20%. Here, using density functional theory calculations, we develop a core-shell Al13@Pt42 cluster as a catalyst for ORR. Benefit from alloying with Al in this cluster, the covalent Pt-Al bonding effectively activates the Pt atoms at the edge sites, enabling its high utility up to 70%. Valuably, the adsorption energy of O is located at the optimal range with 0.0-0.4 eV weaker than Pt(111), while OH-poisoning does not observed. Moreover, ORR comes from O2 dissociation mechanism where the rate-limiting step is located at OH formation from O and H with a barrier of 0.59 eV, comparable with 0.50 eV of OH formation from O and H2O on Pt(111).

  7. Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

    PubMed Central

    Cheon, Jae Yeong; Kim, Taeyoung; Choi, YongMan; Jeong, Hu Young; Kim, Min Gyu; Sa, Young Jin; Kim, Jaesik; Lee, Zonghoon; Yang, Tae-Hyun; Kwon, Kyungjung; Terasaki, Osamu; Park, Gu-Gon; Adzic, Radoslav R.; Joo, Sang Hoon

    2013-01-01

    The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity. PMID:24056308

  8. Oxygen Reduction Reaction on Cobalt--(6)Pyrrole Cluster: Density Functional Theory Study

    NASA Astrophysics Data System (ADS)

    Saputro, Adhitya G.; Rusydi, Febdian; Kasai, Hideaki; Dipojono, Hermawan K.

    2012-03-01

    We investigate the potential energy surface profile for various water formation reaction schemes on an unsupported cobalt--(6)pyrrole [Co--(6)Ppy] cluster in the vacuum state by density functional theory (DFT) calculations. We find that in the Co--(6)Ppy cluster, the formation of H2O2 is energetically not favorable. Instead of forming H2O2ad, the \\text{HO\\text{2ad} + H reaction forms 2OHad or \\text{O\\text{ad} + H2O immediately. The adsorption of H2O2 on the Co--(6)Ppy cluster is possible only if the H2O2 molecule comes from or forms outside of the cluster. The formation of two OH molecules instead of H2O2 on the Co--(6)Ppy cluster suggests that the oxygen reduction reaction (ORR) mechanism on the unsupported Co--(6)Ppy cluster in the vacuum state prefers the direct four-electron reduction to water.

  9. ORR Deer Hunt Monitoring Program

    SciTech Connect

    Scofield, P.A.; Teasley, N.A.

    1999-09-01

    The primary purpose for the initiation of deer hunts on the Oak Ridge Reservation (ORR) was deer population control to reduce collisions with vehicles and maintain a healthy herd and habitat. As of 1997, thirteen annual deer hunts have been conducted on the ORR. The deer hunt monitoring program (DHMP) has two components -- a field screening monitoring program and a confirmatory laboratory analysis program of both retained and randomly selected released deer samples.

  10. Oxygen reduction reaction induced pH-responsive chemo-mechanical hydrogel actuators.

    PubMed

    Yu, Cunjiang; Yuan, Peixi; Erickson, Evan M; Daly, Christopher M; Rogers, John A; Nuzzo, Ralph G

    2015-10-28

    We describe and characterize elementary designs for electrochemical micro- and macro-scale chemomechanical hydrogel actuators. The actuation of a pH-sensitive cross-linked polyacrylic acid (PAA) hydrogel is driven in the model devices through the oxygen reduction reaction (ORR) occurring at the electrodes of an embedded Au mesh micro-electrochemical array. Proton consumption by the ORR at the cathode of the embedded electrochemical cell leads to the formation of a localized pH gradient that in turn drives the strain response in the composite actuators. The dynamics result from the ionization of the carboxylic acid moieties of the PAA network in the high pH region, yielding an osmotic pressure that drives a volumetric expansion due to water imbibition. This system actuates both stably and reversibly; when the electrochemically-induced ORR is halted, the localized pH gradient dissipates due to diffusive mixing, which in turn relaxes the induced strains. Two approaches to the fabrication of hydrogel actuators were examined in this work. The first method adopted a design based on small flagella (∼0.2 mm × 1.5 mm × 60 μm, width × length × height) in which the actuating PAA structures are molded atop a set of fixed electrodes mounted on a supporting substrate. These hydrogel actuators show fast, large-amplitude, and largely reversible responses in the ORR mediated chemomechanical dynamics. We also investigated larger hydrogel actuators (∼4.5 mm × 11 mm × 1 mm, width × length × height), based on an autonomous design that embeds an open mesh stretchable micro-electrode array within the hydrogel. The significant and design-dependent impacts of mass transfer on the chemomechanical dynamics are evidenced in each case, a feature examined to elucidate more efficient mesoscopic design rules for actuators of this form. PMID:26323563

  11. High resolution mapping of oxygen reduction reaction kinetics at polycrystalline platinum electrodes.

    PubMed

    Chen, Chang-Hui; Meadows, Katherine E; Cuharuc, Anatolii; Lai, Stanley C S; Unwin, Patrick R

    2014-09-14

    The scanning droplet-based technique, scanning electrochemical cell microscopy (SECCM), combined with electron backscatter diffraction (EBSD), is demonstrated as a powerful approach for visualizing surface structure effects on the rate of the oxygen reduction reaction (ORR) at polycrystalline platinum electrodes. Elucidating the effect of electrode structure on the ORR is of major interest in connection to electrocatalysis for energy-related applications. The attributes of the approach herein stem from: (i) the ease with which the polycrystalline substrate electrode can be prepared; (ii) the wide range of surface character open to study; (iii) the possibility of mapping reactivity within a particular facet (or grain), in a pseudo-single-crystal approach, and acquiring a high volume of data as a consequence; (iv) the ready ability to measure the activity at grain boundaries; and (v) an experimental arrangement (SECCM) that mimics the three-phase boundary in low temperature fuel cells. The kinetics of the ORR was analyzed and a finite element method model was developed to explore the effect of the three-phase boundary, in particular to examine pH variations in the droplet and the differential transport rates of the reactants and products. We have found a significant variation of activity across the platinum substrate, inherently linked to the crystallographic orientation, but do not detect any enhanced activity at grain boundaries. Grains with (111) and (100) contributions exhibit considerably higher activity than those with (110) and (100) contributions. These results, which can be explained by reference to previous single-crystal measurements, enhance our understanding of ORR structure-activity relationships on complex high-index platinum surfaces, and further demonstrate the power of high resolution flux imaging techniques to visualize and understand complex electrocatalyst materials. PMID:25072300

  12. Palladium-coated manganese dioxide catalysts for oxygen reduction reaction in alkaline media

    NASA Astrophysics Data System (ADS)

    Sun, Wei; Hsu, Andrew; Chen, Rongrong

    2011-05-01

    Pd-coated manganese dioxide catalysts (Pd@MnO2) were synthesized by depositing Pd on the surface of β-MnO2 nanorod particles in aqueous solutions at room temperature. TEM, XRD and electrochemical characterizations indicated that the MnO2 nanorods were successfully coated with Pd particles when the Pd weight percentage was more than 4.6%. The activities of the Pd@MnO2 catalysts for oxygen reduction reaction (ORR) were investigated using a rotating disk electrode (RDE) and a rotating ring-disk electrode (RRDE). The ORR onset potentials on the Pd@MnO2 catalyst shifted positively for more than 250 mV compared with the MnO2 catalyst without Pd coatings. Both the ORR onset potentials and the limiting current density obtained by the RDE measurements on the Pd@MnO2 catalysts were close to those on the Pd black catalyst. The mass activity of the Pd@MnO2 catalysts (normalized by Pd mass) was 2.5 times higher than that of the Pd black catalyst. Based on the Tafel slopes of the Pd@MnO2 catalysts (which is about 60 mV dec-1 at low overpotentials), and based on the fact that the activation energies of the Pd@MnO2 catalysts are very close to the activation energies of the Pd catalysts, one may conclude that the small amount of Pd coating provides the primary ORR activity of the Pd@MnO2 catalysts.

  13. Oxygen reduction reaction: A framework for success

    DOE PAGESBeta

    Allendorf, Mark D.

    2016-05-06

    Oxygen reduction at the cathode of fuel cells typically requires a platinum-based material to catalyse the reaction, but lower-cost, more stable catalysts are sought. Here, an intrinsically conductive metal–organic framework based on cheaper elements is shown to be a durable, structurally well-defined catalyst for this reaction.

  14. Oxygen reduction reaction: A framework for success

    NASA Astrophysics Data System (ADS)

    Allendorf, Mark D.

    2016-05-01

    Oxygen reduction at the cathode of fuel cells typically requires a platinum-based material to catalyse the reaction, but lower-cost, more stable catalysts are sought. Now, an intrinsically conductive metal–organic framework based on cheaper elements is shown to be a durable, structurally well-defined catalyst for this reaction.

  15. On the importance of correcting for the uncompensated Ohmic resistance in model experiments of the oxygen reduction reaction.

    SciTech Connect

    van der Vliet, D.; Strmcnik, D. S.; Wang, C.; Stamenkovic, V. R.; Markovic, N. M; Koper, M. T. M.; Materials Science Division; Leiden Univ.

    2010-08-15

    When measuring the current due to the Oxygen Reduction Reaction (ORR) and hydrogen oxidation reaction (HOR) on Pt and Pt alloys in aqueous electrolyte, it is important to take care of two major sources of error that are relatively easy to correct for. First, when measuring ORR voltammetry, adsorption processes are superimposed on the current. Second, the system resistance causes an Ohmic drop that may have a profound effect on the measured curves, especially at the higher currents close to the diffusion limiting current. More importantly, we show that it also influences the kinetic part of the potential curve in such a way that the Tafel slope may be determined incorrectly when failing to correct for Ohmic drop. Finally, because electrolyte resistance lowers with increasing temperature, failure to compensate for Ohmic.

  16. Sulfur, trace nitrogen and iron codoped hierarchically porous carbon foams as synergistic catalysts for oxygen reduction reaction.

    PubMed

    Guo, Zhaoyan; Jiang, Congcong; Teng, Chao; Ren, Guangyuan; Zhu, Ying; Jiang, Lei

    2014-12-10

    Sulfur, trace nitrogen and iron codoped, hierarchically porous carbon foams (HPCFs) were fabricated by directly pyrolyzing sulfur-enriched conductive polymer, poly(3,4-ethylenedioxythiphene)-polystyrenesulfonic acid (PEDOT-PSS) aerogels under argon atmosphere. This simple pyrolysis treatment results in the molecular rearrangement of heteroatom sulfur, adjacent carbons and trace nitrogen/iron from oxidants to form active catalytic sites of HPCFs. At the same time, the high porosity of HPCFs provides the large surface area for the uniform distribution of active sites, and allows rapid oxygen transport and diffusion. As a result, these HPCFs exhibit the enhanced catalytic performances for oxygen reduction reaction (ORR) via a direct four-electron reduction pathway in alkaline electrolyte. Besides, they also display a higher stability and better methanol/CO tolerance than the commercial Pt/C catalyst, which makes them promising low cost, non-precious-metal ORR catalysts for practical application in fuel cells and metal-air batteries. PMID:25402945

  17. Oxygen reduction reaction activity and structural stability of Pt-Au nanoparticles prepared by arc-plasma deposition.

    PubMed

    Takahashi, Shuntaro; Chiba, Hiroshi; Kato, Takashi; Endo, Shota; Hayashi, Takehiro; Todoroki, Naoto; Wadayama, Toshimasa

    2015-07-28

    The oxygen reduction reaction (ORR) activity and durability of various Au(x)/Pt100 nanoparticles (where x is the atomic ratio of Au against Pt) are evaluated herein. The samples were fabricated on a highly-oriented pyrolytic graphite substrate at 773 K through sequential arc-plasma depositions of Pt and Au. The electrochemical hydrogen adsorption charges (electrochemical surface area), particularly the characteristic currents caused by the corner and edge sites of the Pt nanoparticles, decrease with increasing Au atomic ratio (x). In contrast, the specific ORR activities of the Au(x)/Pt100 samples were dependent on the atomic ratios of Pt and Au: the Au28/Pt100 sample showed the highest specific activity among all the investigated samples (x = 0-42). As for ORR durability evaluated by applying potential cycles between 0.6 and 1.0 V in oxygen-saturated 0.1 M HClO4, Au28/Pt100 was the most durable sample against the electrochemical potential cycles. The results clearly showed that the Au atoms located at coordinatively-unsaturated sites, e.g. at the corners or edges of the Pt nanoparticles, can improve the ORR durability by suppressing unsaturated-site-induced degradation of the Pt nanoparticles. PMID:26118789

  18. Nitrogen-doped porous carbon nanosheets made from biomass as highly active electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Pan, Fuping; Cao, Zhongyue; Zhao, Qiuping; Liang, Hongyu; Zhang, Junyan

    2014-12-01

    The successful commercialization of fuel cells requires the efficient electrocatalyst to make the oxygen reduction reaction (ORR) fast because of the sluggish nature of ORR and the high cost of the platinum catalysts. In this work, we report the excellent performance of metal-free nitrogen-doped porous carbon nanosheets (NPCN) with hierarchical porous structure and a high surface area of 1436.02 m2 g-1 for catalyzing ORR. The active NPCN is synthesized via facile high-temperature carbonization of natural ginkgo leaves followed by purification and ammonia post-treatment without using additional supporting templates and activation processes. In O2-saturated 0.1 M KOH solution, the resultant NPCN exhibits a high kinetic-limiting current density of 13.57 mA cm-2 at -0.25 V (vs. Ag/AgCl) approaching that of the commercial Pt/C catalyst (14 mA cm-2) and long-term electrochemical stability. Notably, the NPCN shows a slightly negative ORR half-wave potential in comparison with Pt/C (ΔE1/2 = 19 mV). The excellent electrocatalytic properties of NPCN originate from the combined effect of optimal nitrogen doping, high surface area, and porous architecture, which induce the high-density distribution of highly active and stable catalytic sites.

  19. Highly efficient nonprecious metal catalysts towards oxygen reduction reaction based on three-dimensional porous carbon nanostructures.

    PubMed

    Zhu, Chengzhou; Li, He; Fu, Shaofang; Du, Dan; Lin, Yuehe

    2016-02-01

    Developing a low cost, highly active, durable cathode towards an oxygen reduction reaction (ORR) is one of the high-priority research directions for commercialization of low-temperature polymer electrolyte membrane fuel cells (PEMFCs). However, the electrochemical performance of PEMFCs is still hindered by the high cost and insufficient durability of the traditional Pt-based cathode catalysts. Under these circumstances, the search for efficient alternatives to replace Pt for constructing highly efficient nonprecious metal catalysts (NPMCs) has been growing intensively and has received great interest. Combining with the compositional effects, the accurate design of NPMCs with 3D porous nanostructures plays a significant role in further enhancing ORR performance. These 3D porous architectures are able to provide higher specific surface areas and larger pore volumes, not only maximizing the availability of electron transfer within the nanosized electrocatalyst surface area but also providing better mass transport of reactants to the electrocatalyst. In this Tutorial Review, we focus on the rational design and synthesis of different 3D porous carbon-based nanomaterials, such as heteroatom-doped carbon, metal-nitrogen-carbon nanostructures and a series of carbon/nonprecious metal-based hybrids. More importantly, their enhanced ORR performances are also demonstrated by virtue of their favorably porous morphologies and compositional effects. Finally, the future trends and perspectives for the highly efficient porous NPMCs regarding the material design are discussed, with an emphasis on substantial development of advanced carbon-based NPMCs for ORR in the near future. PMID:26658546

  20. The enhanced electrocatalytic activity of okara-derived N-doped mesoporous carbon for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Wang, Rongfang; Wang, Hui; Zhou, Tianbao; Key, Julian; Ma, Yanjiao; Zhang, Zheng; Wang, Qizhao; Ji, Shan

    2015-01-01

    Nitrogen-doped carbon (N-C) catalysts can potentially offer high ORR (oxygen reduction reaction) electrocatalytic activity comparable to Pt/C catalysts. Here, we establish a correlation between N-species (pyridinic-N and graphitic-N) with high ORR activity and a key role for Fe in their preparation. N-C catalysts are prepared from okara (a cheap, nitrogen-rich, biomass precursor) using a facile synthesis method with inclusion of FeCl3 at different steps of synthesis. Mesoporous N-C catalyst is produced that had ORR activity comparable to that of commercial Pt/C catalyst. High ORR-activity N-C results from the presence of FeCl3 at a specific step during synthesis. Detailed investigation by XPS reveals that increased levels of pyridinic-N and graphitic-N arose from pyridinic-N-oxide conversion in the presence of Fe. We conclude that transforming inert N species to active N species underlies the increase in active catalytic sites on the carbon surface and offers a means to improve N-C catalyst performance.

  1. Low Pt-Loaded Mesoporous Sodium Germanate as a High-Performance Electrocatalyst for the Oxygen Reduction Reaction.

    PubMed

    Zhou, Xiaoxia; Chen, Lisong; Wan, Gang; Chen, Yu; Kong, Qinglu; Chen, Hangrong; Shi, Jianlin

    2016-09-01

    Although Pt/C catalysts show relatively high activities for the oxygen reduction reaction (ORR) and great potential for use in polymer electrolyte membrane fuel cells, the large amount of Pt required and the poor stability of Pt/C-based catalysts remain big challenges. Herein, mesoporous Na4 Ge9 O20 micro-crystals have been successfully synthesized to serve as a new kind of electrocatalyst support owing to its special structural characteristics and high structural stability. After loading a low amount of Pt (5 wt %) nanoparticles of 2-5 nm in diameter, the obtained mesoporous Pt/Na4 Ge9 O20 composite shows not only high electrocatalytic activity for ORR in both acidic and alkaline electrolyte media, which are comparable to those of conventional 20 wt % Pt/C, but also remarkably enhanced Pt mass-specified ORR current density and durability. Synergetic catalytic effects between loaded Pt and the support for the ORR activity has been proposed. PMID:27539826

  2. Nitrogen-doped mesoporous graphene as a synergistic electrocatalyst matrix for high-performance oxygen reduction reaction.

    PubMed

    Xiao, Jingjing; Bian, Xiaojun; Liao, Lei; Zhang, Song; Ji, Chang; Liu, Baohong

    2014-10-22

    To balance the anchoring sites and conductivity of the catalyst supports is a dilemma in electrocatalytic oxygen reduction reaction (ORR). Nitrogen-doped mesoporous graphene (N-MG) with large surface area, high porosity, and superior intrinsic conductivity has been developed to address this issue. Using N-MG as the backbone, a hybrid catalyst of Co3O4 nanocrystals embedded on N-MG (Co3O4/N-MG) was prepared for the electrocatalytic ORR in alkaline media. The Co3O4/N-MG showed high catalytic activity for the four-electron ORR, giving a more positive onset potential (0.93 V vs RHE) and a higher current density. The unique property of N-MG and the synergetic effect of Co3O4 and N-MG are prominent for ORR. With improved electrocatalytic activity and durability, the Co3O4/N-MG can be an efficient nonprecious metal catalyst and potentially used to substitute the platinum-based cathode catalysts in fuel cells and metal-air batteries. PMID:25264608

  3. Heteroatoms ternary-doped porous carbons derived from MOFs as metal-free electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Li, Ji-Sen; Li, Shun-Li; Tang, Yu-Jia; Li, Kui; Zhou, Lei; Kong, Ning; Lan, Ya-Qian; Bao, Jian-Chun; Dai, Zhi-Hui

    2014-05-01

    The nitrogen (N), phosphorus (P) and sulphur (S) ternary-doped metal-free porous carbon materials have been successfully synthesized using MOFs as templates (denoted as NPS-C-MOF-5) for oxygen reduction reaction (ORR) for the first time. The influences of porous carbons from carbonizing different MOFs and carbonization temperature on ORR have been systematically investigated. Due to the synergistic effect of N, P and S ternary-doping, the NPS-C-MOF-5 catalyst shows a higher onset potential as a metal-free electrocatalyst for ORR among the currently reported metal-free electrocatalysts, very close to the commercial Pt-C catalyst. In particular, the kinetic limiting current density of NPS-C-MOF-5 catalyst at -0.6 V is up to approximate -11.6 mA cm-2, which is 1.2 times higher than that of the commercial Pt-C catalyst. Furthermore, the outstanding methanol tolerance and excellent long-term stability of NPS-C-MOF-5 are superior to those of the commercial Pt-C catalyst for ORR in alkaline media.

  4. Heteroatoms ternary-doped porous carbons derived from MOFs as metal-free electrocatalysts for oxygen reduction reaction

    PubMed Central

    Li, Ji-Sen; Li, Shun-Li; Tang, Yu-Jia; Li, Kui; Zhou, Lei; Kong, Ning; Lan, Ya-Qian; Bao, Jian-Chun; Dai, Zhi-Hui

    2014-01-01

    The nitrogen (N), phosphorus (P) and sulphur (S) ternary-doped metal-free porous carbon materials have been successfully synthesized using MOFs as templates (denoted as NPS-C-MOF-5) for oxygen reduction reaction (ORR) for the first time. The influences of porous carbons from carbonizing different MOFs and carbonization temperature on ORR have been systematically investigated. Due to the synergistic effect of N, P and S ternary-doping, the NPS-C-MOF-5 catalyst shows a higher onset potential as a metal-free electrocatalyst for ORR among the currently reported metal-free electrocatalysts, very close to the commercial Pt-C catalyst. In particular, the kinetic limiting current density of NPS-C-MOF-5 catalyst at −0.6 V is up to approximate −11.6 mA cm−2, which is 1.2 times higher than that of the commercial Pt-C catalyst. Furthermore, the outstanding methanol tolerance and excellent long-term stability of NPS-C-MOF-5 are superior to those of the commercial Pt-C catalyst for ORR in alkaline media. PMID:24875253

  5. High-performance of bare and Ti-doped α-MnO2 nanoparticles in catalyzing the Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Pargoletti, E.; Cappelletti, G.; Minguzzi, A.; Rondinini, S.; Leoni, M.; Marelli, M.; Vertova, A.

    2016-09-01

    Nanostructured MnO2 has unique electrocatalytic properties towards the Oxygen Reduction Reaction (ORR, the main cathodic reaction in metal-air devices), representing an excellent alternative to the expensive platinum. Herein, we report the hydrothermal synthesis of bare and 5% Ti-doped α-MnO2 nanoparticles using two different oxidizing agents, namely ammonium persulfate for MH_N samples and potassium permanganate for MH_K ones. The physico-chemical characterizations show that oxidant cations induce different structural, morphological and surface properties of the final powders. Hence, correlations between the different α-MnO2 characteristics and their electrocatalytic performances towards the ORR are drawn, highlighting the diverse effect even on the kinetic point of view. The ORR activity in alkaline media is examined by means of Staircase - Linear Sweep Voltammetry (S-LSV), using Gas Diffusion Electrode (GDE) as the air-cathode. The presence of these nanoparticles in the GDEs leads to a significant shift of the ORR onset potential (∼100 mV) towards less cathodic values, underlining the electrocatalytic efficiency of all the nanopowders. Furthermore, high exchange current densities (j0) are determined for GDEs with Ti-doped MnO2, comparable to the well-performing Pd45Pt5Sn50, and making it a promising material for the ORR.

  6. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    NASA Astrophysics Data System (ADS)

    Sun, Yu; Hsieh, Yu-Chi; Chang, Li-Chung; Wu, Pu-Wei; Lee, Jyh-Fu

    2015-03-01

    Nanoparticles of PdRu, Pd3Ru, and Pd9Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x = 1/3/9), suggest successful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd9Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1 M aqueous HClO4 solution. Subsequently, the Pd9Ru/C undergoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd9Ru surface (Pd9Ru@Pt). The Pd9Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg-1Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg-1Pt). The mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd9Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.

  7. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    DOE PAGESBeta

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; Wu, Pu -Wei; Lee, Jyh -Fu

    2014-11-22

    Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1more » M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.« less

  8. Transition metal/nitrogen dual-doped mesoporous graphene-like carbon nanosheets for the oxygen reduction and evolution reactions

    NASA Astrophysics Data System (ADS)

    Liu, Xiaobo; Amiinu, Ibrahim Saana; Liu, Shaojun; Cheng, Kun; Mu, Shichun

    2016-07-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been considered as a key step in energy conversion processes. Here, a novel and simple Mg(OH)2 nanocasting method is adopted to fabricate Co and N co-doped porous graphene-like carbon nanosheets (Co@N-PGCS) by using chitosan as both carbon and N sources. The as-obtained Co@N-PGCS shows a mesopore-dominated structure as well as a high specific surface area (1716 cm2 g-1). As a bifunctional electrocatalyst towards both the ORR and OER, it shows favorable ORR performance compared with the commercial Pt/C catalyst with an onset potential of -0.075 V and a half-wave potential of -0.151 V in 0.1 M KOH solutions. Furthermore, it also displays considerable OER properties compared with commercial IrO2. The effective catalytic activity could originate from the introduction of transition metal species and few-layer mesoporous carbon structures.The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been considered as a key step in energy conversion processes. Here, a novel and simple Mg(OH)2 nanocasting method is adopted to fabricate Co and N co-doped porous graphene-like carbon nanosheets (Co@N-PGCS) by using chitosan as both carbon and N sources. The as-obtained Co@N-PGCS shows a mesopore-dominated structure as well as a high specific surface area (1716 cm2 g-1). As a bifunctional electrocatalyst towards both the ORR and OER, it shows favorable ORR performance compared with the commercial Pt/C catalyst with an onset potential of -0.075 V and a half-wave potential of -0.151 V in 0.1 M KOH solutions. Furthermore, it also displays considerable OER properties compared with commercial IrO2. The effective catalytic activity could originate from the introduction of transition metal species and few-layer mesoporous carbon structures. Electronic supplementary information (ESI) available: The XPS fitted results, SEM and TEM images, the K-L equation, and some of the electrochemical

  9. Oxygen reduction reaction on palladium-cobalt alloy catalysts for polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Oishi, Kentaro

    The Oxygen Reduction Reaction (ORR) activity in acid medium on Pd-Co was studied in this work. The catalysts were synthesized by two techniques; physical vapor deposition technique and ultrasonic spray reaction technique. The last technique was developed for the first time in our laboratory for the supported electro catalyst preparation and direct deposition onto the carbon paper or gas diffusion electrode the for PEMFC applications. The electrochemical properties such as the amount of hydrogen adsorption/desorption, the oxide formation/reduction of Pd-Co alloy catalyst have not been sufficiently studied before. Therefore these electrochemical properties were investigated by using the Pd-Co thin films prepared by sputtering method. A thin film catalyst cannot be directly used as an electrode of working PEMFCs, however the sputtering method is very useful since the chemical composition of alloy and surface area of the electrode can be controlled easily. Thus the fundamental electrochemical properties such as the amount of hydrogen adsorption/desorption, oxide formation/reduction and oxide reduction peak position on thin films of Pd-Co alloy, Pd and Pt catalysts were determined and their correlations to ORR catalytic activities in acid medium were studied. Enhancements of the catalytic activities for ORR by Pd-Co binary alloys were found to be in agreement with results obtained in previous studies. Ultrasonic spray reaction method was developed for the first time in our laboratory for carbon supported nano-scale catalyst for PEMFC application. Fine catalyst particles supported on high surface area carbon powder are required to apply the catalyst as the PEMFC cathode materials for the commercialization, but none of the studies done before were able to successfully obtain the Pd-Co fine particles which are comparable with the existing carbon supported platinum catalyst (ϕ2-4nm). Therefore the establishment of the catalyst synthesis method for Pd-Co fine particles are

  10. Tuning the Catalytic Activity of Ru@Pt Core-Shell Nanoparticles for the Oxygen Reduction Reaction by Varying the Shell Thickness

    SciTech Connect

    Yang, Lijun; Vukmirovic, Miomir B.; Su, Dong; Sasaki, Kotaro; Herron, Jeffrey A.; Mavrikakis, Manos; Liao, Shijun; Adzic, Radoslav R.

    2013-01-31

    The kinetics of the oxygen reduction reaction (ORR) was investigated in acid solutions on Pt monolayers that were deposited on carbon-supported Ru nanoparticles using the rotating disk electrode technique. The Pt mass and specific ORR activities greatly depend on the number of Pt monolayers, and the optimum activity occurs with two Pt monolayers. Density functional theory calculations showed that Pt overlayers destabilize O* and OH* with respect to pure Pt, leading to more favorable hydrogenation kinetics. However, with only a single Pt overlayer, the destabilization is too much, and O–O bond breaking becomes rate limiting. Two to three Pt monolayers supported on the Ru core of our nanoparticles lead to increased activity. This work demonstrates that one can modulate the ORR activity of Pt monolayers supported on other metals by eliminating a part of the ligand effect by increasing the thickness of the Pt shell on top of the supporting metal surface.

  11. Porous Mn2 O3 : A Low-Cost Electrocatalyst for Oxygen Reduction Reaction in Alkaline Media with Comparable Activity to Pt/C.

    PubMed

    Wang, Wenhai; Geng, Jing; Kuai, Long; Li, Min; Geng, Baoyou

    2016-07-11

    Preparing nonprecious metal catalysts with high activity in the oxygen reduction reaction (ORR) can promote the development of energy conversion devices. Support-free porous Mn2 O3 was synthesized by a facile aerosol-spray-assisted approach (ASAA) and subsequent thermal treatment, and exhibited ORR activity that is comparable to commercial Pt/C The catalyst also exhibits notably higher activity than other Mn-based oxides, such as Mn3 O4 and MnO2 . The rotating ring disk electrode (RRDE) study indicates a typical 4-electron ORR pathway on Mn2 O3 . Furthermore, the porous Mn2 O3 demonstrates considerable stability and a good methanol tolerance in alkaline media. In light of the low cost and high earth abundance of Mn, the highly active Mn2 O3 is a promising candidate to be used as a cathode material in metal-air batteries and alkaline fuel cells. PMID:27258474

  12. Individual Reactions of Permanganate & Various Reductants

    SciTech Connect

    Gauger, Amber M.; Hallen, Richard T. )

    2000-11-01

    Tank waste on the Hanford Site contains radioactive elements that need to be removed from solution prior to disposal. One effective way to do this is to precipitate the radioactive elements with manganese solids, produced by permanganate oxidation. When added to tank waste, the permanganate, Mn(VII), reacts quickly producing manganese (IV) dioxide precipitate. Because of the speed of reaction it is difficult to tell what exactly is happening. Individual reactions using non-radioactive reductants found in the tanks were done to determine reaction kinetics, what permanganate was reduced to, and what oxidation products were formed. In this project sodium formate, sodium nitrite, glycolic acid, glycine, and sodium oxalate were studied using various concentrations of reductant in alkaline sodium hydroxide solutions. It was determined that formate reacted the quickest, followed by glycine and glycolic acid. Oxalate and nitrite did not appear to react with the permanganate solutions. The formate reactions quickly reduced permanganate, Mn(VII), to manganate, Mn(VI), and then to manganese (IV) dioxide. These reactions oxidized formate to carbonate and water. The glycolic acid was oxidized slower producing oxalate, water, and manganate, which would disproportionate to permanganate and manganese (IV) dioxide solids. The rate at which Mn(VI) disproportionates is usually slower than the rate at which Mn(VII) is reduced to Mn(VI), however in this case the rates were about equal. The glycine reactions formed some ammonia in solution, oxalate, and water. They reacted similar to the glycolic acid reactions, producing manganese dioxide precipitate before the solution turned totally green from Mn(VI). The formate reactions consumed one mole of hydroxide for every 3 moles of formate, while the glycolic acid and glycine reactions consumed 7 moles of hydroxide for every 3 moles of reductant. These reactions should help to determine the majority of products found in mixtures of solutions.

  13. Two dimensional N-containing carbon materials for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Feng, Yexin; Hu, Zhenpeng; Zhang, Lixin

    2013-03-01

    Seeking Pt replacement catalysts for cathode oxygen reduction reaction (ORR) is very important for the application of some new energy technologies like fuel cells and lithium-air batteries. N-doped graphene and carbon nitride sheets are two kinds of promising materials. For the N-doped graphene, it is found that nitrogen clusters other than isolated substitutionals are the active sites for oxygen reduction. Clusters with three or four N atoms are found to be the most active. Codoping boron (or Fe, Co) can effectively stabilize these high energy clusters while keep the cluster's high activity. For the carbon nitride sheets, in the C:N ratio range of 2.0-3.0, they are stable enough and can potentially catalyze the oxygen reduction as efficiently as Pt. It is revealed that the concentration of nitrogen can tune the Fermi level of the material and thus the catalytic property. The catalytic sites are located at those carbon atoms with special configurations rather than the nitrogen atoms. These results are helpful in designing N-containing carbon materials for ORR.

  14. Surface segregation effects in electrocatalysis: Kinetics ofoxygen reduction reaction on polycrystalline Pt3Ni alloy surfaces

    SciTech Connect

    Stamenkovic, V.; Schmidt, T.J.; Ross, P.N.; Markovic, N.M.

    2002-11-01

    Effects of surface segregation on the oxygen reduction reaction (ORR) have been studied on a polycrystalline Pt3Ni alloy in acid electrolyte using ultra high vacuum (UHV) surface sensitive probes and the rotating ring disk electrode (RRDE) method. Preparation, modification and characterization of alloy surfaces were done in ultra high vacuum (UHV). Depending on the preparation method, two different surface compositions of the Pt3Ni alloy are produced: a sputtered surface with 75 % Pt and an annealed surface (950 K ) with 100 % Pt. The latter surface is designated as the 'Pt-skin' structure, and is a consequence of surface segregation, i.e., replacement of Ni with Pt atoms in the first few atomic layers. Definitive surface compositions were established by low energy ion scattering spectroscopy (LEISS). The cyclic voltammetry of the 'Pt-skin' surface as well as the pseudocapacitance in the hydrogen adsorption/desorption potential region is similar to a polycrystalline Pt electrode. Activities of ORR on Pt3Ni alloy surfaces were compared to polycrystalline Pt in 0.1M HClO4 electrolyte for the observed temperature range of 293 < T < 333 K. The order of activities at 333 K was: 'Pt-skin' > Pt3Ni (75% Pt) > Pt with the maximum catalytic enhancement obtained for the 'Pt-skin' being 4 times that for pure Pt. Catalytic improvement of the ORR on Pt3Ni and 'Pt-skin' surfaces was assigned to the inhibition of Pt-OHad formation (on Pt sites) versus polycrystalline Pt. Production of H2O2 on both surfaces were similar compared to the pure Pt. Kinetic analyses of RRDE data confirmed that kinetic parameters for the ORR on the Pt3Ni and 'Pt-skin' surfaces are the same as on pure Pt: reaction order, m=1, two identical Tafel slopes, activation energy, {approx} 21-25 kJ/mol. Therefore the reaction mechanism on both Pt3Ni and 'Pt-skin' surfaces is the same as one proposed for pure Pt i.e. 4e{sup -} reduction pathway.

  15. Urchin-like CoP Nanocrystals as Hydrogen Evolution Reaction and Oxygen Reduction Reaction Dual-Electrocatalyst with Superior Stability.

    PubMed

    Yang, Hongchao; Zhang, Yejun; Hu, Feng; Wang, Qiangbin

    2015-11-11

    High-performance electrocatalysts with superior stability are critically important for their practical applications in hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). Herein, we report a facile method to fabricate urchin-like CoP nanocrystals (NCs) as catalyst for both HER and ORR with desirable electrocatalytic activities and long-term stability. The urchin-like CoP NCs with a diameter of 5 μm were successfully prepared by a hydrothermal reaction following a phosphidation treatment in N2 atmosphere and present excellent HER catalytic performance with a low onset overpotential of 50 mV, a small Tafel slope of 46 mV/decade, and an exceptional low overpotential of ~180 mV at a current density of 100 mA cm(-2) with a mass loading density of 0.28 mg/cm(2). Meanwhile, a remarkable ORR catalytic activity was observed with a half-potential of 0.7 V and an onset potential of 0.8 V at 1600 rpm and a scan rate of 5 mV s(-1). More importantly, the urchin-like CoP NCs present superior stability and keep their catalytic activity for at least 10 000 CV cycles for HER in 0.5 M H2SO4 and over 30 000 s for ORR in 0.1 M KOH, which is ascribed to their robust three-dimensional structure. This urchin-like CoP NCs might be a promising replacement to the Pt-based electrocatalysts in water splitting and fuel cells. PMID:26474359

  16. H2O2 detection analysis of oxygen reduction reaction on cathode and anode catalysts for polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Kishi, Akira; Shironita, Sayoko; Umeda, Minoru

    2012-01-01

    The generation percentage of H2O2 during oxygen reduction reaction (ORR) at practical powder electrocatalysts was evaluated using a scanning electrochemical microscope (SECM). We employed a porous microelectrode that contains electrocatalysts, namely, Pt/C, Pt-Co/C, and Pt-Ru/C as the oxygen reduction electrode of the SECM, and the Pt microelectrode was used as the H2O2 detector. First, the H2O2 generation amount at Pt/Cs was measured by changing the Pt loading amount. A Pt/C with a higher Pt loading has a higher ORR activity and generates a larger amount of H2O2. However, the percentage of H2O2 generated with respect to the ORR is the same regardless of the Pt loading amount. Next, H2O2 generation is markedly suppressed at the Pt-Co/C and Pt-Ru/C in the potential ranges of practical fuel cell cathode and anode, respectively. This explains that the Pt-Co/C is effective when used as a cathode, and the anode Pt-Ru/C enables the reduction of the H2O2 generation even if O2 crossleak occurs in the practical polymer electrolyte fuel cell.

  17. Evidences of the presence of different types of active sites for the oxygen reduction reaction with Fe/N/C based catalysts

    NASA Astrophysics Data System (ADS)

    Pérez-Alonso, Francisco J.; Domínguez, Carlota; Al-Thabaiti, Shaeel A.; Al-Youbi, Abdulrahman O.; Abdel Salam, Mohamed; Alshehri, Abdulmohsen A.; Retuerto, María; Peña, Miguel A.; Rojas, Sergio

    2016-09-01

    Fe/N/C catalysts are very active for the oxygen reduction reaction (ORR); however, the nature of the active site(s) is not fully understood. In this work, we study the performance of different types of N/C and Fe/N/C catalysts for the ORR, and the effect of the addition of NaCN. Phthalocyanine and graphene have been studied as model metal-free catalysts for the ORR. Fe-phthalocyanine (FePhcy), Fe-phthalocyanine dispersed in graphene (FePhcy/G) and Fe/N/G, have been used as model Fe-containing catalysts. FePhcy and FePhcy/G only contain Fe atoms coordinated to 4 nitrogen atoms. On the other hand, different species such as Fe-Nx and Fe3C coexist in Fe/N/G. In addition, Csbnd C ensembles are present in the graphene present in FePhcy/G and Fe/N/G. The ORR activity is characteristic of each catalyst, being the highest for the catalysts containing FeN4 ensembles. The addition of CN- results in the selective poisoning of the Fe-containing sites but it does not suppress the ORR activity of the Graphene containing samples. In-situ infrared spectroscopy studies during the ORR reveal that CN- poisoning of the Fe sites is reversible, desorbing at potentials less positive than ca. 600 mV. As a consequence, the ORR activity of the Fe-containing sites is recovered gradually.

  18. A novel cobalt tetranitrophthalocyanine/graphene composite assembled by an in situ solvothermal synthesis method as a highly efficient electrocatalyst for the oxygen reduction reaction in alkaline medium.

    PubMed

    Lv, Guojun; Cui, Lili; Wu, Yanying; Liu, Ying; Pu, Tao; He, Xingquan

    2013-08-21

    A novel micro/nano-composite, based on cobalt(II) tetranitrophthalocyanine (CoTNPc) grown on poly(sodium-p-styrenesulfonate) modified graphene (PGr), as a non-noble-metal catalyst for the oxygen reduction reaction (ORR), is fabricated by an in situ solvothermal synthesis method. The CoTNPc/PGr is characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), respectively. The electrocatalytic activity of the CoTNPc/PGr composite toward the ORR is evaluated using cyclic voltammetry and linear sweep voltammetry methods. The CoTNPc/PGr composite exhibits an unexpected, surprisingly high ORR activity compared to CoTNPc or PGr. The onset potential for ORR on CoTNPc/PGr is found to be around -0.10 V vs. SCE in 0.1 M NaOH solution, which is 30 mV and 70 mV more positive than that on PGr and CoTNPc, respectively. The peak current density on CoTNPc/PGr is about 2 times than that on PGr and CoTNPc, respectively. Rotating disk electrode (RDE) measurements reveal that the ORR mechanism is nearly via a four-electron pathway on CoTNPc/PGr. The current density for ORR on CoTNPc/PGr still remains 69.9% of its initial value after chronoamperometric measurements for 24 h. Pt/C catalyst, on the other hand, only retains 13.3% of its initial current. The peak potential shifts slightly and current barely changes when 3 M methanol is added. The fabricated composite catalyst for ORR displays high activity, good stability and excellent tolerance to the crossover effect, which may be used as a promising Pt-free catalyst in alkaline direct methanol fuel cells (DMFCs). PMID:23820483

  19. 2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction.

    PubMed

    Rowley-Neale, Samuel J; Fearn, Jamie M; Brownson, Dale A C; Smith, Graham C; Ji, Xiaobo; Banks, Craig E

    2016-08-21

    Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm(-2) modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR. PMID:27448174

  20. Nitrogen and phosphorus dual-doped hierarchical porous carbon foams as efficient metal-free electrocatalysts for oxygen reduction reactions.

    PubMed

    Jiang, Hongliang; Zhu, Yihua; Feng, Qian; Su, Yunhe; Yang, Xiaoling; Li, Chunzhong

    2014-03-10

    Despite tremendous progress in developing doped carbocatalysts for the oxygen reduction reaction (ORR), the ORR activity of current metal-free carbocatalysts is still inferior to that of conventional Pt/C catalysts, especially in acidic media and neutral solution. Moreover, it also remains a challenge to develop an effective and scalable method for the synthesis of metal-free carbocatalysts. Herein, we have developed nitrogen and phosphorus dual-doped hierarchical porous carbon foams (HP-NPCs) as efficient metal-free electrocatalysts for ORR. The HP-NPCs were prepared for the first time by copyrolyzing nitrogen- and phosphorus-containing precursors and poly(vinyl alcohol)/polystyrene (PVA/PS) hydrogel composites as in situ templates. Remarkably, the resulting HP-NPCs possess controllable nitrogen and phosphorus content, high surface area, and a hierarchical interconnected macro-/mesoporous structure. In studying the effects of the HP-NPCs on the ORR, we found that the as-prepared HP-NPC materials exhibited not only excellent catalytic activity for ORR in basic, neutral, and acidic media, but also much better tolerance for methanol oxidation and much higher stability than the commercial, state-of-the-art Pt/C catalysts. Because of all these outstanding features, it is expected that the HP-NPC material will be a very suitable catalyst for next-generation fuel cells and lithium-air batteries. In addition, the novel synthetic method described here might be extended to the preparation of many other kinds of hierarchical porous carbon materials or porous carbon that contains metal oxide for wide applications including energy storage, catalysis, and electrocatalysis. PMID:24520023

  1. Bifunctional enhancement of oxygen reduction reaction activity on Ag catalysts due to water activation on LaMnO3 supports in alkaline media

    NASA Astrophysics Data System (ADS)

    Park, Shin-Ae; Lee, Eun-Kyung; Song, Hannah; Kim, Yong-Tae

    2015-08-01

    Ag is considered to be one of the best candidates for oxygen reduction reaction electrocatalysts in alkaline media for application in various electrochemical energy devices. In this study, we demonstrate that water activation is a key factor in enhancing the ORR activity in alkaline media, unlike in acid environments. Ag supported on LaMnO3 having a high oxophilicity showed a markedly higher ORR activity than that on carbon with inert surfaces. Through various electrochemical tests, it was revealed that the origin of the enhanced ORR activity of Ag/LaMnO3 is the bifunctional effect mainly due to the water activation at the interface between Ag and LaMnO3. Furthermore, the ligand effect due to the charge transfer from Mn to Ag leads to the enhancement of both oxygen activation on Ag and water activation on Mn sites, and hence, an improvement in the ORR activity of Ag/LaMnO3. On the other hand, the strain effect based on the fine structure variation in the lattice was negligible. We therefore suggest that the employment of a co-catalyst or support with highly oxophilic nature and the maximization of the interface between catalyst and support should be considered in the design of electrocatalysts for the ORR in alkaline media.

  2. Bifunctional enhancement of oxygen reduction reaction activity on Ag catalysts due to water activation on LaMnO3 supports in alkaline media.

    PubMed

    Park, Shin-Ae; Lee, Eun-Kyung; Song, Hannah; Kim, Yong-Tae

    2015-01-01

    Ag is considered to be one of the best candidates for oxygen reduction reaction electrocatalysts in alkaline media for application in various electrochemical energy devices. In this study, we demonstrate that water activation is a key factor in enhancing the ORR activity in alkaline media, unlike in acid environments. Ag supported on LaMnO3 having a high oxophilicity showed a markedly higher ORR activity than that on carbon with inert surfaces. Through various electrochemical tests, it was revealed that the origin of the enhanced ORR activity of Ag/LaMnO3 is the bifunctional effect mainly due to the water activation at the interface between Ag and LaMnO3. Furthermore, the ligand effect due to the charge transfer from Mn to Ag leads to the enhancement of both oxygen activation on Ag and water activation on Mn sites, and hence, an improvement in the ORR activity of Ag/LaMnO3. On the other hand, the strain effect based on the fine structure variation in the lattice was negligible. We therefore suggest that the employment of a co-catalyst or support with highly oxophilic nature and the maximization of the interface between catalyst and support should be considered in the design of electrocatalysts for the ORR in alkaline media. PMID:26310526

  3. Bifunctional enhancement of oxygen reduction reaction activity on Ag catalysts due to water activation on LaMnO3 supports in alkaline media

    PubMed Central

    Park, Shin-Ae; Lee, Eun-Kyung; Song, Hannah; Kim, Yong-Tae

    2015-01-01

    Ag is considered to be one of the best candidates for oxygen reduction reaction electrocatalysts in alkaline media for application in various electrochemical energy devices. In this study, we demonstrate that water activation is a key factor in enhancing the ORR activity in alkaline media, unlike in acid environments. Ag supported on LaMnO3 having a high oxophilicity showed a markedly higher ORR activity than that on carbon with inert surfaces. Through various electrochemical tests, it was revealed that the origin of the enhanced ORR activity of Ag/LaMnO3 is the bifunctional effect mainly due to the water activation at the interface between Ag and LaMnO3. Furthermore, the ligand effect due to the charge transfer from Mn to Ag leads to the enhancement of both oxygen activation on Ag and water activation on Mn sites, and hence, an improvement in the ORR activity of Ag/LaMnO3. On the other hand, the strain effect based on the fine structure variation in the lattice was negligible. We therefore suggest that the employment of a co-catalyst or support with highly oxophilic nature and the maximization of the interface between catalyst and support should be considered in the design of electrocatalysts for the ORR in alkaline media. PMID:26310526

  4. Simultaneous formation of nitrogen and sulfur-doped transition metal catalysts for oxygen reduction reaction through pyrolyzing carbon-supported copper phthalocyanine tetrasulfonic acid tetrasodium salt

    NASA Astrophysics Data System (ADS)

    Qing, Xin; Shi, Jingjing; Ma, Chengyu; Fan, Mengyang; Bai, Zhengyu; Chen, Zhongwei; Qiao, Jinli; Zhang, Jiujun

    2014-11-01

    In this work, we report a spontaneous formation of copper (Cu-N-S/C) catalysts containing both nitrogen (N) and sulfur (S) elements using a one-step pyrolysis of carbon supported copper phthalocyanine tetrasulfonic acid tetrasodium salt (CuTSPc/C). The obtained catalysts exhibit high catalytic activities for oxygen reduction reaction (ORR) in alkaline media. Through electrochemical measurements and physical characterizations, several observations are reached as follows: (1) different pyrolysis temperatures can result in different catalyst structures and performances, and the optimum pyrolysis temperature is found to be 700 °C; (2) the electron transfer number of the ORR process catalyzed by the unpyrolyzed catalyst is about 2.5, after the pyrolysis, this number is increased to 3.5, indicating that the pyrolysis process can change the ORR pathway from a 2-electron transfer dominated process to a 4-electron transfer dominated one; (3) increasing catalyst loading from 40 μg cm-2 to 505 μg cm-2 can effectively improve the catalytic ORR activity, under which the percentage of H2O2 produced decreases sharply from 39.5% to 7.8%; and (4) the Cu ion can bond on pyridinic-N, graphite-N and C-Sn-C to form Cu-N-S/C catalyst active sites, which play the key role in the ORR activity.

  5. Three Dimensional P-doped Graphene Synthesized by Eco-Friendly Chemical Vapor Deposition for Oxygen Reduction Reactions.

    PubMed

    Li, Xiaoguang; Qiu, Yunfeng; Hu, Ping An

    2016-06-01

    Heteroatom doping provides possibilities for changing the electronic properties of graphene. Three Dimensional P-doped graphene (3DPG) was fabricated via chemical vapor deposition (CVD) using nickel foam as template and triphenylphosphine (TPP) as C and P sources simultaneously without using toxic organic solvent as carrier liquid. The invasion of P atoms into graphene networks make them non-electroneutral and consequently favor the adsorption of oxygen and O-O bond cleavage due to the charge polarization increase of the P-C bond. Thus, the as-prepared 3DPG served as an efficient electrocatalyst for oxygen reduction reaction (ORR). Additionally, the 3D porous structure is favorable for the mass transfer of electrolytes ions, hence 3DPG exhibit better electrocatalytic activity, long-term stability, and tolerance to crossover effect of methanol than pristine 3D graphene and Pt/C for ORR. PMID:27427693

  6. Hydrothermal transformation of dried grass into graphitic carbon-based high performance electrocatalyst for oxygen reduction reaction.

    PubMed

    Zhang, Haimin; Wang, Yun; Wang, Dan; Li, Yibing; Liu, Xiaolu; Liu, Porun; Yang, Huagui; An, Taicheng; Tang, Zhiyong; Zhao, Huijun

    2014-08-27

    In this work, we present a low cost and environmentally benign hydrothermal method using dried grass as the sole starting material without any synthetic chemicals to directly produce high quality nitrogen-doped carbon nanodot/nanosheet aggregates (N-CNAs), achieving a high yield of 25.2%. The fabricated N-CNAs possess an N/C atomic ratio of 3.41%, consist of three typed of doped N at a ratio of 2.6 (pyridinic):1.7 (pyrrolic):1 (graphitic). The experimental results reveal that for oxygen reduction reaction (ORR), the performance of N-CNAs, in terms of electrocatalytic activity, stability and resistance to crossover effects, is better or comparable to the commercial Pt/C electrocatalyst. The theoretical studies further indicate that the doped pyridinic-N plays a key role for N-CNAs' excellent four-electron ORR electrocatalytic activity. PMID:24729520

  7. Ketjenblack carbon supported amorphous manganese oxides nanowires as highly efficient electrocatalyst for oxygen reduction reaction in alkaline solutions.

    PubMed

    Lee, Jang-Soo; Park, Gi Su; Lee, Ho Il; Kim, Sun Tai; Cao, Ruiguo; Liu, Meilin; Cho, Jaephil

    2011-12-14

    A composite air electrode consisting of Ketjenblack carbon (KB) supported amorphous manganese oxide (MnOx) nanowires, synthesized via a polyol method, is highly efficient for the oxygen reduction reaction (ORR) in a Zn-air battery. The low-cost and highly conductive KB in this composite electrode overcomes the limitations due to low electrical conductivity of MnOx while acting as a supporting matrix for the catalyst. The large surface area of the amorphous MnOx nanowires, together with other microscopic features (e.g., high density of surface defects), potentially offers more active sites for oxygen adsorption, thus significantly enhancing ORR activity. In particular, a Zn-air battery based on this composite air electrode exhibits a peak power density of ∼190 mW/cm2, which is far superior to those based on a commercial air cathode with Mn3O4 catalysts. PMID:22050041

  8. Surface spectators and their role in relationships between activity and selectivity of the oxygen reduction reaction in acid environments.

    SciTech Connect

    Ciapina, Eduardo G.; Lopes, Pietro P.; Subbaraman, Ram; Ticianelli, Edson A.; Stamenkovic, Vojislav; Strmcnik, Dusan; Markovic, Nenad M.

    2015-11-01

    We use the rotating ring disk (RRDE) method to study activity-selectivity relationships for the oxygen reduction reaction (ORR) on Pt(111) modified by various surface coverages of adsorbed CNad (ΘCNad). The results demonstrate that small variations in ΘCNad have dramatic effect on the ORR activity and peroxide production, resulting in “volcano-like” dependence with an optimal surface coverage of ΘCNad = 0.3 ML. These relationships can be simply explained by balancing electronic and ensemble effects of co-adsorbed CNad and adsorbed spectator species from the supporting electrolytes, without the need for intermediate adsorption energy arguments. Although this study has focused on the Pt(111)-CNad/H2SO4 interface, the results and insight gained here are invaluable for controlling another dimension in the properties of electrochemical interfaces.

  9. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions.

    PubMed

    Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai; Dai, Liming

    2015-05-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are traditionally carried out with noble metals (such as Pt) and metal oxides (such as RuO₂ and MnO₂) as catalysts, respectively. However, these metal-based catalysts often suffer from multiple disadvantages, including high cost, low selectivity, poor stability and detrimental environmental effects. Here, we describe a mesoporous carbon foam co-doped with nitrogen and phosphorus that has a large surface area of ∼1,663 m(2) g(-1) and good electrocatalytic properties for both ORR and OER. This material was fabricated using a scalable, one-step process involving the pyrolysis of a polyaniline aerogel synthesized in the presence of phytic acid. We then tested the suitability of this N,P-doped carbon foam as an air electrode for primary and rechargeable Zn-air batteries. Primary batteries demonstrated an open-circuit potential of 1.48 V, a specific capacity of 735 mAh gZn(-1) (corresponding to an energy density of 835 Wh kgZn(-1)), a peak power density of 55 mW cm(-2), and stable operation for 240 h after mechanical recharging. Two-electrode rechargeable batteries could be cycled stably for 180 cycles at 2 mA cm(-2). We also examine the activity of our carbon foam for both OER and ORR independently, in a three-electrode configuration, and discuss ways in which the Zn-air battery can be further improved. Finally, our density functional theory calculations reveal that the N,P co-doping and graphene edge effects are essential for the bifunctional electrocatalytic activity of our material. PMID:25849787

  10. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai; Dai, Liming

    2015-05-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are traditionally carried out with noble metals (such as Pt) and metal oxides (such as RuO2 and MnO2) as catalysts, respectively. However, these metal-based catalysts often suffer from multiple disadvantages, including high cost, low selectivity, poor stability and detrimental environmental effects. Here, we describe a mesoporous carbon foam co-doped with nitrogen and phosphorus that has a large surface area of ˜1,663 m2 g-1 and good electrocatalytic properties for both ORR and OER. This material was fabricated using a scalable, one-step process involving the pyrolysis of a polyaniline aerogel synthesized in the presence of phytic acid. We then tested the suitability of this N,P-doped carbon foam as an air electrode for primary and rechargeable Zn-air batteries. Primary batteries demonstrated an open-circuit potential of 1.48 V, a specific capacity of 735 mAh gZn-1 (corresponding to an energy density of 835 Wh kgZn-1), a peak power density of 55 mW cm-2, and stable operation for 240 h after mechanical recharging. Two-electrode rechargeable batteries could be cycled stably for 180 cycles at 2 mA cm-2. We also examine the activity of our carbon foam for both OER and ORR independently, in a three-electrode configuration, and discuss ways in which the Zn-air battery can be further improved. Finally, our density functional theory calculations reveal that the N,P co-doping and graphene edge effects are essential for the bifunctional electrocatalytic activity of our material.

  11. Green synthesis of silver nanoclusters supported on carbon nanodots: enhanced photoluminescence and high catalytic activity for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, Minmin; Chen, Wei

    2013-11-01

    Metal nanoclusters exhibit unusual optical and catalytic properties due to their unique electronic structures. Here, surfactant-free silver nanoclusters supported on carbon nanodots were synthesized through a facile and green approach with only glucose and AgNO3 as precursors and without any other protecting ligands and reducing agents. The hybrid nanoclusters exhibited enhanced blue fluorescence compared to the carbon nanodots. More importantly, the ``surface-clean'' silver nanoclusters have remarkable electrocatalytic performance towards oxygen reduction reaction (ORR) with the most efficient four-electron transfer process. Moreover, compared with commercial Pt/C catalyst, the Pt-free hybrid clusters showed comparable catalytic performance for ORR but much higher tolerance to methanol crossover. Such silver nanoclusters will provide broad applications in fluorescence-related areas and in fuel cells as an efficient Pt-free catalyst with low cost and high catalytic performance.Metal nanoclusters exhibit unusual optical and catalytic properties due to their unique electronic structures. Here, surfactant-free silver nanoclusters supported on carbon nanodots were synthesized through a facile and green approach with only glucose and AgNO3 as precursors and without any other protecting ligands and reducing agents. The hybrid nanoclusters exhibited enhanced blue fluorescence compared to the carbon nanodots. More importantly, the ``surface-clean'' silver nanoclusters have remarkable electrocatalytic performance towards oxygen reduction reaction (ORR) with the most efficient four-electron transfer process. Moreover, compared with commercial Pt/C catalyst, the Pt-free hybrid clusters showed comparable catalytic performance for ORR but much higher tolerance to methanol crossover. Such silver nanoclusters will provide broad applications in fluorescence-related areas and in fuel cells as an efficient Pt-free catalyst with low cost and high catalytic performance. Electronic

  12. Density functional studies of functionalized graphitic materials with late transition metals for Oxygen Reduction Reactions.

    PubMed

    Calle-Vallejo, Federico; Martínez, José Ignacio; Rossmeisl, Jan

    2011-09-14

    Low-temperature fuel cells are appealing alternatives to the conventional internal combustion engines for transportation applications. However, in order for them to be commercially viable, effective, stable and low-cost electrocatalysts are needed for the Oxygen Reduction Reaction (ORR) at the cathode. In this contribution, on the basis of Density Functional Theory (DFT) calculations, we show that graphitic materials with active sites composed of 4 nitrogen atoms and transition metal atoms belonging to groups 7 to 9 in the periodic table are active towards ORR, and also towards Oxygen Evolution Reaction (OER). Spin analyses suggest that the oxidation state of those elements in the active sites should in general be +2. Moreover, our results verify that the adsorption behavior of transition metals is not intrinsic, since it can be severely altered by changes in the local geometry of the active site, the chemical nature of the nearest neighbors, and the oxidation states. Nonetheless, we find that these catalysts trend-wise behave as oxides and that their catalytic activity is limited by exactly the same universal scaling relations. PMID:21796295

  13. In situ probing of the active site geometry of ultrathin nanowires for the oxygen reduction reaction

    DOE PAGESBeta

    Liu, Haiqing; Wong, Stanislaus S.; An, Wei; Li, Yuanyuan; Frenkel, Anatoly I.; Sasaki, Kotaro; Koenigsmann, Christopher; Su, Dong; Anderson, Rachel M.; Crooks, Richard M.; et al

    2015-09-24

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd9Au nanowires, which have been previously shownmore » to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.« less

  14. In situ probing of the active site geometry of ultrathin nanowires for the oxygen reduction reaction

    SciTech Connect

    Liu, Haiqing; Wong, Stanislaus S.; An, Wei; Li, Yuanyuan; Frenkel, Anatoly I.; Sasaki, Kotaro; Koenigsmann, Christopher; Su, Dong; Anderson, Rachel M.; Crooks, Richard M.; Adzic, Radoslav R.; Liu, Ping

    2015-09-24

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd9Au nanowires, which have been previously shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.

  15. In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction.

    PubMed

    Liu, Haiqing; An, Wei; Li, Yuanyuan; Frenkel, Anatoly I; Sasaki, Kotaro; Koenigsmann, Christopher; Su, Dong; Anderson, Rachel M; Crooks, Richard M; Adzic, Radoslav R; Liu, Ping; Wong, Stanislaus S

    2015-10-01

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (∼2 nm) core-shell Pt∼Pd9Au nanowires, which have been previously shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu∼Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Hence, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general. PMID:26402364

  16. PTFE effect on the electrocatalysis of the oxygen reduction reaction in membraneless microbial fuel cells.

    PubMed

    Guerrini, Edoardo; Grattieri, Matteo; Faggianelli, Alessio; Cristiani, Pierangela; Trasatti, Stefano

    2015-12-01

    Influence of PTFE in the external Gas Diffusion Layer (GDL) of open-air cathodes applied to membraneless microbial fuel cells (MFCs) is investigated in this work. Electrochemical measurements on cathodes with different PTFE contents (200%, 100%, 80% and 60%) were carried out to characterize cathodic oxygen reduction reaction, to study the reaction kinetics. It is demonstrated that ORR is not under diffusion-limiting conditions in the tested systems. Based on cyclic voltammetry, an increase of the cathodic electrochemical active area took place with the decrease of PTFE content. This was not directly related to MFC productivity, but to the cathode wettability and the biocathode development. Low electrodic interface resistances (from 1 to 1.5 Ω at the start, to near 0.1 Ω at day 61) indicated a negligible ohmic drop. A decrease of the Tafel slopes from 120 to 80 mV during productive periods of MFCs followed the biological activity in the whole MFC system. A high PTFE content in the cathode showed a detrimental effect on the MFC productivity, acting as an inhibitor of ORR electrocatalysis in the triple contact zone. PMID:26045153

  17. In situ surface characterization and oxygen reduction reaction on shape-controlled gold nanoparticles.

    PubMed

    Hernández, J; Solla-Gullón, J; Herrero, E; Feliu, J M; Aldaz, A

    2009-04-01

    Gold nanoparticles of different shapes/surface structures were synthesized and electrochemically characterized. An in-situ surface characterization of the Au nanoparticles, which was able to obtain qualitative information about the type and relative sizes of the different facets present in the surface of the Au nanoparticles, was carried out by using Pb Under Potential Deposition (UPD) in alkaline solutions as a surface sensitive tool. The results obtained show that the final atomic arrangement on the surface can be different from that expected from the bulk structure of the well-defined shape Au nanoparticles. In this way, the development of precise in-situ methods to measure the distribution of the different sites on the nanoparticle surface, as lead UPD on gold surfaces, is highlighted. Oxygen Reduction Reaction (ORR) was performed on the different Au nanoparticles. In agreement with the particular sensitivity of the oxygen reduction to the presence of Au(100) surface domains, cubic Au nanoparticles show much better electrocatalytic activity for ORR than small spherical particles and long nanorods, in agreement with the presence of a great fraction of (100) terrace sites on the surface of cubic gold nanoparticles. PMID:19437963

  18. Enhancing stability of octahedral PtNi nanoparticles for oxygen reduction reaction by halide treatment

    NASA Astrophysics Data System (ADS)

    Choi, Juhyuk; Lee, Youhan; Kim, Jihan; Lee, Hyunjoo

    2016-03-01

    Because a reduction in the amount of Pt catalysts is essential for the commercialization of fuel cells, various approaches have been tested to maximize the mass activity of Pt-based catalysts. Among these, the most successful results so far were obtained using shaped PtNi alloy nanoparticles, preferably with PtNi(111) facets. However, these nanoparticles typically suffer from much lower activity after the durability tests due to the leaching out of the surface Ni during the oxygen reduction reaction (ORR), which leads to the disappearance of the activity-enhancing effect caused by electronic structure modification. Here, we showed that halide treatment of the octahedral PtNi nanoparticles could significantly enhance their durability. Halides are adsorbed on surface Ni more strongly than on surface Pt, and the surface halides are found to preserve the surface Ni that induces the ORR activity enhancement. Especially, Br can preserve the surface Ni effectively. Durability testing by repeating cyclic voltammetry 10,000 times in the 0.6-1.1 V range showed that the mass activity decreased by 52.6% for the as-prepared PtNi octahedral nanoparticles, whereas the mass activity decreased by only 15.0% for the Br-treated PtNi nanoparticles. The simple treatment significantly enhanced the long-term stability of the highly active PtNi alloy nano-octahedra.

  19. Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

    DOE PAGESBeta

    Sun-Mi Hwang; Choi, YongMan; Kim, Min Gyu; Sohn, Young-Jun; Cheon, Jae Yeong; Joo, Sang Hoon; Yim, Sung-Dae; Kuttiyiel, Kurian A.; Sasaki, Kotaro; Adzic, Radoslav R.; et al

    2016-03-08

    The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities comparedmore » to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.« less

  20. Synthesis of Fe nanoparticles on polyaniline covered carbon nanotubes for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Hu, Tian-Hang; Yin, Zhong-Shu; Guo, Jian-Wei; Wang, Cheng

    2014-12-01

    Fe nanoparticles immobilized on polyaniline-covered carbon nanotube (CNT) surfaces (Fe NPs-PANI/CNT) are prepared by reducing FeCl3 in the mixing solution of aniline and CNT. Significantly, the structure of such composites can be effectively optimized by pretreating FeCl3 with sodium citrate (CA). In the absence of CNTs, we found these two routes have large differences in reduction behaviors and different PANI states with varied conductivities. Therefore, the self-assembly mechanism in the preparation is proposed and the controlled self-assembly manner in the pretreating route is disclosed. Under acid condition, both catalysts demonstrate high oxygen reduction reaction (ORR) activity with four-electron pathway, and high electrochemical durability, revealing a promising application in the proton exchange membrane fuel cells. However, the high Tafel slopes relating to the surface red-ox couple and porous conductivity are still the main obstacles to improve their ORR dynamic, and more efforts on these aspects are needed to drive non-noble catalyst application in future.

  1. Particle-size effect of nanoscale platinum catalysts in oxygen reduction reaction: an electrochemical and 195Pt EC-NMR study.

    PubMed

    Yano, Hiroshi; Inukai, Junji; Uchida, Hiroyuki; Watanabe, Masahiro; Babu, Panakkattu K; Kobayashi, Takeshi; Chung, Jong Ho; Oldfield, Eric; Wieckowski, Andrzej

    2006-11-14

    Oxygen reduction reaction (ORR) measurements and (195)Pt electrochemical nuclear magnetic resonance (EC-NMR) spectroscopy were combined to study a series of carbon-supported platinum nanoparticle electrocatalysts (Pt/CB) with average diameters in the range of roughly 1-5 nm. ORR rate constants and H(2)O(2) yields evaluated from hydrodynamic voltammograms did not show any particle size dependency. The apparent activation energy of 37 kJ mol(-1), obtained for the ORR rate constant, was identical to that obtained for bulk platinum electrodes. Pt/CB catalysts on Nafion produced only 0.7-1% of H(2)O(2), confirming that the direct four-electron reduction of O(2) to H(2)O is the predominant reaction. NMR spectral features showed characteristic size dependence, and the line shapes were reproduced by using the layer-deconvolution model. Namely, the variations in the NMR spectra with particle size can be explained as due to the combined effect of the layer-by-layer variation of the s-type and d-type local density of states. However, the surface peak position of (195)Pt NMR spectra and the spin-lattice relaxation time of surface platinum atoms showed practically no change with the particle size variation. We conclude that there is a negligible difference in the surface electronic properties of these Pt/CB catalysts due to size variations and therefore, the ORR activities are not affected by the differences in the particle size. PMID:17066184

  2. Two-dimensional iron-phthalocyanine (Fe-Pc) monolayer as a promising single-atom-catalyst for oxygen reduction reaction: a computational study

    NASA Astrophysics Data System (ADS)

    Wang, Yu; Yuan, Hao; Li, Yafei; Chen, Zhongfang

    2015-07-01

    Searching for low-cost non-Pt catalysts for oxygen reduction reaction (ORR) has been a key scientific issue in the development of fuel cells. In this work, the potential of utilizing the experimentally available two-dimensional (2D) Fe-phthalocyanine (Fe-Pc) monolayer with precisely-controlled distribution of Fe atoms as a catalyst of ORR was systematically explored by means of comprehensive density functional theory computations. The computations revealed that O2 molecules can be sufficiently activated on the surface of the Fe-Pc monolayer, and the subsequent ORR steps prefer to proceed on the Fe-Pc monolayer through a more efficient 4e pathway with a considerable limiting potential of 0.68 V. Especially, the Fe-Pc monolayer is more stable than the Fe-Pc molecule in acidic medium, and can present good catalytic performance for ORR on the addition of axial ligands. Therefore, the Fe-Pc monolayer is quite a promising single-atom-catalyst with high efficiency for ORR in fuel cells.Searching for low-cost non-Pt catalysts for oxygen reduction reaction (ORR) has been a key scientific issue in the development of fuel cells. In this work, the potential of utilizing the experimentally available two-dimensional (2D) Fe-phthalocyanine (Fe-Pc) monolayer with precisely-controlled distribution of Fe atoms as a catalyst of ORR was systematically explored by means of comprehensive density functional theory computations. The computations revealed that O2 molecules can be sufficiently activated on the surface of the Fe-Pc monolayer, and the subsequent ORR steps prefer to proceed on the Fe-Pc monolayer through a more efficient 4e pathway with a considerable limiting potential of 0.68 V. Especially, the Fe-Pc monolayer is more stable than the Fe-Pc molecule in acidic medium, and can present good catalytic performance for ORR on the addition of axial ligands. Therefore, the Fe-Pc monolayer is quite a promising single-atom-catalyst with high efficiency for ORR in fuel cells. Electronic

  3. Facile Fabrication of N-Doped Graphene as Efficient Electrocatalyst for Oxygen Reduction Reaction.

    PubMed

    Liao, Yongliang; Gao, Yuan; Zhu, Shenmin; Zheng, Junsheng; Chen, Zhixin; Yin, Chao; Lou, Xianghong; Zhang, Di

    2015-09-01

    A facile bottom-up method is reported here for the fabrication of N-doped graphene for oxygen reduction. It consists of a two-step calcination strategy and uses α-hydroxy acids (AHAs) as carbon source and melamine as nitrogen source. Three different AHAs, malic acid, tartaric acid, and citric acid, were chosen as the carbon sources. The prepared N-doped graphenes have a typical thin layered structure with a large specific surface area. It was found that the N content in the obtained N-doped graphenes varies from 4.12 to 8.11 at. % depending on the AHAs used. All of the samples showed high performance in oxygen reduction reaction (ORR). The N-doped graphene prepared from citric acid demonstrated the highest electrocatalytic activity, which is comparable to the commercial Pt/C and exhibited good durability, attributing to the high pyridinic N content in the composite. PMID:26291928

  4. PT AND PT/NI "NEEDLE" ELETROCATALYSTS ON CARBON NANOTUBES WITH HIGH ACTIVITY FOR THE ORR

    SciTech Connect

    Colon-Mercado, H.

    2011-11-10

    Platinum and platinum/nickel alloy electrocatalysts supported on graphitized (gCNT) or nitrogen doped carbon nanotubes (nCNT) are prepared and characterized. Pt deposition onto carbon nanotubes results in Pt 'needle' formations that are 3.5 nm in diameter and {approx}100 nm in length. Subsequent Ni deposition and heat treatment results in PtNi 'needles' with an increased diameter. All Pt and Pt/Ni materials were tested as electrocatalysts for the oxygen reduction reaction (ORR). The Pt and Pt/Ni catalysts showed excellent performance for the ORR, with the heat treated PtNi/gCNT (1.06 mA/cm{sup 2}) and PtNi/nCNT (0.664 mA/cm{sup 2}) showing the highest activity.

  5. Preparation of fibrous titania oxynitride - carbon catalyst and oxygen reduction reaction analysis in both acidic and alkaline media

    NASA Astrophysics Data System (ADS)

    Kinumoto, Taro; Sou, Yoshinori; Ono, Kohei; Matsuoka, Miki; Arai, Yasuhiko; Tsumura, Tomoki; Toyoda, Masahiro

    2015-01-01

    A fibrous catalyst of titania oxynitride and carbon is prepared and its catalytic behavior in the oxygen reduction reaction (ORR) are investigated in both HClO4 and KOH aqueous solutions. TiO2 particles are successfully deposited on activated carbon fibers by a liquid phase deposition technique using (NH4)2TiF6 and H3BO3. The catalyst obtained after subsequent ammonia nitridation at 1273 K had a fibrous structure with TiOxNy and TiN components. Interestingly, the product demonstrates catalytic activity for the ORR in not only HClO4 but also KOH aqueous solution. The onset potential in HClO4 solution is assumed to be moderate, at 0.85 V; on the other hand, that in KOH solution is relatively high at 0.95 V. Furthermore, it is considered from the Tafel plot analysis of the KOH solution result that the ORR mechanism follows a peroxide intermediate pathway and the rate-determining step would be a one-electron-transfer reaction to oxygen molecules adsorbed on the active site.

  6. Transition metal/nitrogen dual-doped mesoporous graphene-like carbon nanosheets for the oxygen reduction and evolution reactions.

    PubMed

    Liu, Xiaobo; Amiinu, Ibrahim Saana; Liu, Shaojun; Cheng, Kun; Mu, Shichun

    2016-07-21

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been considered as a key step in energy conversion processes. Here, a novel and simple Mg(OH)2 nanocasting method is adopted to fabricate Co and N co-doped porous graphene-like carbon nanosheets (Co@N-PGCS) by using chitosan as both carbon and N sources. The as-obtained Co@N-PGCS shows a mesopore-dominated structure as well as a high specific surface area (1716 cm(2) g(-1)). As a bifunctional electrocatalyst towards both the ORR and OER, it shows favorable ORR performance compared with the commercial Pt/C catalyst with an onset potential of -0.075 V and a half-wave potential of -0.151 V in 0.1 M KOH solutions. Furthermore, it also displays considerable OER properties compared with commercial IrO2. The effective catalytic activity could originate from the introduction of transition metal species and few-layer mesoporous carbon structures. PMID:27341409

  7. Effect of component distribution and nanoporosity in CuPt nanotubes on electrocatalysis of the oxygen reduction reaction.

    PubMed

    Guo, Huizhang; Liu, Xiang; Bai, Chengdong; Chen, Yuanzhi; Wang, Laisen; Zheng, Mingsen; Dong, Quanfeng; Peng, Dong-Liang

    2015-02-01

    Pt-based bimetallic electrocatalysts hold great potential in the oxygen reduction reaction (ORR) in current fuel-cell prototypes. However, they also face challenges from drastic dealloying of less-noble metals and coalescence of small nanoparticles. Porous and structure-ordered nanotubes may hold the potential to improve the stability of bimetallic electrocatalysts. Herein, we report a method to prepare CuPt nanotubes and porous Cu3 Pt intermetallic nanorods through a controlled galvanic replacement reaction and heat treatment process. The effect of the geometric features and compositional segregation on the electrocatalysis of the ORR was clarified. The outstanding performance of the Cu3 Pt/C-700 catalyst in the ORR relative to that of CuPt/C-RT was mainly attributed to the nanoporosity of the catalyst, whereas the enhanced specific activity on CuPt/C-RT after potential cycling was attributed to the interaction between the CuPt alloyed core and the Pt shell in the tube wall. PMID:25505002

  8. Theoretical Modelling and Facile Synthesis of a Highly Active Boron-Doped Palladium Catalyst for the Oxygen Reduction Reaction.

    PubMed

    Vo Doan, Tat Thang; Wang, Jingbo; Poon, Kee Chun; Tan, Desmond C L; Khezri, Bahareh; Webster, Richard D; Su, Haibin; Sato, Hirotaka

    2016-06-01

    A highly active alternative to Pt electrocatalysts for the oxygen reduction reaction (ORR), which is the cathode-electrode reaction of fuel cells, is sought for higher fuel-cell performance. Our theoretical modelling reveals that B-doped Pd (Pd-B) weakens the absorption of ORR intermediates with nearly optimal binding energy by lowering the barrier associated with O2 dissociation, suggesting Pd-B should be highly active for ORR. In fact, Pd-B, facile synthesized by an electroless deposition process, exhibits 2.2 times and 8.8 times higher specific activity and 14 times and 35 times less costly than commercial pure Pd and Pt catalysts, respectively. Another computational result is that the surface core level of Pd is negatively shifted by B doping, as confirmed by XPS, and implies that filling the density of states related to the anti-bonding of oxygen to Pd surfaces with excess electrons from B doping, weakens the O bonding to Pd and boosts the catalytic activity. PMID:27086729

  9. Hollow structured carbon-supported nickel cobaltite nanoparticles as an efficient bifunctional electrocatalyst for the oxygen reduction and evolution reaction

    DOE PAGESBeta

    Wang, Jie; Han, Lili; Lin, Ruoqian; Xin, Huolin L.; Wang, Deli; Wu, Zexing

    2016-01-05

    Here, the exploration of efficient electrocatalysts for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is essential for fuel cells and metal-air batteries. In this study, we developed 3D hollow-structured NiCo2O4/C nanoparticles with interconnected pores as bifunctional electrocatalysts, which are transformed from solid NiCo2 alloy nanoparticles through the Kirkendall effect. The unique hollow structure of NiCo2O4 nanoparticles increases the number of active sites and improves contact with the electrolyte to result in excellent ORR and OER performances. In addition, the hollow-structured NiCo2O4/C nanoparticles exhibit superior long-term stability for both the ORR and OER compared to commercial Pt/C.more » The template- and surfactant-free synthetic strategy could be used for the low-cost and large-scale synthesis of hollow-structured materials, which would facilitate the screening of high-efficiency catalysts for energy conversion.« less

  10. Synthetic control of FePtM nanorods (M = Cu, Ni) to enhance the oxygen reduction reaction.

    PubMed

    Zhu, Huiyuan; Zhang, Sen; Guo, Shaojun; Su, Dong; Sun, Shouheng

    2013-05-15

    To further enhance the catalytic activity and durability of nanocatalysts for the oxygen reduction reaction (ORR), we synthesized a new class of 20 nm × 2 nm ternary alloy FePtM (M = Cu, Ni) nanorods (NRs) with controlled compositions. Supported on carbon support and treated with acetic acid as well as electrochemical etching, these FePtM NRs were converted into core/shell FePtM/Pt NRs. These core/shell NRs, especially FePtCu/Pt NRs, exhibited much improved ORR activity and durability. The Fe10Pt75Cu15 NRs showed a mass current densities of 1.034 A/mgPt at 512 mV vs Ag/AgCl and 0.222 A/mgPt at 557 mV vs Ag/AgCl, which are much higher than those for a commercial Pt catalyst (0.138 and 0.035 A/mgPt, respectively). Our controlled synthesis provides a general approach to core/shell NRs with enhanced catalysis for the ORR or other chemical reactions. PMID:23634823

  11. Structural disordering of de-alloyed Pt bimetallic nanocatalysts: the effect on oxygen reduction reaction activity and stability.

    PubMed

    Spanos, Ioannis; Dideriksen, Knud; Kirkensgaard, Jacob J K; Jelavic, Stanislav; Arenz, Matthias

    2015-11-14

    Platinum bimetallic alloys are well-known for their ability to catalyze the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Pt(x)Co(1-x) colloidal nanoparticles were synthesized with varying initial Pt : Co ratios, but constant size to investigate how the initial metal composition affects their electrocatalytic performance. The results show that upon contact with acid environment the Co leaches out of the particles leading to almost identical compositions, independent of the initial differences. Surprisingly the data show a clear trend in ORR activity, although the Pt(x)Co(1-x) nanoparticles almost completely de-alloy during acid leaching, i.e. under reaction conditions in a fuel cell. To scrutinize the resulting particle structure after de-alloying we used pair distribution function (PDF) analysis and X-ray diffraction (XRD) gaining insight into the structural disorder and its dependence on the initial metal composition. Our results suggest that not only the ORR activity, but also the corrosion resistance of the synthesized NPs, are dependent on the structural disorder resulting from the de-alloying process. PMID:25537262

  12. Stable silver nanoclusters electrochemically deposited on nitrogen-doped graphene as efficient electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Jin, Shi; Chen, Man; Dong, Haifeng; He, Bingyu; Lu, Huiting; Su, Lei; Dai, Wenhao; Zhang, Qiaochu; Zhang, Xueji

    2015-01-01

    Metal nanoclusters exhibit unusually high catalytic activity toward oxygen reduction reaction (ORR) due to their small size and unique electronic structures. However, controllable synthesis of stable metal nanoclusters is a challenge, and the durability of metal clusters suffers from the deficiency of dissolution, aggregation, and sintering during catalysis reactions. Herein, silver nanoclusters (AgNCs) (diameter < 2 nm) were controllably electrochemically reduced on nitrogen-doped graphene (NG) using effective single-stranded oligonucleotide sequences (ssDNA) as the performed template in absence of any other reluctant. The ssDNA is significant for providing AgNCs with growth template and anchoring the cluster on graphene surface. The strong interaction between the AgNCs, ssDNA and NG renders the as-synthesized AgNCs/NG composite with high-performance onset potential, half-wave potential and mass activity for ORR approaching to commercial Pt/C catalyst, and remarkably superior ORR performance than NG and Ag nanoparticle/NG. Importantly, the AgNCs/NG composite shows excellent methanol tolerance and accelerated electrochemical stability (8000 cycles), which is vital in high performance fuel cells, batteries and nanodevices.

  13. Silicon and phosphorus dual doped graphene as the promising metal-free catalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Lu, Zhansheng; Li, Shuo; Yang, Zongxian; Wu, Ruqian

    The pathways of oxygen reduction reaction (ORR) on the metal-free silicon and phosphorus dual doped graphene (Si-P-G) catalyst are systematically investigated based on the dispersion-corrected density functional theory (DFT-D) method. It is found that the Si-P-G can be stable at high temperature from the first-principles molecular dynamics simulation and the local region of dopants displays an important role in the adsorption and reduction of oxygen. Both of the four-electron O2 direct dissociation and the two-electron OOH dissociation pathways are probable for ORR on the Si-P-G, while the latter pathway is mainly followed by the pathway of the OH hydrogenation into H2O. For the OOH dissociation pathway, the hydrogenation of O2 to OOH is the rate-limiting step with a rather small barrier energy of 0.66 eV. The current results indicate that the Si-P-G is a novel metal-free catalyst for ORR, and which is comparable to that of the Pt catalyst. Work was supported by the National Science Foundation Center for Chemical Innovation on Chemistry at the Space-Time Limit (CaSTL) under Grant No. CHE-1414466, and the National Natural Science Foundation of China (Grant Nos. 51401078, and 11474086).

  14. Enhancement in Kinetics of the Oxygen Reduction Reaction on a Nitrogen-Doped Carbon Catalyst by Introduction of Iron via Electrochemical Methods.

    PubMed

    Wu, Jiajia; Zhang, Da; Niwa, Hideharu; Harada, Yoshihisa; Oshima, Masaharu; Ofuchi, Hironori; Nabae, Yuta; Okajima, Takeyoshi; Ohsaka, Takeo

    2015-05-19

    The iron (Fe) electrodeposition-electrochemical dissolution has been employed on nitrogen-doped carbon material (P-PI) prepared via multi-step pyrolysis of a polyimide precursor to achieve the introduction of Fe species, and its influence on the oxygen reduction reaction (ORR) is investigated by cyclic and rotating ring-disk electrode voltammetry in 0.5 M H2SO4. After the electrochemical treatment, the overpotential and H2O2 production percentage of ORR on the P-PI are decreased and the number of electrons transferred is increased in the meanwhile. In combination with the results of X-ray absorption fine structure spectra, the presence of Fe-Nx sites (Fe ions coordinated by nitrogen) is believed to be responsible for the improved ORR performance. Further kinetic analysis indicates that a two-electron reduction of O2 is predominant on the untreated P-PI with coexistence of a direct four-electron transformation of O2 to H2O, while the introduction of Fe species leads to a larger increase in the rate constant for the four-electron reduction than that for the two-electron process, being in good agreement with the view that Fe-Nx sites are active for four-electron ORR. PMID:25901901

  15. A first principles study of oxygen reduction reaction on a Pt(111) surface modified by a subsurface transition metal M (M = Ni, Co, or Fe).

    PubMed

    Duan, Zhiyao; Wang, Guofeng

    2011-12-01

    We have performed first-principle density functional theory calculations to investigate how a subsurface transition metal M (M = Ni, Co, or Fe) affects the energetics and mechanisms of oxygen reduction reaction (ORR) on the outermost Pt mono-surface layer of Pt/M(111) surfaces. In this work, we found that the subsurface Ni, Co, and Fe could down-shift the d-band center of the Pt surface layer and thus weaken the binding of chemical species to the Pt/M(111) surface. Moreover, the subsurface Ni, Co, and Fe could modify the heat of reaction and activation energy of various elementary reactions of ORR on these Pt/M(111) surfaces. Our DFT results revealed that, due to the influence of the subsurface Ni, Co, and Fe, ORR would adopt a hydrogen peroxide dissociation mechanism with an activation energy of 0.15 eV on Pt/Ni(111), 0.17 eV on Pt/Co(111), and 0.16 eV on Pt/Fe(111) surface, respectively, for their rate-determining O2 protonation reaction. In contrast, ORR would follow a peroxyl dissociation mechanism on a pure Pt(111) surface with an activation energy of 0.79 eV for its rate-determining O protonation reaction. Thus, our theoretical study explained why the subsurface Ni, Co, and Fe could lead to multi-fold enhancement in catalytic activity for ORR on the Pt mono-surface layer of Pt/M(111) surfaces. PMID:22187733

  16. Reduction Methods for Total Reaction Cross Sections

    NASA Astrophysics Data System (ADS)

    Gomes, P. R. S.; Mendes Junior, D. R.; Canto, L. F.; Lubian, J.; de Faria, P. N.

    2016-03-01

    The most frequently used methods to reduce fusion and total reaction excitation functions were investigated in a very recent paper Canto et al. (Phys Rev C 92:014626, 2015). These methods are widely used to eliminate the influence of masses and charges in comparisons of cross sections for weakly bound and tightly bound systems. This study reached two main conclusions. The first is that the fusion function method is the most successful procedure to reduce fusion cross sections. Applying this method to theoretical cross sections of single channel calculations, one obtains a system independent curve (the fusion function), that can be used as a benchmark to fusion data. The second conclusion was that none of the reduction methods available in the literature is able to provide a universal curve for total reaction cross sections. The reduced single channel cross sections keep a strong dependence of the atomic and mass numbers of the collision partners, except for systems in the same mass range. In the present work we pursue this problem further, applying the reduction methods to systems within a limited mass range. We show that, under these circumstances, the reduction of reaction data may be very useful.

  17. Size-Controlled Synthesis of Sub-10 nm PtNi3 Alloy Nanoparticles and their Unusual Volcano-Shaped Size Effect on ORR Electrocatalysis.

    PubMed

    Gan, Lin; Rudi, Stefan; Cui, Chunhua; Heggen, Marc; Strasser, Peter

    2016-06-01

    Dealloyed Pt bimetallic core-shell catalysts derived from low-Pt bimetallic alloy nanoparticles (e.g, PtNi3 ) have recently shown unprecedented activity and stability on the cathodic oxygen reduction reaction (ORR) under realistic fuel cell conditions and become today's catalyst of choice for commercialization of automobile fuel cells. A critical step toward this breakthrough is to control their particle size below a critical value (≈10 nm) to suppress nanoporosity formation and hence reduce significant base metal (e.g., Ni) leaching under the corrosive ORR condition. Fine size control of the sub-10 nm PtNi3 nanoparticles and understanding their size dependent ORR electrocatalysis are crucial to further improve their ORR activity and stability yet still remain unexplored. A robust synthetic approach is presented here for size-controlled PtNi3 nanoparticles between 3 and 10 nm while keeping a constant particle composition and their size-selected growth mechanism is studied comprehensively. This enables us to address their size-dependent ORR activities and stabilities for the first time. Contrary to the previously established monotonic increase of ORR specific activity and stability with increasing particle size on Pt and Pt-rich bimetallic nanoparticles, the Pt-poor PtNi3 nanoparticles exhibit an unusual "volcano-shaped" size dependence, showing the highest ORR activity and stability at the particle sizes between 6 and 8 nm due to their highest Ni retention during long-term catalyst aging. The results of this study provide important practical guidelines for the size selection of the low Pt bimetallic ORR electrocatalysts with further improved durably high activity. PMID:27152487

  18. 2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Rowley-Neale, Samuel J.; Fearn, Jamie M.; Brownson, Dale A. C.; Smith, Graham C.; Ji, Xiaobo; Banks, Craig E.

    2016-08-01

    Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.Two-dimensional molybdenum disulphide nanosheets

  19. Enhancing pyridinic nitrogen level in graphene to promote electrocatalytic activity for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Sun, Jiaguang; Wang, Lan; Song, Ranran; Yanga, Shubin

    2016-02-01

    We develop an efficient approach to fabricate nitrogen-doped graphene with tunable pyridinic nitrogen levels (from 1.1 to 1.8 at.%), abundant in-plane holes and high surface areas (623 m2 g-1) via a hydrothermal treatment of graphene oxide with hydrogen peroxide and subsequent annealing under ammonia gas. It is found that the chemical etching is beneficial to the formation of pyridinic nitrogen in graphene during the nitrogen-doping process, which is crucial to enhancing the electrocatalytic properties of graphene for oxygen reduction reaction (ORR). Hence, the optimized NG exhibits good electrocatalytic activity, more positive onset potential than Pt-C (-0.08 V versus -0.09 V), good durability, and high selectivity when it is employed as a metal-free catalyst for ORR. This approach may uncover a mechanism in escalation of pyridinic N atoms doped on the graphene basal edge and provide an efficient platform for the synthesis of a series of heteroatom-doped graphene with tunable heteroatom content for broad applications.

  20. A unique platinum-graphene hybrid structure for high activity and durability in oxygen reduction reaction

    PubMed Central

    Wang, Chengming; Ma, Liang; Liao, Lingwen; Bai, Song; Long, Ran; Zuo, Ming; Xiong, Yujie

    2013-01-01

    It remains a grand challenge to achieve both high activity and durability in Pt electrocatalysts for oxygen reduction reaction (ORR) in fuel cells. Here we develop a class of Pt highly concave cubic (HCC) nanocrystals, which are enriched with high-index facets, to enable high ORR activity. The durability of HCC nanocrystals can be significantly improved via assembly with graphene. Meanwhile, the unique hybrid structure displays further enhanced specific activity, which is 7-fold greater than the state-of-the-art Pt/C catalysts. Strikingly, it exhibits impressive performance in terms of half-wave potential (E1/2). The E1/2 of 0.967 V at the Pt loading as low as 46 μg cm−2, which stands as 63 mV higher than that of the Pt/C catalysts, is slightly superior to the record observed for the most active porous Pt-Ni catalyst in literature. This work paves the way to designing high-performance electrocatalysts by modulating their surface and interface with loading substrates. PMID:23999570

  1. One-step synthesis of nitrogen-iron coordinated carbon nanotube catalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Choi, Woongchul; Yang, Gang; Kim, Suk Lae; Liu, Peng; Sue, Hung-Jue; Yu, Choongho

    2016-05-01

    Prohibitively expensive precious metal catalysts for oxygen reduction reaction (ORR) have been one of the major hurdles in a wide use of electrochemical cells. Recent significant efforts to develop precious metal free catalysts have resulted in excellent catalytic activities. However, complicated and time-consuming synthesis processes have negated the cost benefit. Moreover, detailed analysis about catalytically active sites and the role of each element in these high-performance catalysts containing nanomaterials for large surface areas are often lacking. Here we report a facile one-step synthesis method of nitrogen-iron coordinated carbon nanotube (CNT) catalysts without precious metals. Our catalysts show excellent long-term stability and onset ORR potential comparable to those of other precious metal free catalysts, and the maximum limiting current density from our catalysts is larger than that of the Pt-based catalysts. We carry out a series of synthesis and characterization experiments with/without iron and nitrogen in CNT, and identify that the coordination of nitrogen and iron in CNT plays a key role in achieving the excellent catalytic performances. We anticipate our one-step process could be used for mass production of precious metal free electrocatalysts for a wide range of electrochemical cells including fuel cells and metal-air batteries.

  2. Electrochemical deposition of silver on manganese dioxide coated reduced graphene oxide for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Lee, Kyungmi; Ahmed, Mohammad Shamsuddin; Jeon, Seungwon

    2015-08-01

    We have prepared a reduced graphene oxide (rGO)-supported silver (Ag) and manganese dioxide (MnO2) deposited porous-like catalyst (denoted as rGO/MnO2/Ag) through a facile electrochemical deposition route and have been used as a cathode catalyst for oxygen reduction reaction (ORR) in alkaline fuel cells. The physical properties of rGO/MnO2/Ag have been investigated via several instrumental methods. This material exhibits a polycrystalline structure characterized by Ag/MnO2 microsphere formation as a result of Ostwald ripening. The X-ray diffraction and X-ray photoelectron spectroscopy data reveal that the MnO2 and Ag have been slightly alloyed and Mn presents with the dioxide form on rGO. The electrochemical properties of the electrocatalyst have been studied via several voltammetric methods. The results demonstrated that the rGO/MnO2/Ag has an excellent catalytic activity for ORR in alkaline media compared to the other tested electrodes. Particularly, it shows 1.2 times higher current density and better electron transfer rate at 0.3 V per O2 than that of 20 wt% Pt/C. The other kinetic analysis reveals that the O2 has reduced directly to H2O through a nearly four-electron pathway with better anodic fuel tolerance and duration performance than that of 20% Pt/C.

  3. Oxygen-reduction reaction strongly electrocatalyzed by Pt electrodeposited onto graphene or graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Fortunato, Guilherme V.; de Lima, Fábio; Maia, Gilberto

    2016-01-01

    Pt nanoclusters with Pt porous dendritic structures on top (high porosity materials) were electrodeposited at a low overpotential onto glassy carbon (GC) electrodes modified with graphite (GR), multiwalled carbon nanotubes (MWCNT), graphene oxide (GO), graphene oxide nanoribbons (GONR), chemically converted graphene (CCG), and graphene nanoribbons (GNR). The electrochemical profiles of these materials were investigated using cyclic voltammetry and microgravimetry (electrochemical quartz microbalance). Their electrocatalytic activity towards the oxygen-reduction reaction (ORR) was studied employing hydrodynamic cyclic voltammetry. Physical characterization of the samples was based on transmission electron microscopy (TEM), scanning electron microscope (SEM), atomic force microscopy (AFM), and energy-dispersive X-ray microanalysis (EDX). Pt electrocatalysts electrodeposited onto CCG and GNR exhibited high electrocatalytic activity towards ORR when compared with commercial Pt (10 wt.%) on carbon and high stability after 10 000 potential scans, suggesting the possibility of applying these catalysts to acid fuel cells-viable even in economic terms, as very low amounts of finely dispersed Pt per cm2 onto thin CCG or GNR films were required to produce the electrocatalysts. GC electrodes modified with Pt electrodeposited onto GR, MWCNT, GO, or GONR exhibited poor electrocatalytic activity.

  4. High performance and bifunctional cobalt-embedded nitrogen doped carbon/nanodiamond electrocatalysts for oxygen reduction and oxygen evolution reactions in alkaline media

    NASA Astrophysics Data System (ADS)

    Wu, Yanzhuo; Zang, Jianbing; Dong, Liang; Zhang, Yan; Wang, Yanhui

    2016-02-01

    A bifunctional noble metal-free catalyst with a cobalt-embedded nitrogen doped graphitized carbon shell covering a nanodiamond (ND) core (Co-N-C/ND) is synthesized. The resulting Co-N-C/ND exhibits excellent catalytic activities for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media. The average electron transfer number of ORR on the Co-N-C/ND is 3.82 between -0.4 and -0.7 V (vs. Hg/HgO), indicating a near four-electron transfer mechanism for ORR. Moreover, the catalytic activity of the Co-N-C/ND for ORR is comparable to the 20 wt% Pt reference catalyst supported on carbon black. The OER onset potential on the Co-N-C/ND is 0.43 V (vs. Hg/HgO) and the current density at 0.7 V is 3.19 mA cm-2, demonstrating excellent catalytic activity for OER. In comparison to the Co-N-C derived from carbon black, the Co-N-C/ND exhibits better durability. The superior electrocatalytic performance of the Co-N-C/ND could be attributed to the synergistic effect of the Co-N moieties in the carbon shell and the high stability could be ascribed to the ND core.

  5. Using nitrogen-rich polymeric network and iron(II) acetate as precursors to synthesize highly efficient electrocatalyst for oxygen reduction reaction in alkaline media

    NASA Astrophysics Data System (ADS)

    Yang, Mei; Chen, Hongbiao; Yang, Duanguang; Gao, Yong; Li, Huaming

    2016-03-01

    Carbon-supported transition metal/nitrogen (M-N/C) materials are considered as one of the most promising electrocatalysts for the oxygen reduction reaction (ORR) owing to their high ORR electrocatalytic activity, long-term stability, and excellent methanol tolerance. So far only a few examples of such catalysts are prepared from N-containing polymers. Herein, we report a novel Fe-N/C catalyst using a nitrogen-rich polymeric network and iron(II) acetate as the precursors. The porous polymeric network is fabricated by one-step Friedel-Crafts reaction of a low-cost cross-linker, formaldehyde dimethyl acetal, with 2,4,6-tripyrrol-1,3,5-triazine. Compared to commercial Pt/C catalyst, the as-prepared Fe-N/C electrocatalyst exhibits superior ORR activity in alkaline electrolyte, and comparable ORR activity in acidic medium. The results obtained are significant for the development of new Fe-N/C electrocatalysts for fuel cells.

  6. Cobalt sulfide/N,S codoped porous carbon core-shell nanocomposites as superior bifunctional electrocatalysts for oxygen reduction and evolution reactions.

    PubMed

    Chen, Binling; Li, Rong; Ma, Guiping; Gou, Xinglong; Zhu, Yanqiu; Xia, Yongde

    2015-12-28

    Exploring highly-efficient and low-cost bifunctional electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reactions (OER) in the renewable energy area has gained momentum but still remains a significant challenge. Here we present a simple but efficient method that utilizes ZIF-67 as the precursor and template for the one-step generation of homogeneous dispersed cobalt sulfide/N,S-codoped porous carbon nanocomposites as high-performance electrocatalysts. Due to the favourable molecular-like structural features and uniform dispersed active sites in the precursor, the resulting nanocomposites, possessing a unique core-shell structure, high porosity, homogeneous dispersion of active components together with N and S-doping effects, not only show excellent electrocatalytic activity towards ORR with the high onset potential (around -0.04 V vs.-0.02 V for the benchmark Pt/C catalyst) and four-electron pathway and OER with a small overpotential of 0.47 V for 10 mA cm(-2) current density, but also exhibit superior stability (92%) to the commercial Pt/C catalyst (74%) in ORR and promising OER stability (80%) with good methanol tolerance. Our findings suggest that the transition metal sulfide-porous carbon nanocomposites derived from the one-step simultaneous sulfurization and carbonization of zeolitic imidazolate frameworks are excellent alternative bifunctional electrocatalysts towards ORR and OER in the next generation of energy storage and conversion technologies. PMID:26599403

  7. Phosphorus-doped carbon nanotubes supported low Pt loading catalyst for the oxygen reduction reaction in acidic fuel cells

    NASA Astrophysics Data System (ADS)

    Liu, Ziwu; Shi, Qianqian; Zhang, Rufan; Wang, Quande; Kang, Guojun; Peng, Feng

    2014-12-01

    To develop low-cost and efficient cathode electrocatalysts for fuel cells in acidic media, phosphorus-doped carbon nanotubes (P-CNTs) supported low Pt loading catalyst (0.85% Pt) is designed. The as-prepared Pt/P-CNTs exhibit significantly enhanced electrocatalytic oxygen reduction reaction (ORR) activity and long-term stability due to the stronger interaction between Pt and P-CNTs, which is proven by X-ray photoelectron spectroscopic analysis and density functional theory calculations. Moreover, the as-prepared Pt/P-CNTs also display much better tolerance to methanol crossover effects, showing a good potential application for future proton exchange membrane fuel cell devices.

  8. Design of Pt-Pd Binary Superlattices Exploiting Shape Effects and Synergistic Effects for Oxygen Reduction Reactions

    SciTech Connect

    Kang, YJ; Ye, XC; Chen, J; Cai, Y; Diaz, RE; Adzic, RR; Stach, EA; Murray, CB

    2013-01-09

    Large-area icosahedral-AB(13)-type Pt-Pd binary superlattices (BNSLs) are fabricated through self-assembly of 6 nm Pd nanocrystals (NCs) and 13 nm Pt octahedra at a liquid air interface. The Pt-Pd BNSLs enable a high activity toward electrocatalysis of oxygen reduction reaction (ORR) by successfully exploiting the shape effects of Pt-NCs and synergistic effects of Pt-Pd into a single crystalline nanostructure. The Pt-Pd BNSLs are promising catalysts for the oxygen electrode of fuel cells.

  9. Rationalization of Au concentration and distribution in AuNi@Pt core-shell nanoparticles for oxygen reduction reaction

    SciTech Connect

    An, Wei; Liu, Ping

    2015-09-18

    Improving the activity and stability of Pt-based core–shell nanocatalysts for proton exchange membrane fuel cells while lowering Pt loading has been one of the big challenges in electrocatalysis. Here, using density functional theory, we report the effect of adding Au as the third element to enhance the durability and activity of Ni@Pt core–shell nanoparticles (NPs) during the oxygen reduction reaction (ORR). Our results show that the durability and activity of a Ni@Pt NP can be finely tuned by controlling Au concentration and distribution. For a NiAu@Pt NP, the durability can be greatly promoted by thermodynamically favorable segregation of Au to replace the Pt atoms at vertex, edge, and (100) facets on the shell, while still keeping the ORR activity on the active Pt(111) shell as high as that of Ni@Pt nanoparticles. Such behavior strongly depends on a direct interaction with the Ni interlayer. The results not only highlight the importance of interplay between surface strain on the shell and the interlayer–shell interaction in determining the durability and activity but also provide guidance on how to maximize the usage of Au to optimize the performance of core–shell (Pt) nanoparticles. As a result, such understanding has allowed us to discover a novel NiAu@Pt nanocatalyst for the ORR.

  10. Rationalization of Au concentration and distribution in AuNi@Pt core-shell nanoparticles for oxygen reduction reaction

    DOE PAGESBeta

    An, Wei; Liu, Ping

    2015-09-18

    Improving the activity and stability of Pt-based core–shell nanocatalysts for proton exchange membrane fuel cells while lowering Pt loading has been one of the big challenges in electrocatalysis. Here, using density functional theory, we report the effect of adding Au as the third element to enhance the durability and activity of Ni@Pt core–shell nanoparticles (NPs) during the oxygen reduction reaction (ORR). Our results show that the durability and activity of a Ni@Pt NP can be finely tuned by controlling Au concentration and distribution. For a NiAu@Pt NP, the durability can be greatly promoted by thermodynamically favorable segregation of Au tomore » replace the Pt atoms at vertex, edge, and (100) facets on the shell, while still keeping the ORR activity on the active Pt(111) shell as high as that of Ni@Pt nanoparticles. Such behavior strongly depends on a direct interaction with the Ni interlayer. The results not only highlight the importance of interplay between surface strain on the shell and the interlayer–shell interaction in determining the durability and activity but also provide guidance on how to maximize the usage of Au to optimize the performance of core–shell (Pt) nanoparticles. As a result, such understanding has allowed us to discover a novel NiAu@Pt nanocatalyst for the ORR.« less

  11. Synthesis of halogen-doped reduced graphene oxide nanosheets as highly efficient metal-free electrocatalyst for oxygen reduction reaction.

    PubMed

    Kakaei, Karim; Balavandi, Amin

    2016-02-01

    We demonstrate F-, Cl-, Br- and I-doped reduced graphene oxide (XRGO) as metal-free graphene electro-catalysts for oxygen reduction reaction (ORR) in alkaline media. Reduced graphene oxide (GO) is prepared from graphite electrode using electrochemical exfoliation. In situ doping of halide in a graphene film has many problems. In this technique, different halides individually or all of them were mixed with the RGO and ionic liquids precursor at H2SO4 solution. Then we have evaluated the effectiveness of doping and performed electrochemical measurements of the ORR activity on XRGO. Fourier-transform infrared spectroscopy spectra show a variety of the halogen-containing functional groups. Energy-dispersive X-ray spectroscopy analysis confirmed the presence of doped halogens in RGO. Raman spectroscopy shows a high density of defects in the RGO layer. The electrochemical properties of the XRGO catalysts on carbon paper as a gas diffusion electrode (GDE) are investigated by several electrochemical methods in oxygen saturated alkaline solutions. The catalytic activity of the XRGO and Pt-C electrodes for ORR is 50 and 30mAcm(-2) at -1V in GDEs. This enhanced efficiency is the result of the influence of the nature and percentage of the halogen, especially fluorine presence in the graphene layer. PMID:26513736

  12. Facile synthesis of nitrogen and sulfur codoped carbon from ionic liquid as metal-free catalyst for oxygen reduction reaction.

    PubMed

    She, Yiyi; Lu, Zhouguang; Ni, Meng; Li, Li; Leung, Michael K H

    2015-04-01

    Developing metal-free catalysts for oxygen reduction reaction (ORR) is a great challenge in the development of fuel cells. Nitrogen and sulfur codoped carbon with remarkably high nitrogen content up to 13.00 at % was successfully fabricated by pyrolysis of homogeneous mixture of exfoliated graphitic flakes and ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bimi][Tf2N]). The exfoliated graphite flakes served as a structure-directing substance as well as additional carbon source in the fabrication. It was demonstrated that the use of graphite flakes increased the nitrogen doping level, optimized the composition of active nitrogen configurations, and enlarged the specific surface area of the catalysts. Electrochemical characterizations revealed that the N and S codoped carbon fabricated by this method exhibited superior catalytic activities toward ORR under both acidic and alkaline conditions. Particularly in alkaline solution, the current catalyst compared favorably to the conventional 20 wt % Pt/C catalyst via four-electron transfer pathway with better ORR selectivity. The excellent catalytic activity was mainly ascribed to high nitrogen doping content, appropriate constitution of active nitrogen configurations, large specific surface area, and synergistic effect of N and S codoping. PMID:25781628

  13. Advanced oxygen reduction reaction catalyst based on nitrogen and sulfur co-doped graphene in alkaline medium.

    PubMed

    Li, Yongfeng; Li, Meng; Jiang, Liqing; Lin, Lin; Cui, Lili; He, Xingquan

    2014-11-14

    A novel nitrogen and sulfur co-doped graphene (N-S-G) catalyst for oxygen reduction reaction (ORR) has been prepared by pyrolysing graphite oxide and poly[3-amino-5-mercapto-1,2,4-triazole] composite (PAMTa). The atomic percentage of nitrogen and sulfur for the prepared N-S-G can be adjusted by controlling the pyrolysis temperature. Furthermore, the catalyst pyrolysed at 1000 °C, denoted N-S-G 1000, exhibits the highest catalytic activity for ORR, which displays the highest content of graphitic-N and thiophene-S among all the pyrolysed samples. The electrocatalytic performance of N-S-G 1000 is significantly better than that of PAMTa and reduced graphite oxide composite. Remarkably, the N-S-G 1000 catalyst is comparable with Pt/C in terms of the onset and half-wave potentials, and displays larger kinetic limiting current density and better methanol tolerance and stability than Pt/C for ORR in an alkaline medium. PMID:25255312

  14. Synthesis of PtCu nanowires in nonaqueous solvent with enhanced activity and stability for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Chen, Bing; Cheng, Daojian; Zhu, Jiqin

    2014-12-01

    Pt-based core-shell electrocatalysts with one-dimensional (1D) nanostructure show a great opportunity to improve the catalytic activity and durability of pure Pt catalyst for oxygen reduction reaction (ORR). Here, we synthesize Cu@CuPt core@shell nanowires (NWs) with 1D nanostructure by using Cu NWs as templates in organic solvent medium. The ORR mass activity and specific activity of PtCu NWs are 0.216 A mgpt-1 and 0.404 mA cm-2 at 0.9 V, respectively, which are 3.1 and 3.7 times larger than that of the commercial Pt/C catalyst (0.07 A mgpt-1 and 0.110 mA cm-2, respectively). Theoretical studies suggest that the electronic effect of the Cu substrate on the Pt monolayer could be the main reason for the higher activity of PtCu NWs than that of the commercial Pt/C catalyst. In addition, the PtCu NWs show much better durability than the commercial Pt/C catalyst after stability test. It is expected that the as-synthesized PtCu NWs in organic solvent medium could be excellent candidates as high performance catalysts for ORR.

  15. A novel iron (Ⅱ) polyphthalocyanine catalyst assembled on graphene with significantly enhanced performance for oxygen reduction reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Lin, Lin; Li, Meng; Jiang, Liqing; Li, Yongfeng; Liu, Dajun; He, Xingquan; Cui, Lili

    2014-12-01

    To realize the large-scale commercial application of direct methanol fuel cells (DMFCs), the catalysts for oxygen reduction reaction (ORR) are the crucial obstacle. Here, an efficient non-noble-metal catalyst for ORR, denoted FePPc/PSS-Gr, has been obtained by anchoring p-phenyl-bis(3,4-dicyanophenyl) ether iron(Ⅱ) polyphthalocyanine (FePPc) on poly(sodium-p-styrenesulfonate) (PSS) modified graphene (PSS-Gr) through a solvothermally assisted π-π assembling approach. The Ultraviolet-visible (UV-vis) spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results reveal the π-π interaction between FePPc and PSS-Gr. The rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) measurements show that the proposed catalyst possesses an excellent catalytic performance towards ORR comparable with the commercial Pt/C catalyst in alkaline medium, such as high onset potential (-0.08 V vs. SCE), half-wave potential (-0.19 V vs. SCE), better tolerance to methanol crossover, excellent stability (81.1%, retention after 10,000 s) and an efficient four-electron pathway. The enhanced electrocatalytic performance could be chiefly attributed to its large electrochemically accessible surface area, fast electron transfer rate of PSS-Gr, in particular, the synergistic effect between the FePPc moieties and the PSS-Gr sheets.

  16. Porous Dendritic Platinum Nanotubes with Extremely High Activity and Stability for Oxygen Reduction Reaction

    PubMed Central

    Zhang, Gaixia; Sun, Shuhui; Cai, Mei; Zhang, Yong; Li, Ruying; Sun, Xueliang

    2013-01-01

    Controlling the morphology of Pt nanostructures can provide opportunities to greatly increase their activity and stability. Porous dendritic Pt nanotubes were successfully synthesized by a facile, cost-effective aqueous solution method at room temperature in large scale. These unique structures are porous, hollow, hierarchical, and single crystalline, which not only gives them a large surface area with high catalyst utilization, but also improves mass transport and gas diffusion. These novel Pt structures exhibited significantly improved catalytic activity (4.4 fold) for oxygen reduction reaction (ORR) and greatly enhanced durability (6.1 fold) over that of the state-of-the-art commercial Pt/C catalyst. This work provides a promising approach to the design of highly efficient next-generation electrocatalysts. PMID:23524665

  17. PGM-free Fe-N-C catalysts for oxygen reduction reaction: Catalyst layer design

    NASA Astrophysics Data System (ADS)

    Stariha, Sarah; Artyushkova, Kateryna; Workman, Michael J.; Serov, Alexey; Mckinney, Sam; Halevi, Barr; Atanassov, Plamen

    2016-09-01

    This work studies the morphology of platinum group metal-free (PGM-free) iron-nitrogen-carbon (Fe-N-C) catalyst layers for the oxygen reduction reaction (ORR) and compares catalytic performance via polarization curves. Three different nitrogen-rich organic precursors are used to prepare the catalysts. Using scanning electron microscopy (SEM) and focused ion beam (FIB) tomography, the porosity, Euler number (pore connectivity), overall roughness, solid phase size and pore size are calculated for catalyst surfaces and volumes. Catalytic activity is determined using membrane electrode assembly (MEA) testing. It is found that the dominant factor in MEA performance is transport limitations. Through the 2D and 3D metrics it is concluded that pore connectivity has the biggest effect on transport performance.

  18. The secondary coordination sphere and axial ligand effects on oxygen reduction reaction by iron porphyrins: a DFT computational study.

    PubMed

    Ohta, Takehiro; Nagaraju, Perumandla; Liu, Jin-Gang; Ogura, Takashi; Naruta, Yoshinori

    2016-09-01

    Oxygen reduction reaction (ORR) catalyzed by a bio-inspired iron porphyrin bearing a hanging carboxylic acid group over the porphyrin ring, and a tethered axial imidazole ligand was studied by DFT calculations. BP86 free energy calculations of the redox potentials and pK a's of reaction components involved in the proton coupled electron transfer (PCET) reactions of the ferric-hydroxo and -superoxo complexes were performed based on Born-Haber thermodynamic cycle in conjunction with a continuum solvation model. The comparison was made with iron porphyrins that lack either in the hanging acid group or axial ligand, suggesting that H-bond interaction between the carboxylic acid and iron-bound hydroxo, aquo, superoxo, and peroxo ligands (de)stabilizes the Fe-O bonding, resulting in the increase in the reduction potential of the ferric complexes. The axial ligand interaction with the imidazole raises the affinity of the iron-bound superoxo and peroxo ligands for proton. In addition, a low-spin end-on ferric-hydroperoxo intermediate, a key precursor for O-O cleavage, can be stabilized in the presence of axial ligation. Thus, selective and efficient ORR of iron porphyrin can be achieved with the aid of the secondary coordination sphere and axial ligand interactions. PMID:27501847

  19. Metal-Support Interactions of Platinum Nanoparticles Decorated N-Doped Carbon Nanofibers for the Oxygen Reduction Reaction.

    PubMed

    Melke, Julia; Peter, Benedikt; Habereder, Anja; Ziegler, Juergen; Fasel, Claudia; Nefedov, Alexei; Sezen, Hikmet; Wöll, Christof; Ehrenberg, Helmut; Roth, Christina

    2016-01-13

    N-doped carbon materials are discussed as catalyst supports for the electrochemical oxygen reduction reaction (ORR) in fuel cells. This work deals with the preparation of Pt nanoparticles (NPs) supported on N-doped carbon nanofibers (N-CNF) from a polyaniline nanofiber (PANI NF) precursor, and investigates the ORR activity of the produced materials. Initially, Pt NPs are deposited on PANI NFs. The PANI NF precursors are characterized by near-edge X-ray absorption fine structure (NEXAFS) and transmission electron microscopy (TEM) measurements. It is shown, that in the PANI NF precursor materials electrons from the Pt are being transferred toward the π-conjugated systems of the aromatic ring. This strong interaction of Pt atoms with PANI explains the high dispersion of Pt NPs on the PANI NF. Subsequently, the PANI NF precursors are carbonized at different heat-treatment conditions resulting in structurally different N-CNFs which are characterized by NEXAFS, X-ray photoelectron spectroscopy (XPS) ,and TEM measurements. It is shown that an interaction between N-groups and Pt NPs exists in all investigated N-CNFs. However, the N-CNFs differ in the composition of the N-species and the dispersion of the Pt NPs. A small mean Pt NP size with a narrow size distribution is attributed to the presence of pyrdinic N-groups in the N-CNFs, whereas, for the N-CNFs with mainly graphitic and pyrrolic N-groups, an increase in the average Pt NP size with a broad size distribution is found. The ORR activity in alkaline media investigated by Koutecky-Levich analysis of rotating disk electrode measurements showed a largely enhanced ORR activity in comparison to a conventional Pt/C catalyst. PMID:26673813

  20. Functional MoS2 by the Co/Ni doping as the catalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Xiao, B. B.; Zhang, P.; Han, L. P.; Wen, Z.

    2015-11-01

    Since the discovery of the oxygen reduction reaction (ORR) activity of the metal phthalocyanine, the great enthusiasm is ignited for searching the catalysts with low price replacing Pt-based catalysts. Here, the catalytic activities for the ORR on the Co or Ni doped MoS2 are studied by using density-functional theory (DFT). It is found that Co/MoS2 resembles FeN4 active site while Ni/MoS2 is similar with CoN4 active site. In details, for Co/MoS2, under the acid medium, the rate-determining step (RDS) is located at the second H2O formation with a barrier of 1.49 eV. While under the alkaline medium, RDS is the final OH- formation with the barrier of 0.94 eV. For Ni/MoS2, under the acid medium, the RDS is the same as that of Co/MoS2 with a barrier of 0.87 eV. However, RDS is the O formation with the barrier of 0.92 eV under the alkaline medium. Furthermore, due to the intact HOOH adsorption, it is expected that the 2e- ORR is present on Ni/MoS2, which means inferior activity compared with Co/MoS2. Our calculation demonstrates the ability to functionalize inert materials for the ORR and provides new materials to design effective Pt-free catalysts for fuel-cell technology.

  1. A General Method for Multimetallic Platinum Alloy Nanowires as Highly Active and Stable Oxygen Reduction Catalysts.

    PubMed

    Bu, Lingzheng; Ding, Jiabao; Guo, Shaojun; Zhang, Xu; Su, Dong; Zhu, Xing; Yao, Jianlin; Guo, Jun; Lu, Gang; Huang, Xiaoqing

    2015-11-25

    An unconventional class of high-performance Pt alloy multimetallic nanowires (NWs) is produced by a general method. The obtained PtNi NWs exhibit amazingly specific and mass oxygen reduction reaction (ORR) activities with improvement factors of 51.1 and 34.6 over commercial Pt/C catalysts, respectively, and are also stable in ORR conditions, making them among the most efficient electrocatalysts for ORR. PMID:26459261

  2. Coordination Chemistry of [Co(acac)2 ] with N-Doped Graphene: Implications for Oxygen Reduction Reaction Reactivity of Organometallic Co-O4 -N Species.

    PubMed

    Han, Jongwoo; Sa, Young Jin; Shim, Yeonjun; Choi, Min; Park, Noejung; Joo, Sang Hoon; Park, Sungjin

    2015-10-19

    Hybridization of organometallic complexes with graphene-based materials can give rise to enhanced catalytic performance. Understanding the chemical structures within hybrid materials is of primary importance. In this work, archetypical hybrid materials are synthesized by the reaction of an organometallic complex, [Co(II) (acac)2 ] (acac=acetylacetonate), with N-doped graphene-based materials at room temperature. Experimental characterization of the hybrid materials and theoretical calculations reveal that the organometallic cobalt-containing species is coordinated to heterocyclic groups in N-doped graphene as well as to its parental acac ligands. The hybrid material shows high electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media, and superior durability and methanol tolerance to a Pt/C catalyst. Based on the chemical structures and ORR experiments, the catalytically active species is identified as a Co-O4 -N structure. PMID:26331625

  3. Pt-Decorated PdCo@Pd/C Core-Shell Nanoparticles with Enhanced Stability and Electrocatalytic Activity for the Oxygen Reduction Reaction

    SciTech Connect

    Wang, Deli; Xin, Huolin L.; Yu, Yingchao; Wang, Hongsen; Rus, Eric; Muller, David A.; Abruña, Héctor D.

    2010-11-24

    A simple method for the preparation of PdCo@Pd core-shell nanoparticles supported on carbon based on an adsorbate-induced surface segregation effect has been developed. The stability of these PdCo@Pd nanoparticles and their electrocatalytic activity for the oxygen reduction reaction (ORR) were enhanced by decoration with a small amount of Pt deposited via a spontaneous displacement reaction. The facile method described herein is suitable for large-scale, lower-cost production and significantly lowers the Pt loading and thus the cost. The as-prepared PdCo@Pd and Pd-decorated PdCo@Pd nanocatalysts have a higher methanol tolerance than Pt/C in the ORR and are promising cathode catalysts for fuel cell applications.

  4. Synthesis of boron and nitrogen co-doped graphene nano-platelets using a two-step solution process and catalytic properties for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Han, Jongwoo; Cheon, Jae Yeong; Joo, Sang Hoon; Park, Sungjin

    2014-07-01

    Chemically modified graphenes (CMGs) show great promise for various applications owing to the feasibility of their low-cost mass production and good solution processability. Recently, hetero-atom-doped CMGs have been suggested as good candidate materials for electrochemical catalysts in oxygen reduction reaction (ORR). In this study, we synthesized B, N co-doped graphene nano-platelets (BN-rG-O) using a two-step solution process with sequential reaction of graphene oxide with borane tetrahydrofuran and hydrazine monohydrate. In the ORR measured in a basic medium (0.1 M KOH), BN-rG-O exhibits an onset potential of 0.81 V (vs. reversible hydrogen electrode), follows near four electron pathway, and shows excellent stability against methanol poisoning and during durability tests.

  5. A Simple Synthesis of an N-Doped Carbon ORR Catalyst: Hierarchical Micro/Meso/Macro Porosity and Graphitic Shells.

    PubMed

    Eisenberg, David; Stroek, Wowa; Geels, Norbert J; Sandu, Cosmin S; Heller, Adam; Yan, Ning; Rothenberg, Gadi

    2016-01-11

    Replacing platinum as an oxygen reduction catalyst is an important scientific and technological challenge. Herein we report a simple synthesis of a complex carbon with very good oxygen reduction reaction (ORR) activity at pH 13. Pyrolysis of magnesium nitrilotriacetate yields a carbon with hierarchical micro/meso/macro porosity, resulting from in situ templating by spontaneously forming MgO nanoparticles and from etching by pyrolysis gases. The mesopores are lined with highly graphitic shells. The high ORR activity is attributed to a good balance between high specific surface area and mass transport through the hierarchical porosity, and to improved electronic conductivity through the graphitic shells. This novel carbon has a high surface area (1320 m(2) g(-1) ), and high nitrogen content for a single precursor synthesis (∼6 %). Importantly, its synthesis is both cheap and easily scalable. PMID:26574917

  6. Effect of post heat-treatment of composition-controlled PdFe nanoparticles for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Kang, Yun Sik; Choi, Kwang-Hyun; Ahn, Docheon; Lee, Myeong Jae; Baik, Jaeyoon; Chung, Dong Young; Kim, Mi-Ju; Lee, Stanfield Youngwon; Kim, Minhyoung; Shin, Heejong; Lee, Kug-Seung; Sung, Yung-Eun

    2016-01-01

    Composition-controlled and carbon-supported PdFe nanoparticles (NPs) were prepared via a modified chemical synthesis after heat-treatment at high temperature under a reductive atmosphere. This novel synthesis, which combines the polyol reduction method and hydride method, was used to obtain monodispersed PdFe NPs. In addition, to induce structural modifications, the as-prepared PdFe NPs received heat-treatment under a reductive atmosphere. Structural characterization, including high-resolution powder diffraction (HRPD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS) analysis, indicated that heat-treated PdFe NPs exhibited a higher degree of alloying and surface Pd atomic composition compared with as-prepared ones. Furthermore, new crystalline phases were detected after heat-treatment. Thanks to the structural alterations, heat-treated PdFe NPs showed ∼3 and ∼18 times higher mass- and area-normalized oxygen reduction reaction (ORR) activities, respectively than commercial Pt/C. Single cell testing with heat-treated PdFe catalysts exhibited a ∼2.5 times higher mass-normalized maximum power density than the reference cell. Surface structure analyses, including cyclic voltammetry (CV), COad oxidation, and XPS, revealed that, after heat-treatment, a downshift of the Pd d-band center occurred, which led to a decrease in the affinity of Pd for oxygen species, resulting in more favorable ORR kinetics.

  7. Non-precious metal nanoparticles supported on nitrogen-doped graphene as a promising catalyst for oxygen reduction reaction: Synthesis, characterization and electrocatalytic performance

    NASA Astrophysics Data System (ADS)

    Ghanbarlou, Hosna; Rowshanzamir, Soosan; Kazeminasab, Bagher; Parnian, Mohammad Javad

    2015-01-01

    Nitrogen-doped graphene (NG) based non-precious metal catalysts is used as a catalyst for oxygen reduction reaction (ORR). Nanoflower-like NG with designed nitrogen types is directly synthesized using a low temperature solvothermal process and then Fe, Co and Fe-Co nanoparticles are precipitated onto the NG using a modified polyol method. The morphology of the NG is studied using scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The synthesized M/NG (M = Fe, Co, Fe-Co) electrocatalysts are characterized using transmission electron microscopy, X-ray diffraction and energy-dispersive X-ray spectroscopy. Electrochemical characterizations reveal that NG acts as a catalyst for ORR in an alkaline solution. The electrocatalytic properties of NG and M/NG catalysts are investigated for ORR in 0.1 M KOH. Cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy are used to measure electrocatalytic activity. M/NG catalysts exhibit higher electrocatalytic activity than NG and the highest activity is observed for the Co/NG electrode. Chronoamperometric results demonstrate that the Co/NG catalyst is more stable than commercial Pt/C for ORR in an alkaline solution.

  8. Fog-like fluffy structured N-doped carbon with a superior oxygen reduction reaction performance to a commercial Pt/C catalyst.

    PubMed

    You, Chenghang; Zen, Xiaoyuan; Qiao, Xiaochang; Liu, Fangfang; Shu, Ting; Du, Li; Zeng, Jianhuang; Liao, Shijun

    2015-02-28

    A high-performance N-doped carbon catalyst with a fog-like, fluffy structure was prepared through pyrolyzing a mixture of polyacrylonitrile, melamine and iron chloride. The catalyst exhibits an excellent oxygen reduction reaction (ORR) performance, with a half-wave potential 27 mV more positive than that of a commercial Pt/C catalyst (-0.120 vs. -0.147 V) and a higher diffusion-limiting current density than that of Pt/C (5.60 vs. 5.33 mA cm(-2)) in an alkaline medium. Moreover, it also shows outstanding methanol tolerance, remarkable stability and nearly 100% selectivity for the four-electron ORR process. To our knowledge, it is one of the most active doped carbon ORR catalysts in alkaline media to date. By comparing catalysts derived from precursors containing different amounts of melamine, we found that the added melamine not only gives the catalyst a fluffy structure but also modifies the N content and the distribution of N species in the catalyst, which we believe to be the origins for the catalyst's excellent ORR performance. PMID:25648746

  9. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

    PubMed Central

    Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

    2016-01-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm−2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production. PMID:26839148

  10. Activity of dealloyed PtCo 3 and PtCu 3 nanoparticle electrocatalyst for oxygen reduction reaction in polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Oezaslan, Mehtap; Strasser, Peter

    We report a comparative study of the alloy formation and electrochemical activity of dealloyed PtCo 3 and PtCu 3 nanoparticle electrocatalysts for the oxygen reduction reaction (ORR). For the Pt-Co system the maximum annealing temperatures were 650 °C, 800 °C and 900 °C for 7 h to drive the Pt-Co alloy formation and the particle growth. EDS and XRD were employed for the characterization of catalyst powders. The RDE and RRDE experiments were conducted in 0.1 M HClO 4 at room temperature. We demonstrate that the mass and surface area specific ORR activities of Pt-Co and Pt-Cu alloys after voltammetric activation exhibit a considerable improvement compared to those of pure Pt/C. The dealloyed PtCo 3 (800 °C/7 h) electrocatalyst performs 3 times higher in terms of Pt-based mass activity and 4-5 times higher in terms of ECSA-based specific activity than a 28.2 wt.% Pt/C. Dealloyed Pt-Co catalysts (800 °C/7 h) show the most favorable balance between mass and specific ORR activity with a particle size of 2.2 ± 0.1 nm. We hypothesize that geometric strain effects of the dealloyed Pt-Co nanoparticles, similar to those found in dealloyed PtCu 3 nanoparticles, are responsible for the improvement in ORR activity [1].

  11. Nanoporous PdZr surface alloy as highly active non-platinum electrocatalyst toward oxygen reduction reaction with unique structure stability and methanol-tolerance

    NASA Astrophysics Data System (ADS)

    Duan, Huimei; Xu, Caixia

    2016-06-01

    Nanoporous (NP) PdZr alloy with controllable bimetallic ratio is successfully fabricated by a simple dealloying method. By leaching out the more reactive Al from PdZrAl precursor alloy, NP-PdZr alloy with smaller ligament size was generated, characterized by the nanoscaled interconnected network skeleton and hollow channels extending in all three dimensions. Upon voltammetric scan in acid solution, the dissolution of surface Zr atoms generates the highly active Pd-Zr surface alloy with a nearly pure Pd surface and Pd-Zr alloy core. The NP-Pd80Zr20 surface alloy exhibits markedly enhanced specific and mass activities as well as higher catalytic stability toward oxygen reduction reaction (ORR) compared with NP-Pd and the state-of-the-art Pt/C catalysts. In addition, the NP-Pd80Zr20 surface alloy shows a better selectivity for ORR than methanol in the 0.1 M HClO4 and 0.1 M methanol mixed solution. X-ray photoelectron spectroscopy and density functional theory calculations both demonstrate that the weakened Pd-O bond and improved ORR performances in turn depend on the downshifted d-band center of Pd due to the alloying Pd with Zr (20 at.%). The as-made NP-PdZr alloy holds prospective applications as a cathode electrocatalyst in fuel-cell-related technologies with the advantages of superior overall ORR performances, unique structure stability, and easy preparation.

  12. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction.

    PubMed

    Vij, Varun; Tiwari, Jitendra N; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S

    2016-01-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp(2) carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm(-2) at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production. PMID:26839148

  13. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

    2016-02-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

  14. Microwave Assisted Wolff-Kishner Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Parquet, Eric; Lin, Qun

    1997-10-01

    A Wolff-Kishner reduction of a carbonyl group was carried out in a household microwave oven. Isatin was first converted to the hydrazone with 55% hydrazine and ethylene glycol by irradiation in the microwave oven at medium power for 30 seconds. Then, isatin 3-hydrazone was mixed with ethylene glycol and potassium hydroxide and irradiated in the microwave oven for only 10 seconds. After simple work-up and recrystallization, oxindole was obtained in a yield of 32.4%. The two step syntheses described here offer several advantages: (1) very short reaction time with no need for special microscale glassware, (2) mild experimental conditions (hot oil baths and heating mantles are not required), (3) the reagents are easy to handle (students do not need to prepare sodium ethoxide from sodium metal and absolute ethanol).

  15. Nitrogen-doped graphene/carbon nanotube hybrids: in situ formation on bifunctional catalysts and their superior electrocatalytic activity for oxygen evolution/reduction reaction.

    PubMed

    Tian, Gui-Li; Zhao, Meng-Qiang; Yu, Dingshan; Kong, Xiang-Yi; Huang, Jia-Qi; Zhang, Qiang; Wei, Fei

    2014-06-12

    There is a growing interest in oxygen electrode catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), as they play a key role in a wide range of renewable energy technologies such as fuel cells, metal-air batteries, and water splitting. Nevertheless, the development of highly-active bifunctional catalysts at low cost for both ORR and OER still remains a huge challenge. Herein, we report a new N-doped graphene/single-walled carbon nanotube (SWCNT) hybrid (NGSH) material as an efficient noble-metal-free bifunctional electrocatalyst for both ORR and OER. NGSHs were fabricated by in situ doping during chemical vapor deposition growth on layered double hydroxide derived bifunctional catalysts. Our one-step approach not only provides simultaneous growth of graphene and SWCNTs, leading to the formation of three dimensional interconnected network, but also brings the intrinsic dispersion of graphene and carbon nanotubes and the dispersion of N-containing functional groups within a highly conductive scaffold. Thus, the NGSHs possess a large specific surface area of 812.9 m(2) g(-1) and high electrical conductivity of 53.8 S cm(-1) . Despite of relatively low nitrogen content (0.53 at%), the NGSHs demonstrate a high ORR activity, much superior to two constituent components and even comparable to the commercial 20 wt% Pt/C catalysts with much better durability and resistance to crossover effect. The same hybrid material also presents high catalytic activity towards OER, rendering them high-performance cheap catalysts for both ORR and OER. Our result opens up new avenues for energy conversion technologies based on earth-abundant, scalable, noble-metal-free catalysts. PMID:24574006

  16. Covalent functionalization based heteroatom doped graphene nanosheet as a metal-free electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Park, Minju; Lee, Taemin; Kim, Byeong-Su

    2013-11-01

    Oxygen reduction reaction (ORR) is an important reaction in energy conversion systems such as fuel cells and metal-air batteries. Carbon nanomaterials doped with heteroatoms are highly attractive materials for use as electrocatalysts by virtue of their excellent electrocatalytic activity, high conductivity, and large surface area. This study reports the synthesis of highly efficient electrocatalysts based on heteroatom-doped graphene nanosheets prepared through covalent functionalization using various small organic molecules and a subsequent thermal treatment. A series of nitrogen-doped reduced graphene oxide (NRGOn) nanosheets exhibited varying degrees and configurations of nitrogen atoms within the graphitic framework depending on the type of precursors used. On the basis of the rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) experiments, NRGO3, with a high degree of pyridinic-N content, displayed the desired one-step, quasi-four-electron transfer pathway during ORR, similar to commercial Pt/C. We also demonstrated the potential of covalent functionalization of sulfur and boron-doped graphene nanosheets.Oxygen reduction reaction (ORR) is an important reaction in energy conversion systems such as fuel cells and metal-air batteries. Carbon nanomaterials doped with heteroatoms are highly attractive materials for use as electrocatalysts by virtue of their excellent electrocatalytic activity, high conductivity, and large surface area. This study reports the synthesis of highly efficient electrocatalysts based on heteroatom-doped graphene nanosheets prepared through covalent functionalization using various small organic molecules and a subsequent thermal treatment. A series of nitrogen-doped reduced graphene oxide (NRGOn) nanosheets exhibited varying degrees and configurations of nitrogen atoms within the graphitic framework depending on the type of precursors used. On the basis of the rotating disk electrode (RDE) and rotating ring-disk electrode

  17. Cobalt-manganese-based spinels as multifunctional materials that unify catalytic water oxidation and oxygen reduction reactions.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Strasser, Peter; Driess, Matthias

    2015-01-01

    Recently, there has been much interest in the design and development of affordable and highly efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts that can resolve the pivotal issues that concern solar fuels, fuel cells, and rechargeable metal-air batteries. Here we present the synthesis and application of porous CoMn2 O4 and MnCo2 O4 spinel microspheres as highly efficient multifunctional catalysts that unify the electrochemical OER with oxidant-driven and photocatalytic water oxidation as well as the ORR. The porous materials were prepared by the thermal degradation of the respective carbonate precursors at 400 °C. The as-prepared spinels display excellent performances in electrochemical OER for the cubic MnCo2 O4 phase in comparison to the tetragonal CoMn2 O4 material in an alkaline medium. Moreover, the oxidant-driven and photocatalytic water oxidations were performed and they exhibited a similar trend in activity to that of the electrochemical OER. Remarkably, the situation is reversed in ORR catalysis, that is, the oxygen reduction activity and stability of the tetragonal CoMn2 O4 catalyst outperformed that of cubic MnCo2 O4 and rivals that of benchmark Pt catalysts. The superior catalytic performance and the remarkable stability of the unifying materials are attributed to their unique porous and robust microspherical morphology and the intrinsic structural features of the spinels. Moreover, the facile access to these high-performance materials enables a reliable and cost-effective production on a large scale for industrial applications. PMID:25394186

  18. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    SciTech Connect

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; Wu, Pu -Wei; Lee, Jyh -Fu

    2014-11-22

    Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1 M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.

  19. Facile preparation of nitrogen-doped graphene as a metal-free catalyst for oxygen reduction reaction.

    PubMed

    Lin, Ziyin; Song, Min-kyu; Ding, Yong; Liu, Yan; Liu, Meilin; Wong, Ching-ping

    2012-03-14

    Nitrogen-doped graphene (nG) is a promising metal-free catalyst for oxygen reduction reaction (ORR) on the cathode of fuel cells. Here we report a facile preparation of nG via pyrolysis of graphene oxide with melamine. The morphology of the nG is revealed using scanning electron microscopy and transmission electron microscopy while the successful N doping is confirmed by electron energy loss spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The resulting nG shows high electrocatalytic activity toward ORR in an alkaline solution with an onset potential of -0.10 V vs. Ag/AgCl reference electrode. The nG catalyzed oxygen reduction exhibits a favorable formation of water via a four-electron pathway. Good stability and anti-crossover property are also observed, which are advantageous over the Pt/C catalyst. Furthermore, the effect of pyrolysis temperature on the structure and activity of nG is systematically studied to gain some insights into the chemical reactions during pyrolysis. PMID:22307527

  20. Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction

    PubMed Central

    Huang, K.; Bi, K.; Liang, C.; Lin, S.; Wang, W. J.; Yang, T. Z.; Liu, J.; Zhang, R.; Fan, D. Y.; Wang, Y. G.; Lei, M.

    2015-01-01

    Novel graphite-molybdenum carbide nanocomposites (G-Mo2C) are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR) benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon. PMID:26381266

  1. Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction.

    PubMed

    Huang, K; Bi, K; Liang, C; Lin, S; Wang, W J; Yang, T Z; Liu, J; Zhang, R; Fan, D Y; Wang, Y G; Lei, M

    2015-01-01

    Novel graphite-molybdenum carbide nanocomposites (G-Mo2C) are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR) benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon. PMID:26381266

  2. Synergistic Effect of Nitrogen in Cobalt Nitride and Nitrogen-Doped Hollow Carbon Spheres for Oxygen Reduction Reaction

    SciTech Connect

    Zhong, Xing; Liu, Lin; Jiang, Yu; Wang, Xinde; Wang, Lei; Zhuang, Guilin; Li, Xiaonian; Mei, Donghai; Wang, Jian-guo; Su, Dang S.

    2015-06-15

    The need for inexpensive and high-activity oxygen reduction reaction (ORR) electrocatalysts has attracted considerable research interest over the past years. Here we report a novel hybrid that contains cobalt nitride/nitrogen-rich hollow carbon spheres (CoxN/NHCS) as a high-performance catalyst for ORR. The CoxN nanoparticles were uniformly dispersed and confined in the hollow NHCS shell. The performance of the resulting CoxN/NHCS hybrid was comparable with that of a commercial Pt/C at the same catalyst loading toward ORR, but the mass activity of the former was 5.7 times better than that of the latter. The nitrogen in both CoxN and NHCS, especially CoxN, could weaken the adsorption of reaction intermediates (O and OOH), which follows the favourable reaction pathway on CoxN/NHCS according to the DFT-calculated Gibbs free energy diagrams. Our results demonstrated a new strategy for designing and developing inexpensive, non-precious metal electrocatalysts for next-generation fuels. The authors acknowledge the financial support from the National Basic Research Program (973 program, No. 2013CB733501) and the National Natural Science Foundation of China (No. 21306169, 21101137, 21136001, 21176221 and 91334013). Dr. D. Mei is supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.

  3. Co/CoO/CoFe2O4/G nanocomposites derived from layered double hydroxides towards mass production of efficient Pt-free electrocatalysts for oxygen reduction reaction.

    PubMed

    Huo, Ruijie; Jiang, Wen-Jie; Xu, Sailong; Zhang, Fazhi; Hu, Jin-Song

    2014-01-01

    Development of a simple, reproducible and cost-effective protocol for mass production of non-precious-metal electrocatalysts for oxygen reduction reaction (ORR) is still challenging but highly desirable for their practical applications in industry. Herein, we developed a facile and scalable method to directly produce graphene (G) supported CoFe-LDHs and successfully used them as a precursor for mass production of Co/CoO/CoFe2O4/G as a low-cost and Pt-free efficient electrocatalyst, which exhibits comparable electrocatalytic activity and much better durability for ORR in comparison with commercial Pt/C catalysts. The result may provide a way for cost-effective production of ORR electrocatalysts on a large scale for practical applications. PMID:24247636

  4. Selective catalysts for the hydrogen oxidation and oxygen reduction reactions by patterning of platinum with calix[4]arene molecules.

    SciTech Connect

    Genorio, B.; Strmcnik, D.; Subbaraman, R.; Tripkovic, D.; Karapetrov, G.; Stamenkovic, V. R.; Pejovnik, S.; Markovic, N. M.; Univ. Ljubljana; National Inst. of Chemistry

    2010-12-01

    The design of new catalysts for polymer electrolyte membrane fuel cells must be guided by two equally important fundamental principles: optimization of their catalytic behaviour as well as the long-term stability of the metal catalysts and supports in hostile electrochemical environments. The methods used to improve catalytic activity are diverse, ranging from the alloying and de-alloying of platinum to the synthesis of platinum core-shell catalysts. However, methods to improve the stability of the carbon supports and catalyst nanoparticles are limited, especially during shutdown (when hydrogen is purged from the anode by air) and startup (when air is purged from the anode by hydrogen) conditions when the cathode potential can be pushed up to 1.5 V. Under the latter conditions, stability of the cathode materials is strongly affected (carbon oxidation reaction) by the undesired oxygen reduction reaction (ORR) on the anode side. This emphasizes the importance of designing selective anode catalysts that can efficiently suppress the ORR while fully preserving the Pt-like activity for the hydrogen oxidation reaction. Here, we demonstrate that chemically modified platinum with a self-assembled monolayer of calix[4]arene molecules meets this challenging requirement.

  5. Highly graphitized nitrogen-doped porous carbon nanopolyhedra derived from ZIF-8 nanocrystals as efficient electrocatalysts for oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Linjie; Su, Zixue; Jiang, Feilong; Yang, Lingling; Qian, Jinjie; Zhou, Youfu; Li, Wenmu; Hong, Maochun

    2014-05-01

    Nitrogen-doped graphitic porous carbons (NGPCs) have been synthesized by using a zeolite-type nanoscale metal-organic framework (NMOF) as a self-sacrificing template, which simultaneously acts as both the carbon and nitrogen sources in a facile carbonization process. The NGPCs not only retain the nanopolyhedral morphology of the parent NMOF, but also possess rich nitrogen, high surface area and hierarchical porosity with well-conducting networks. The promising potential of NGPCs as metal-free electrocatalysts for oxygen reduction reactions (ORR) in fuel cells is demonstrated. Compared with commercial Pt/C, the optimized NGPC-1000-10 (carbonized at 1000 °C for 10 h) catalyst exhibits comparable electrocatalytic activity via an efficient four-electron-dominant ORR process coupled with superior methanol tolerance as well as cycling stability in alkaline media. Furthermore, the controlled experiments reveal that the optimum activity of NGPC-1000-10 can be attributed to the synergetic contributions of the abundant active sites with high graphitic-N portion, high surface area and porosity, and the high degree of graphitization. Our findings suggest that solely MOF-derived heteroatom-doped carbon materials can be a promising alternative for Pt-based catalysts in fuel cells.Nitrogen-doped graphitic porous carbons (NGPCs) have been synthesized by using a zeolite-type nanoscale metal-organic framework (NMOF) as a self-sacrificing template, which simultaneously acts as both the carbon and nitrogen sources in a facile carbonization process. The NGPCs not only retain the nanopolyhedral morphology of the parent NMOF, but also possess rich nitrogen, high surface area and hierarchical porosity with well-conducting networks. The promising potential of NGPCs as metal-free electrocatalysts for oxygen reduction reactions (ORR) in fuel cells is demonstrated. Compared with commercial Pt/C, the optimized NGPC-1000-10 (carbonized at 1000 °C for 10 h) catalyst exhibits comparable

  6. CuCo2O4 ORR/OER Bi-functional catalyst: Influence of synthetic approach on performance

    DOE PAGESBeta

    Serov, Alexey; Andersen, Nalin I.; Roy, Aaron J.; Matanovic, Ivana; Artyushkova, Kateryna; Atanassov, Plamen

    2015-02-07

    A series of CuCo2O4 catalysts were synthesized by pore forming, sol-gel, spray pyrolysis and sacrificial support methods. Catalysts were characterized by XRD, SEM, XPS and BET techniques. The electrochemical activity for the oxygen reduction and oxygen evolution reactions (ORR and OER) was evaluated in alkaline media by RRDE. Density Functional Theory was used to identify two different types of active sites responsible for ORR/OER activity of CuCo2O4 and it was found that CuCo2O4 can activate the O-O bond by binding molecular oxygen in bridging positions between Co or Co and Cu atoms. It was found that the sacrificial support methodmore » (SSM) catalyst has the highest performance in both ORR and OER and has the highest content of phase-pure CuCo2O4. It was shown that the presence of CuO significantly decreases the activity in oxygen reduction and oxygen evolution reactions. As a result, the half-wave potential (E1/2) of CuCo2O4-SSM was found as 0.8 V, making this material a state-of-the-art, unsupported oxide catalyst.« less

  7. Nitrogen-doped graphene prepared by a transfer doping approach for the oxygen reduction reaction application

    NASA Astrophysics Data System (ADS)

    Mo, Zaiyong; Zheng, Ruiping; Peng, Hongliang; Liang, Huagen; Liao, Shijun

    2014-01-01

    Well defined nitrogen-doped graphene (NG) is prepared by a transfer doping approach, in which the graphene oxide (GO) is deoxidized and nitrogen doped by the vaporized polyaniline, and the GO is prepared by a thermal expansion method from graphite oxide. The content of doped nitrogen in the doped graphene is high up to 6.25 at% by the results of elements analysis, and oxygen content is lowered to 5.17 at%. As a non-precious metal cathode electrocatalyst, the NG catalyst exhibits excellent activity toward the oxygen reduction reaction, as well as excellent tolerance toward methanol. In 0.1 M KOH solution, its onset potential, half-wave potential and limiting current density for the oxygen reduction reaction reach 0.98 V (vs. RHE), 0.87 V (vs. RHE) and 5.38 mA cm-2, respectively, which are comparable to those of commercial 20 wt% Pt/C catalyst. The well defined graphene structure of the catalyst is revealed clearly by HRTEM and Raman spectra. It is suggested that the nitrogen-doping and large surface area of the NG sheets give the main contribution to the high ORR catalytic activity.

  8. In-Situ Formation of Cobalt-Phosphate Oxygen-Evolving Complex-Anchored Reduced Graphene Oxide Nanosheets for Oxygen Reduction Reaction

    PubMed Central

    Zhao, Zhi-Gang; Zhang, Jing; Yuan, Yinyin; Lv, Hong; Tian, Yuyu; Wu, Dan; Li, Qing-Wen

    2013-01-01

    Oxygen conversion process between O2 and H2O by means of electrochemistry or photochemistry has lately received a great deal of attention. Cobalt-phosphate (Co-Pi) catalyst is a new type of cost-effective artificial oxygen-evolving complex (OEC) with amorphous features during photosynthesis. However, can such Co-Pi OEC also act as oxygen reduction reaction (ORR) catalyst in electrochemical processes? The question remains unanswered. Here for the first time we demonstrate that Co-Pi OEC does be rather active for the ORR. Particularly, Co-Pi OEC anchoring on reduced graphite oxide (rGO) nanosheet is shown to possess dramatically improved electrocatalytic activities. Differing from the generally accepted role of rGO as an “electron reservoir”, we suggest that rGO serves as “peroxide cleaner” in enhancing the electrocatalytic behaviors. The present study may bridge the gap between photochemistry and electrochemistry towards oxygen conversion. PMID:23877331

  9. In-Situ Formation of Cobalt-Phosphate Oxygen-Evolving Complex-Anchored Reduced Graphene Oxide Nanosheets for Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Zhao, Zhi-Gang; Zhang, Jing; Yuan, Yinyin; Lv, Hong; Tian, Yuyu; Wu, Dan; Li, Qing-Wen

    2013-07-01

    Oxygen conversion process between O2 and H2O by means of electrochemistry or photochemistry has lately received a great deal of attention. Cobalt-phosphate (Co-Pi) catalyst is a new type of cost-effective artificial oxygen-evolving complex (OEC) with amorphous features during photosynthesis. However, can such Co-Pi OEC also act as oxygen reduction reaction (ORR) catalyst in electrochemical processes? The question remains unanswered. Here for the first time we demonstrate that Co-Pi OEC does be rather active for the ORR. Particularly, Co-Pi OEC anchoring on reduced graphite oxide (rGO) nanosheet is shown to possess dramatically improved electrocatalytic activities. Differing from the generally accepted role of rGO as an ``electron reservoir'', we suggest that rGO serves as ``peroxide cleaner'' in enhancing the electrocatalytic behaviors. The present study may bridge the gap between photochemistry and electrochemistry towards oxygen conversion.

  10. In-situ formation of cobalt-phosphate oxygen-evolving complex-anchored reduced graphene oxide nanosheets for oxygen reduction reaction.

    PubMed

    Zhao, Zhi-Gang; Zhang, Jing; Yuan, Yinyin; Lv, Hong; Tian, Yuyu; Wu, Dan; Li, Qing-Wen

    2013-01-01

    Oxygen conversion process between O₂ and H₂O by means of electrochemistry or photochemistry has lately received a great deal of attention. Cobalt-phosphate (Co-Pi) catalyst is a new type of cost-effective artificial oxygen-evolving complex (OEC) with amorphous features during photosynthesis. However, can such Co-Pi OEC also act as oxygen reduction reaction (ORR) catalyst in electrochemical processes? The question remains unanswered. Here for the first time we demonstrate that Co-Pi OEC does be rather active for the ORR. Particularly, Co-Pi OEC anchoring on reduced graphite oxide (rGO) nanosheet is shown to possess dramatically improved electrocatalytic activities. Differing from the generally accepted role of rGO as an "electron reservoir", we suggest that rGO serves as "peroxide cleaner" in enhancing the electrocatalytic behaviors. The present study may bridge the gap between photochemistry and electrochemistry towards oxygen conversion. PMID:23877331

  11. Sulfur and nitrogen co-doped, few-layered graphene oxide as a highly efficient electrocatalyst for the oxygen-reduction reaction.

    PubMed

    Xu, Jiaoxing; Dong, Guofa; Jin, Chuanhong; Huang, Meihua; Guan, Lunhui

    2013-03-01

    S and N co-doped, few-layered graphene oxide is synthesized by using pyrimidine and thiophene as precursors for the application of the oxygen reduction reaction (ORR). The dual-doped catalyst with pyrrolic/graphitic N-dominant structures exhibits competitive catalytic activity (10.0 mA cm(-2) kinetic-limiting current density at -0.25 V) that is superior to that for mono N-doped carbon nanomaterials. This is because of a synergetic effect of N and S co-doping. Furthermore, the dual-doped catalyst also shows an efficient four-electron-dominant ORR process, which has excellent methanol tolerance and improved durability in comparison to commercial Pt/C catalysts. PMID:23404829

  12. Porous nitrogen-doped carbon nanosheet on graphene as metal-free catalyst for oxygen reduction reaction in air-cathode microbial fuel cells.

    PubMed

    Wen, Qing; Wang, Shaoyun; Yan, Jun; Cong, Lijie; Chen, Ye; Xi, Hongyuan

    2014-02-01

    Porous nitrogen-doped carbon nanosheet on graphene (PNCN) was used as an alternative cathode catalyst for oxygen reduction reaction (ORR) in air-cathode microbial fuel cells (MFCs). Here we report a novel, low-cost, scalable, synthetic method for preparation of PNCN via the carbonization of graphite oxide-polyaniline hybrid (GO-PANI), subsequently followed by KOH activation treatment. Due to its high concentration of nitrogen and high specific surface area, PNCN exhibited an excellent catalytic activity for ORR. As a result, the maximum power density of 1159.34mWm(-2) obtained with PNCN catalyst was higher than that of Pt/C catalyst (858.49mWm(-2)) in a MFC. Therefore, porous nitrogen-doped carbon nanosheet could be a good alternative to Pt catalyst in MFCs. PMID:24239870

  13. Facial synthesis of PtM (M = Fe, Co, Cu, Ni) bimetallic alloy nanosponges and their enhanced catalysis for oxygen reduction reaction.

    PubMed

    Zhu, Zhijun; Zhai, Yanling; Dong, Shaojun

    2014-10-01

    Constructing electrocatalysts with enhanced activity and stability is necessary due to the increasing demands of the fuel cell industry. This work demonstrates a facile approach to synthesize well-defined three-dimensional (3D) PtM (M = Fe, Co, Cu, Ni) bimetallic alloy nanosponges (BANs) in the presence of Al. Significantly, with the aid of Al, the as-prepared BANs exhibit greatly enhanced electrochemistry catalytic activity in an oxygen reduction reaction (ORR), and PtFe BANs appear the best ORR property among the four BANs and commercial Pt/C catalysts. This work may provide a universal approach for convenient and large-scale fabrication of porous bimetallic nanocatalysts, thus providing promising potential application as an efficient cathodic component in fuel cells for industrial production. PMID:25223424

  14. Anion adsorption, CO oxidation, and oxygen reduction reaction on a Au(100) surface: The pH effect

    SciTech Connect

    Blizanac, Berislav B.; Lucas, Chris A.; Gallagher, Mark E.; Arenz, Matthias; Ross, Philip N.; Markovic, Nenad M.

    2004-07-29

    The effects of pH on the surface reconstruction of Au(100), on CO oxidation, and on the oxygen reduction reaction (ORR) have been studied by a combination of surface X-ray scattering (SXS), Fourier transform infrared (FTIR) spectroscopy, and rotating ring-disk electrode (RRDE) measurements. In harmony with previous SXS and scanning tunneling microscopy (STM) results, the potential-induced hexagonal (''hex'') to (1 x 1) transition occurs faster in an alkaline electrolyte than in acidic media. In alkaline solution, CO adsorption facilitates the formation of a ''hex'' phase; in acid solution, however, CO has negligible effect on the potential range of thermodynamic stability of the ''hex'' <--> (1 x 1) transition. We propose that in KOH the continuous removal of OHad in the Langmuir-Hinshelwood reaction (CO + OH) CO2 + H+ + e- may stabilize the ''hex'' phase over a much wider potential range than in CO-free solution. In acid solution, where specifically adsorbing anions cannot be displaced by CO from the Au(100) surface, CO has negligible effect on the equilibrium potential for the ''hex'' <--> (1 x 1) transition. Such a mechanism is in agreement with the pH-dependent oxidation of CO. The ORR is also affected by the pH of solution. It is proposed that the pH-dependent kinetics of the ORR on Au(100) can be unraveled by finding the relationship between kinetic rates and two terms: (i) the energetic term of the Au(100)-O2- interaction determines the potential regions where the rate-determining step O2 + e = O2- occurs, and (ii) the preexponential term determines the availability of active sites for the adsorption of O2-.

  15. Cobalt nanoparticles embedded in N-doped carbon as an efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions

    NASA Astrophysics Data System (ADS)

    Su, Yunhe; Zhu, Yihua; Jiang, Hongliang; Shen, Jianhua; Yang, Xiaoling; Zou, Wenjian; Chen, Jianding; Li, Chunzhong

    2014-11-01

    Cobalt based catalysts are promising bifunctional electrocatalysts for both oxygen reduction and oxygen evolution reactions (ORR and OER) in unitized regenerative fuel cells (URFCs) operating with alkaline electrolytes. Here we report a hybrid composite of cobalt nanoparticles embedded in nitrogen-doped carbon (Co/N-C) via a solvothermal carbonization strategy. With the synergistic effect arising from the N-doped carbon and cobalt nanoparticles in the composite, the Co/N-C hybrid catalyst exhibits highly efficient bifunctional catalytic activity and excellent stability toward both ORR and OER. The ΔE (oxygen electrode activity parameter for judging the overall electrocatalytic activity of a bifunctional electrocatalyst) value for Co/N-C is 0.859 V, which is smaller than those of Pt/C and most of the non-precious metal catalysts in previous studies. Furthermore, the Co/N-C composite also shows better bifunctional catalytic activity than its oxidative counterparts, which could be attributed to the high specific surface area and the efficient charge transfer ability of the composite, as well as the good synergistic effect between N-doped carbon and the Co nanoparticles in the Co/N-C composite.Cobalt based catalysts are promising bifunctional electrocatalysts for both oxygen reduction and oxygen evolution reactions (ORR and OER) in unitized regenerative fuel cells (URFCs) operating with alkaline electrolytes. Here we report a hybrid composite of cobalt nanoparticles embedded in nitrogen-doped carbon (Co/N-C) via a solvothermal carbonization strategy. With the synergistic effect arising from the N-doped carbon and cobalt nanoparticles in the composite, the Co/N-C hybrid catalyst exhibits highly efficient bifunctional catalytic activity and excellent stability toward both ORR and OER. The ΔE (oxygen electrode activity parameter for judging the overall electrocatalytic activity of a bifunctional electrocatalyst) value for Co/N-C is 0.859 V, which is smaller than those

  16. Gas phase contributions to topochemical hydride reduction reactions

    NASA Astrophysics Data System (ADS)

    Kobayashi, Yoji; Li, Zhaofei; Hirai, Kei; Tassel, Cédric; Loyer, François; Ichikawa, Noriya; Abe, Naoyuki; Yamamoto, Takafumi; Shimakawa, Yuichi; Yoshimura, Kazuyoshi; Takano, Mikio; Hernandez, Olivier J.; Kageyama, Hiroshi

    2013-11-01

    Alkali and alkali earth hydrides have been used as solid state reductants recently to yield many interesting new oxygen-deficient transition metal oxides. These reactions have tacitly been assumed to be a solid phase reaction between the reductant and parent oxide. We have conducted a number of experiments with physical separation between the reductant and oxides, and find that in some cases reduction proceeds even when the reagents are physically separated, implying reactions with in-situ generated H2 and, to a lesser extent, getter mechanisms. Our findings change our understanding of these topochemical reactions, and should enhance the synthesis of additional new oxides and nanostructures.

  17. Oxygen Reduction Reaction on Platinum-Terminated “Onion-structured” Alloy Catalysts

    SciTech Connect

    Herron, Jeffrey A.; Jiao, Jiao; Hahn, Konstanze; Peng, Guowen; Adzic, Radoslav R.; Mavrikakis, Manos

    2012-12-17

    Using periodic, self-consistent density functional theory (GGA-PW91) calculations, a series of onion-structured metal alloys have been investigated for their catalytic performance towards the oxygen reduction reaction (ORR). The onion-structures consist of a varying number of atomic layers of one or two metals each, pseudomorphically deposited on top of one another to form the overall structure. All catalysts studied feature a Pt overlayer, and often consist of at least one Pd layer below the surface. Three distinct ORR mechanisms were analyzed on the close-packed facets of all the structures considered. These mechanisms include a direct route of O2 dissociation and two hydrogen-assisted routes of O–O bond-breaking in peroxyl (OOH) and in hydrogen peroxide (HOOH) intermediates. A thermochemical analysis of the elementary steps provides information on the operating potential, and thereby energy efficiency of each electrocatalyst. A Sabatier analysis of catalytic activity based on thermochemistry of proton/electron transfer steps and activation energy barrier for O–O bond-breaking steps leads to a “volcano” relation between the surfaces’ activity and the binding energy of O. Several of the onion-structured alloys studied here show promise for achieving energy efficiency higher than that of Pt, by being active at potentials higher than the operating potential of Pt. Furthermore, some have at least as good activity as pure Pt at that operating potential. Thus, a number of the onion-structured alloys studied here are promising as cathode electrocatalysts in proton exchange membrane fuel cells.

  18. Tuning oxygen reduction reaction activity via controllable dealloying: a model study of ordered Cu3Pt/C intermetallic nanocatalysts.

    PubMed

    Wang, Deli; Yu, Yingchao; Xin, Huolin L; Hovden, Robert; Ercius, Peter; Mundy, Julia A; Chen, Hao; Richard, Jonah H; Muller, David A; DiSalvo, Francis J; Abruña, Héctor D

    2012-10-10

    A promising electrocatalyst prototype of low Pt mole fraction, intermetallic nanoparticles of Cu(3)Pt, has been prepared using a simple impregnation-reduction method, followed by a post heat-treatment. Two dealloying methods (electrochemical and chemical) were implemented to control the atomic-level morphology and improve performance for the oxygen reduction reaction (ORR). The morphology and elemental composition of the dealloyed nanoparticles were characterized at angstrom resolution using an aberration-corrected scanning transmission electron microscope equipped with an electron energy loss spectrometer. We found that the electrochemical dealloying method led to the formation of a thin Pt skin of ca. 1 nm in thickness with an ordered Cu(3)Pt core structure, while chemical leaching gave rise to a "spongy" structure with no ordered structure being preserved. A three-dimensional tomographic reconstruction indicated that numerous voids were formed in the chemically dealloyed nanoparticles. Both dealloying methods yielded enhanced specific and mass activities toward the ORR and higher stability relative to Pt/C. The spongy nanoparticles exhibited better mass activity with a slightly lower specific activity than the electrochemically dealloyed nanoparticles after 50 potential cycles. In both cases, the mass activity was still enhanced after 5000 potential cycles. PMID:22954373

  19. Quasi-in-situ single-grain photoelectron microspectroscopy of Co/PPy nanocomposites under oxygen reduction reaction.

    PubMed

    Bocchetta, Patrizia; Amati, Matteo; Bozzini, Benedetto; Catalano, Massimo; Gianoncelli, Alessandra; Gregoratti, Luca; Taurino, Antonietta; Kiskinova, Maya

    2014-11-26

    This paper reports an investigation into the aging of pyrolyzed cobalt/polypyrrole (Co/PPy) oxygen reduction reaction (ORR) electrocatalysts, based on quasi-in-situ photoelectron microspectroscopy. The catalyst precursor was prepared by potentiostatic reverse-pulse coelectrodeposition from an acetonitrile solution on graphite. Accelerated aging was obtained by quasi-in-situ voltammetric cycling in an acidic electrolyte. Using photoelectron imaging and microspectroscopy of single Co/PPy grains at a resolution of 100 nm, we tracked the ORR-induced changes in the morphology and chemical state of the pristine material, consisting of uniformly distributed ∼20 nm nanoparticles, initially consisting of a mixture of Co(II) and Co(III) oxidation states in almost equal amounts. The evolution of the Co 2p, O 1s, and N 1s spectra revealed that the main effects of aging are a gradual loss of the Co present at the surface and the reduction of Co(III) to Co(II), accompanied by the emergence and growth of a N 1s signal, corresponding to electrocatalytically active C-N sites. PMID:25369153

  20. Composition effects of spinel MnxCo3-xO4 nanoparticles on their electrocatalytic properties in oxygen reduction reaction in alkaline media

    NASA Astrophysics Data System (ADS)

    Lee, Eunjik; Jang, Ji-Hoon; Kwon, Young-Uk

    2015-01-01

    In this work, we synthesized a series of manganese cobalt spinel oxide (MnxCo3-xO4) nanoparticles (NPs) covering the whole composition range (x = 0.0. 0.4, 0.8, 1.4, 1.9, and 3.0) and investigated their electrocatalytic properties in relation with the oxygen reduction reaction (ORR) in alkaline media. The NP samples were synthesized by sonochemical reactions of Mn(OAc)2 and Co(OAc)2 (Ac = acetyl) in a water-dimethylformamide mixed solvent. The four samples in the Co-rich side have the cubic structure whereas the other two samples in the Mn-rich side have the tetragonal structure. The X-ray photoelectron spectroscopy and electrochemical analyses data indicate that the distribution of manganese and cobalt ions between the two metal ion sites of the spinel structure in our NP samples conforms to that of the bulk counterparts in the literature. The electrocatalytic data show that the ORR mechanism is changed when the structure is changed from cubic to tetragonal. The highest ORR activity was observed with the x = 0.4 sample. The electrochemical stability of this sample is higher than that of commercial Pt/C.

  1. Mesoporous TiN as a noncarbon support of Ag-rich PtAg nanoalloy catalysts for oxygen reduction reaction in alkaline media.

    PubMed

    Cui, Zhiming; Yang, Minghui; Chen, Hao; Zhao, Mengtian; DiSalvo, Francis J

    2014-12-01

    There has been growing interest in noncarbon supports for fuel cell reactions, especially for the oxygen reduction reaction (ORR) in alkaline media. Herein, we report a robust mesoporous titanium nitride (TiN) which is not only kinetically stable in alkaline media, but also electrochemically stable in the potential range of fuel cell operation. This binary nitride exhibits an order of magnitude higher electronic conductivity than carbon black. Bimetallic Ag-rich PtAg nanoalloy is selected as the catalyst for the ORR in alkaline media due to their superior activity and relatively low cost. TiN-supported Pt1 Ag9 nanoalloy catalysts are synthesized by a new and efficient approach with KEt3 BH as reducing agent and THF as solvent. Pt1 Ag9 /TiN exhibits much higher mass activity and durability for the ORR in alkaline media than Pt1 Ag9 /C, Pt/C and Ag/C catalysts, suggesting that mesoporous TiN is a very promising support in alkaline media. PMID:25320003

  2. Interaction Induced High Catalytic Activities of CoO Nanoparticles Grown on Nitrogen-Doped Hollow Graphene Microspheres for Oxygen Reduction and Evolution Reactions

    NASA Astrophysics Data System (ADS)

    Jiang, Zhong-Jie; Jiang, Zhongqing

    2016-06-01

    Nitrogen doped graphene hollow microspheres (NGHSs) have been used as the supports for the growth of the CoO nanoparticles. The nitrogen doped structure favors the nucleation and growth of the CoO nanoparticles and the CoO nanoparticles are mostly anchored on the quaternary nitrogen doped sites of the NGHSs with good monodispersity since the higher electron density of the quaternary nitrogen favors the nucleation and growth of the CoO nanoparticles through its coordination and electrostatic interactions with the Co2+ ions. The resulting NGHSs supported CoO nanoparticles (CoO/NGHSs) are highly active for the oxygen reduction reaction (ORR) with activity and stability higher than the Pt/C and for the oxygen evolution reaction (OER) with activity and stability comparable to the most efficient catalysts reported to date. This indicates that the CoO/NGHSs could be used as efficient bi-functional catalysts for ORR and OER. Systematic analysis shows that the superior catalytic activities of the CoO/NGHSs for ORR and OER mainly originate from the nitrogen doped structure of the NGHSs, the small size of the CoO nanoparticles, the higher specific and electroactive surface area of the CoO/NGHSs, the good electric conductivity of the CoO/NGHSs, the strong interaction between the CoO nanoparticles and the NGHSs, etc.

  3. Interaction Induced High Catalytic Activities of CoO Nanoparticles Grown on Nitrogen-Doped Hollow Graphene Microspheres for Oxygen Reduction and Evolution Reactions

    PubMed Central

    Jiang, Zhong-Jie; Jiang, Zhongqing

    2016-01-01

    Nitrogen doped graphene hollow microspheres (NGHSs) have been used as the supports for the growth of the CoO nanoparticles. The nitrogen doped structure favors the nucleation and growth of the CoO nanoparticles and the CoO nanoparticles are mostly anchored on the quaternary nitrogen doped sites of the NGHSs with good monodispersity since the higher electron density of the quaternary nitrogen favors the nucleation and growth of the CoO nanoparticles through its coordination and electrostatic interactions with the Co2+ ions. The resulting NGHSs supported CoO nanoparticles (CoO/NGHSs) are highly active for the oxygen reduction reaction (ORR) with activity and stability higher than the Pt/C and for the oxygen evolution reaction (OER) with activity and stability comparable to the most efficient catalysts reported to date. This indicates that the CoO/NGHSs could be used as efficient bi-functional catalysts for ORR and OER. Systematic analysis shows that the superior catalytic activities of the CoO/NGHSs for ORR and OER mainly originate from the nitrogen doped structure of the NGHSs, the small size of the CoO nanoparticles, the higher specific and electroactive surface area of the CoO/NGHSs, the good electric conductivity of the CoO/NGHSs, the strong interaction between the CoO nanoparticles and the NGHSs, etc. PMID:27255562

  4. Nitrogen- and boron-co-doped core-shell carbon nanoparticles as efficient metal-free catalysts for oxygen reduction reactions in microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Zhong, Shengkui; Zhou, Lihua; Wu, Ling; Tang, Lianfeng; He, Qiyi; Ahmed, Jalal

    2014-12-01

    The most severe bottleneck hindering the widespread application of fuel cell technologies is the difficulty in obtaining an inexpensive and abundant oxygen reduction reaction (ORR) catalyst. The concept of a heteroatom-doped carbon-based metal-free catalyst has recently attracted interest. In this study, a metal-free carbon nanoparticles-based catalyst hybridized with dual nitrogen and boron components was synthesized to catalyze the ORR in microbial fuel cells (MFCs). Multiple physical and chemical characterizations confirmed that the synthetic method enabled the incorporation of both nitrogen and boron dopants. The electrochemical measurements indicated that the co-existence of nitrogen and boron could enhance the ORR kinetics by reducing the overpotential and increasing the current density. The results from the kinetic studies indicated that the nitrogen and boron induced an oxygen adsorption mechanism and a four-electron-dominated reaction pathway for the as-prepared catalyst that was very similar to those induced by Pt/C. The MFC results showed that a maximum power density of ∼642 mW m-2 was obtained using the as-prepared catalyst, which is comparable to that obtained using expensive Pt catalyst. The prepared nitrogen- and boron-co-doped carbon nanoparticles might be an alternative cathode catalyst for MFC applications if large-scale applications and price are considered.

  5. Interaction Induced High Catalytic Activities of CoO Nanoparticles Grown on Nitrogen-Doped Hollow Graphene Microspheres for Oxygen Reduction and Evolution Reactions.

    PubMed

    Jiang, Zhong-Jie; Jiang, Zhongqing

    2016-01-01

    Nitrogen doped graphene hollow microspheres (NGHSs) have been used as the supports for the growth of the CoO nanoparticles. The nitrogen doped structure favors the nucleation and growth of the CoO nanoparticles and the CoO nanoparticles are mostly anchored on the quaternary nitrogen doped sites of the NGHSs with good monodispersity since the higher electron density of the quaternary nitrogen favors the nucleation and growth of the CoO nanoparticles through its coordination and electrostatic interactions with the Co(2+) ions. The resulting NGHSs supported CoO nanoparticles (CoO/NGHSs) are highly active for the oxygen reduction reaction (ORR) with activity and stability higher than the Pt/C and for the oxygen evolution reaction (OER) with activity and stability comparable to the most efficient catalysts reported to date. This indicates that the CoO/NGHSs could be used as efficient bi-functional catalysts for ORR and OER. Systematic analysis shows that the superior catalytic activities of the CoO/NGHSs for ORR and OER mainly originate from the nitrogen doped structure of the NGHSs, the small size of the CoO nanoparticles, the higher specific and electroactive surface area of the CoO/NGHSs, the good electric conductivity of the CoO/NGHSs, the strong interaction between the CoO nanoparticles and the NGHSs, etc. PMID:27255562

  6. Template-free synthesis of hierarchical yolk-shell Co and N codoped porous carbon microspheres with enhanced performance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Chao, Shujun; Cui, Qian; Wang, Kui; Bai, Zhengyu; Yang, Lin; Qiao, Jinli

    2015-08-01

    The structures and compositions of materials have important influences on their performance. Herein, hierarchically structured yolk-shell Co and N codoped porous carbon microspheres (YS-Co/N-PCMs) have been successfully synthesized by using low-cost melamine, formaldehyde and cobalt acetate as raw materials via a facile template-free hydrothermal method and a subsequent pyrolysis. The formation process of the yolk-shell precursor is systematically investigated, involving a morphological evolution process from solid microspheres, ultrathin and wrinkled shells wrap, to yolk-shell structure formation. More importantly, the unique structure combines the favorable features towards oxygen reduction reaction (ORR), such as high surface area, sufficient Co-Nx and graphitic N active sites and suitable pore structures. As a result, the YS-Co/N-PCMs catalyst shows high catalytic activity for ORR in alkaline media for fuel cells, which not only outperforms commercial Pt-based catalysts in terms of resistance to methanol crossover and long-time stability, but is also better than many non-precious metal doped carbon-based catalysts reported previously. In addition, the YS-Co/N-PCMs catalyst also has high catalytic activity toward oxygen evolution reaction (OER). Therefore, the YS-Co/N-PCMs catalyst may serve as a promising alternative to Pt/C catalyst for ORR and OER in alkaline media.

  7. Covalent entrapment of cobalt-iron sulfides in N-doped mesoporous carbon: extraordinary bifunctional electrocatalysts for oxygen reduction and evolution reactions.

    PubMed

    Shen, Mengxia; Ruan, Changping; Chen, Yan; Jiang, Chunhuan; Ai, Kelong; Lu, Lehui

    2015-01-21

    To alleviate the kinetic barriers associated with ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) in electrochemical systems, efficient nonprecious electrocatalysts are urgently required. Here we report a facile soft-template mediated approach for fabrication of nanostructured cobalt-iron double sulfides that are covalently entrapped in nitrogen-doped mesoporous graphitic carbon (Co0.5Fe0.5S@N-MC). Notably, with a positive half-wave potential (0.808 V) and a high diffusion-limiting current density, the composite material delivers unprecedentedly striking ORR electrocatalytic activity among recently reported nonprecious late transition metal chalcogenide materials in alkaline medium. Various characterization techniques, including X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction, are conducted to elucidate the correlation between structural features and catalytic activities of the composite. Moderate substitution and well-dispersion of iron in bimetallic sulfide composites are believed to have positive effect on the adsorption and activation of oxygen-containing species, thus leading to conspicuous ORR and OER catalytic enhancement compared to their monometallic counterparts. Besides, the covalent bridge between active sulfide particles and mesoporous carbon shells provides facile pathways for electron and mass transport. Beneficially, the intimate coupling interaction renders prolonged electrocatalytic performances to the composite. Our results may possibly lend a new impetus to the rational design of bi- or multimetallic sulfides encapsulated in porous carbon with improved performance for electrocatalysis and energy storage applications. PMID:25531776

  8. Synthesis of an efficient heteroatom-doped carbon electro-catalyst for oxygen reduction reaction by pyrolysis of protein-rich pulse flour cooked with SiO2 nanoparticles.

    PubMed

    Gokhale, Rohan; Unni, Sreekuttan M; Puthusseri, Dhanya; Kurungot, Sreekumar; Ogale, Satishchandra

    2014-03-01

    Development of a highly durable, fuel-tolerant, metal-free electro-catalyst for oxygen reduction reaction (ORR) is essential for robust and cost-effective Anion Exchange Membrane Fuel Cells (AEMFCs). Herein, we report the development of a nitrogen-doped (N-doped) hierarchically porous carbon-based efficient ORR electrocatalyst from protein-rich pulses. The process involves 3D silica nanoparticle templating of the pulse flour(s) followed by their double pyrolysis. The detailed experiments are performed on gram flour (derived from chickpeas) without any in situ/ex situ addition of dopants. The N-doped porous carbon thus generated shows remarkable electrocatalytic activity towards ORR in the alkaline medium. The oxygen reduction on this material follows the desired 4-electron transfer mechanism involving the direct reduction pathway. Additionally, the synthesized carbon catalyst also exhibits good electrochemical stability and fuel tolerance. The results are also obtained and compared with the case of soybean flour having higher nitrogen content to highlight the significance of different parameters in the ORR catalyst performance. PMID:24452060

  9. N,N‧-Bis(salicylidene)ethylenediamine as a nitrogen-rich precursor to synthesize electrocatalysts with high methanol-tolerance for polymer electrolyte membrane fuel cell oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhou, Xuejun; Xu, Pan; Xu, Li; Bai, Zhengyu; Chen, Zhongwei; Qiao, Jinli; Zhang, Jiujun

    2014-08-01

    A cost-effective chemical, N,N‧-bis(salicylidene)ethylenediamine (salen), is used as a ligand to form a carbon-supported Co-salen complex (Co-salen/C) by a simple solid-sate reaction. The Co-salen/C is then pyrolyzed at 600, 700, 800, 900, and 1000 °C to form carbon-supported Co-N-S/C catalysts for the oxygen reduction reaction (ORR). XRD, EDX, TEM, and XPS are used to characterize the catalysts' composition, crystalline nature, morphology, and possible surface groups induced by heat-treatment. Investigation of the catalytic activity and the ORR mechanisms using rotating disk electrode and rotating ring-disk electrode techniques demonstrates that all of these Co-N-S/C catalysts are highly active for the ORR in an O2-saturated 0.1 M KOH solution, but the catalyst heat treated at 700 °C gives the best ORR activity. The overall electron transfer number for the catalyzed ORR was determined to be 3.6-3.9, with 3.7-19.9% H2O2 production over the potential range of -0.05 to -0.60 V, suggesting that the ORR catalyzed by Co-N-S/C catalysts is dominated by a 4-electron transfer pathway from O2 to H2O. In addition, these catalysts exhibit superior methanol tolerance to commercial 40% Pt/C catalyst, thus the Co-N-S/C catalysts are promising for use as electrocatalysts in alkaline polymer electrolyte membrane fuel cells.

  10. Cobalt sulfide/N,S codoped porous carbon core-shell nanocomposites as superior bifunctional electrocatalysts for oxygen reduction and evolution reactions

    NASA Astrophysics Data System (ADS)

    Chen, Binling; Li, Rong; Ma, Guiping; Gou, Xinglong; Zhu, Yanqiu; Xia, Yongde

    2015-12-01

    Exploring highly-efficient and low-cost bifunctional electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reactions (OER) in the renewable energy area has gained momentum but still remains a significant challenge. Here we present a simple but efficient method that utilizes ZIF-67 as the precursor and template for the one-step generation of homogeneous dispersed cobalt sulfide/N,S-codoped porous carbon nanocomposites as high-performance electrocatalysts. Due to the favourable molecular-like structural features and uniform dispersed active sites in the precursor, the resulting nanocomposites, possessing a unique core-shell structure, high porosity, homogeneous dispersion of active components together with N and S-doping effects, not only show excellent electrocatalytic activity towards ORR with the high onset potential (around -0.04 V vs. -0.02 V for the benchmark Pt/C catalyst) and four-electron pathway and OER with a small overpotential of 0.47 V for 10 mA cm-2 current density, but also exhibit superior stability (92%) to the commercial Pt/C catalyst (74%) in ORR and promising OER stability (80%) with good methanol tolerance. Our findings suggest that the transition metal sulfide-porous carbon nanocomposites derived from the one-step simultaneous sulfurization and carbonization of zeolitic imidazolate frameworks are excellent alternative bifunctional electrocatalysts towards ORR and OER in the next generation of energy storage and conversion technologies.Exploring highly-efficient and low-cost bifunctional electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reactions (OER) in the renewable energy area has gained momentum but still remains a significant challenge. Here we present a simple but efficient method that utilizes ZIF-67 as the precursor and template for the one-step generation of homogeneous dispersed cobalt sulfide/N,S-codoped porous carbon nanocomposites as high-performance electrocatalysts. Due to the

  11. PdCu Nanoalloy Electrocatalysts in Oxygen Reduction Reaction: Role of Composition and Phase State in Catalytic Synergy.

    PubMed

    Wu, Jinfang; Shan, Shiyao; Luo, Jin; Joseph, Pharrah; Petkov, Valeri; Zhong, Chuan-Jian

    2015-11-25

    The catalytic synergy of nanoalloy catalysts depends on the nanoscale size, composition, phase state, and surface properties. This report describes findings of an investigation of their roles in the enhancement of electrocatalytic activity of PdCu alloy nanoparticle catalysts for oxygen reduction reaction (ORR). Pd(n)Cu(100-n) nanoalloys with controlled composition and subtle differences in size and phase state were synthesized by two different wet chemical methods. Detailed electrochemical characterization was performed to determine the surface properties and the catalytic activities. The atomic-scale structures of these catalysts were also characterized by high-energy synchrotron X-ray diffraction coupled with atomic pair distribution function analysis. The electrocatalytic activity and stability were shown to depend on the size, composition, and phase structure. With Pd(n)Cu(100-n) catalysts from both methods, a maximum ORR activity was revealed at Pd/Cu ratio close to 50:50. Structurally, Pd50Cu50 nanoalloys feature a mixed phase consisting of chemically ordered (body-centered cubic type) and disordered (face-centered cubic type) domains. The phase-segregated structure is shown to change to a single phase upon electrochemical potential cycling in ORR condition. While the surface Cu dissolution occurred in PdCu catalysts from the two different synthesis methods, the PdCu with a single-phase character is found to exhibit a tendency of a much greater dissolution than that with the phase segregation. Analysis of the results, along theoretical modeling based on density functional theory calculation, has provided new insights for the correlation between the electrocatalytic activity and the catalyst structures. PMID:26569372

  12. Synthesis and Characterization of Bimetallic Core-Shell-Supported Platinum Monolayer Electrocatalysts for the Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Kuttiyiel, Kurian Abraham

    Fuel cells are expected to be one of the major clean energy sources in the near future. However, the slow kinetics of electrocatalytic oxygen reduction reaction (ORR) and the high loading of Platinum (Pt) for the cathode material are the urgent issues to be addressed since they determine the efficiency and the cost of this energy source. In this study, a new approach was developed for designing electrocatalysts for the ORR in fuel cells. These electrocatalysts consist of only one Pt monolayer on suitable carbon-supported Iridium-Nickel (IrNi) core-shell nanoparticles. The synthesis involved depositing a monolayer of Copper (Cu) on IrNi metal alloy surface at under-potentials, followed by galvanic displacement of the Cu monolayer with Pt. It was found that the electronic properties of Pt monolayer could be fine-tuned by the electronic and geometric effects introduced by the substrate metal. The Pt mass activity of the new Pt monolayer IrNi electrocatalysts was up to six times higher than the state-of-the-art commercial Pt/C catalysts. The structure and composition of the core-shell nanoparticles were verified using transmission electron microscopy and in situ X-ray absorption spectroscopy, while potential cycling test was employed to confirm the stability of the electrocatalyst. The formation of Ir shell on IrNi alloy during annealing due to thermal segregation was monitored by time-resolved synchrotron XRD measurements. Our experimental results, supported by computations, demonstrated an effective way of using Pt that can resolve key ORR problems which include inadequate activity and durability while minimizing the Pt loading.

  13. Shewanella-mediated biosynthesis of manganese oxide micro-/nanocubes as efficient electrocatalysts for the oxygen reduction reaction.

    PubMed

    Jiang, Congcong; Guo, Zhaoyan; Zhu, Ying; Liu, Huan; Wan, Meixiang; Jiang, Lei

    2015-01-01

    Developing efficient electrocatalysts for the oxygen reduction reaction (ORR) is critical for promoting the widespread application of fuel cells and metal-air batteries. Here, we develop a biological low-cost, ecofriendly method for the synthesis of Mn2 O3 micro-/nanocubes by calcination of MnCO3 precursors in an oxygen atmosphere. Microcubic MnCO3 precursors with an edge length of 2.5 μm were fabricated by dissimilatory metal-reducing Shewanella loihica PV-4 in the presence of MnO4 (-) as the sole electron acceptor under anaerobic conditions. After calcining the MnCO3 precursors at 500 and 700 °C, porous Mn2 O3 -500 and Mn2 O3 -700 also showed microcubic morphology, while their edge lengths decreased to 1.8 μm due to thermal decomposition. Moreover, the surfaces of the Mn2 O3 microcubes were covered by granular nanoparticles with average diameters in the range of 18-202 nm, depending on the calcination temperatures. Electrochemical measurements demonstrated that the porous Mn2 O3 -500 micro-/nanocubes exhibit promising catalytic activity towards the ORR in an alkaline medium, which should be due to a synergistic effect of the overlapping molecular orbitals of oxygen/manganese and the hierarchically porous structures that are favorable for oxygen absorption. Moreover, these Mn2 O3 micro-/nanocubes possess better stability than commercial Pt/C catalysts and methanol-tolerance property in alkaline solution. Thus the Shewanella-mediated biosynthesis method we provided here might be a new strategy for the preparation of various transition metal oxides as high-performance ORR electrocatalysts at low cost. PMID:25425435

  14. NiCo2O4/N-doped graphene as an advanced electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Li, Huiyong; Wang, Haiyan; He, Kejian; Wang, Shuangyin; Tang, Yougen; Chen, Jiajie

    2015-04-01

    Developing low-cost catalyst for high-performance oxygen reduction reaction (ORR) is highly desirable. Herein, NiCo2O4/N-doped reduced graphene oxide (NiCo2O4/N-rGO) hybrid is proposed as a high-performance catalyst for ORR for the first time. The well-formed NiCo2O4/N-rGO hybrid is studied by cyclic voltammetry (CV) curves and linear-sweep voltammetry (LSV) performed on the rotating-ring-disk-electrode (RDE) in comparison with N-rGO-free NiCo2O4 and the bare N-rGO. Due to the synergistic effect, the NiCo2O4/N-rGO hybrid exhibits significant improvement of catalytic performance with an onset potential of -0.12 V, which mainly favors a direct four electron pathway in ORR process, close to the behavior of commercial carbon-supported Pt. Also, the benefits of N-incorporation are investigated by comparing NiCo2O4/N-rGO with NiCo2O4/rGO, where higher cathodic currents, much more positive half-wave potential and more electron transfer numbers are observed for the N-doping one, which should be ascribed to the new highly efficient active sites created by N incorporation into graphene. The NiCo2O4/N-rGO hybrid could be used as a promising catalyst for high power metal/air battery.

  15. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun; Liu, Baocang; Gong, Xia; Zheng, Dafang; Zhang, Jun; Wang, Qin

    2016-12-01

    The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg-1) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  16. New mechanistic insight into the oxygen reduction reaction on Ruddlesden–Popper cathodes for intermediate-temperature solid oxide fuel cells

    SciTech Connect

    Li, Wenyuan; Guan, Bo; Zhang, Xinxin; Yan, Jianhua; Zhou, Yue; Liu, Xingbo

    2016-01-01

    Ruddlesden–Popper (R–P) phase materials have been investigated widely as cathode candidates for IT-SOFCs. However, widespread application of R–P phase cathodes demands further improvement in electrode activity whose progress is hindered by the limited information in the oxygen reduction reaction (ORR). The ORR mechanism for the R–P phase is therefore investigated in this paper using (LaSr)2NiO4#2;d as an example. Accurate characterization of the surface oxygen exchange process is realized by developing thin and dense polycrystalline LSNO layers via a versatile spray-modified pressing method we invented before to avoid perceptible bulk diffusion contribution, surface enrichment and geometry complication. The governing factors of the ORR are identified as oxygen adsorption and incorporation based on the findings in reaction orders from electrochemical impedance spectroscopy (EIS), stoichiometryrelated chemical capacitance and intrinsic anisotropic properties. The incorporation rate is proven to drastically depend on the amount of interstitial oxygen O00 i #2;#3;. Since the unfilled interstitial sites V#3; i #2;#3; in the R–P phase serve to accommodate the adsorbed oxygen during incorporation, like vacancies in the perovskite structure V#4;#4; O #2;#3;, moreO00 i would seem to suppress the kinetics of this process. In regards to this, for the first time, a physical model is proposed to reconcile the discrepancy between the experimental results and intuitive reasoning. Based on supporting evidence, this model illustrates a possibility of how O00 i works to regulate the exchange rate, and how the contradiction between V#4;#4; O and O00 i is harmonized so that the latter in the R–P structure also positively promotes the incorporation rate in the ORR

  17. Rapid Synthesis and Efficient Electrocatalytic Oxygen Reduction/Evolution Reaction of CoMn2O4 Nanodots Supported on Graphene.

    PubMed

    Du, Jing; Chen, Chengcheng; Cheng, Fangyi; Chen, Jun

    2015-06-01

    Transition-metal oxides have attracted extensive interest as oxygen-reduction/evolution reaction (ORR/OER) catalyst alternatives to precious Pt-based materials but generally exhibit limited electrocatalytic performance due to their large overpotential and low specific activity. We here report a rapid synthesis of spinel-type CoMn2O4 nanodots (NDs, below 3 nm) monodispersed on graphene for highly efficient electrocatalytic ORR/OER in 0.1 M KOH solution. The preparation of the composite involves the reaction of manganese and cobalt salts in mixed surfactant-solvent-water solution at mild temperature (120 °C) and air. CoMn2O4 NDs homogeneously distributed on carbonaceous substrates show strong coupling and facile charge transfer. Remarkably, graphene-supported CoMn2O4 NDs showed 20 mV higher ORR half-wave potential, twice the kinetic current, and better catalytic durability compared to the benchmark carbon-supported Pt nanoparticles (Pt/C). Moreover, CoMn2O4/reduced graphene oxide afforded electrocatalytic OER with a current density of 10 mA cm(-2) at a low potential of 1.54 V and a small Tafel slope of ∼56 mV/dec. This indicates that the composite of CoMn2O4 nanodots monodispersed on graphene is promising as highly efficient bifunctional electrocatalysts of ORR and OER that can be used in the areas of fuel cells and rechargeable metal-air batteries. PMID:25989252

  18. Core-shell Co@Co3O4 nanoparticle-embedded bamboo-like nitrogen-doped carbon nanotubes (BNCNTs) as a highly active electrocatalyst for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Xiao, Junwu; Chen, Chen; Xi, Jiangbo; Xu, Yangyang; Xiao, Fei; Wang, Shuai; Yang, Shihe

    2015-04-01

    The current bottleneck for fuel cells and metal-air batteries lies in the sluggish oxygen reduction reaction (ORR) on the cathode side. Despite tremendous efforts, to develop a highly efficient ORR catalyst at low cost remains a great challenge. Herein, we have synthesized core-shell Co@Co3O4 nanoparticles embedded in the bamboo-like N-doped carbon tubes (BNCNTs) by a simple approach comprising thermal treatment of cobalt carbonate hydroxide and urea and oxidization. The ORR catalytic activities of the Co@Co3O4/BNCNT composites are closely dependent on the oxidization degree of the Co nanoparticles and the N content in the BNCNTs. When oxidized at 300 °C, the as-formed Co@Co3O4/BNCNTs-300 composite catalyst with an N/C molar ratio of ~1.6% achieves the maximum ORR catalytic activity. The composite catalyst also exhibits a higher ORR catalytic activity than the Co3O4/carbon nanotube (CNT) catalyst. The tolerance for methanol molecules and the cycle stability performance of the composite catalyst are even superior to those of the highly efficient Pt/C catalyst. Such an excellent ORR catalytic activity can be ascribed to (1) the core-shell Co@Co3O4 nanoparticles embedded in BNCNTs, (2) the N-doping in BNCNTs, and (3) the synergetic effect of (1) and (2) on Co3O4 firmly attached to both Co nanoparticles and BNCNTs, resulting in accelerated electron transport and enhanced charge delocalization.The current bottleneck for fuel cells and metal-air batteries lies in the sluggish oxygen reduction reaction (ORR) on the cathode side. Despite tremendous efforts, to develop a highly efficient ORR catalyst at low cost remains a great challenge. Herein, we have synthesized core-shell Co@Co3O4 nanoparticles embedded in the bamboo-like N-doped carbon tubes (BNCNTs) by a simple approach comprising thermal treatment of cobalt carbonate hydroxide and urea and oxidization. The ORR catalytic activities of the Co@Co3O4/BNCNT composites are closely dependent on the oxidization degree of

  19. Strontium-doped samarium manganite as cathode materials for oxygen reduction reaction in solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Li, W.; Xiong, C. Y.; Jia, L. C.; Pu, J.; Chi, B.; Chen, X.; Schwank, J. W.; Li, J.

    2015-06-01

    SmxSr1-xMnO3 with x = 0.3, 0.5 and 0.8, denoted as SSM37, SSM55 and SSM82, respectively, have been prepared via a sol-gel route as materials for cathodes in solid oxide fuel cells. Their activities in the oxygen reduction reaction (ORR) have been evaluated in comparison with the state-of-the-art cathode material La0.8Sr0.2MnO3 (LSM82) by electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and thermogravimetry (TG). Among all the prepared cathodes, the SSM55 exhibits the lowest values, while the LSM82 exhibits the highest polarization resistance, at open circuit voltage (OCV) and temperatures from 650 to 800 °C. This result indicates that the prepared SmxSr1-xMnO3 is a promising replacement for LSM82 as cathode material for SOFCs, and the SSM55 represents the optimal concentration in SmxSr1-xMnO3 series. The remarkably high ORR activity of the SSM55 is ascribed to its high surface Mn4+/Mn3+ and Oad/Olattice ratios and fast surface oxygen exchange kinetics.

  20. Electrospun interconnected Fe-N/C nanofiber networks as efficient electrocatalysts for oxygen reduction reaction in acidic media.

    PubMed

    Wu, Nan; Wang, Yingde; Lei, Yongpeng; Wang, Bing; Han, Cheng; Gou, Yanzi; Shi, Qi; Fang, Dong

    2015-01-01

    One-dimensional electrospun nanofibers have emerged as a potential candidate for high-performance oxygen reduction reaction (ORR) catalysts. However, contact resistance among the neighbouring nanofibers hinders the electron transport. Here, we report the preparation of interconnected Fe-N/C nanofiber networks (Fe-N/C NNs) with low electrical resistance via electrospinning followed by maturing and pyrolysis. The Fe-N/C NNs show excellent ORR activity with onset and half-wave potential of 55 and 108 mV less than those of Pt/C catalyst in 0.5 M H2SO4. Intriguingly, the resulting Fe-N/C NNs exhibit 34% higher peak current density and superior durability than generic Fe-N/C ones with similar microstructure and chemical compositions. Additionally, it also displays much better durability and methanol tolerance than Pt/C catalyst. The higher electroactivity is mainly due to the more effective electron transport between the interconnected nanofibers. Thus, our findings provide a novel insight into the design of functional electrospun nanofibers for the application in energy storage and conversion fields. PMID:26615799

  1. Synergistic enhancement of nitrogen and sulfur co-doped graphene with carbon nanospheres insertion for electrocatalytic oxygen reduction reaction

    DOE PAGESBeta

    Wu, Min; Xin, Huolin L.; Wang, Jie; Wu, Zexing; Wang, Deli

    2015-03-13

    A nitrogen and sulfur co-doped graphene/carbon black (NSGCB) nanocomposite for the oxygen reduction reaction (ORR) was synthesized through a one-pot annealing of a precursor mixture containing graphene oxide, thiourea, and acidized carbon black (CB). The NSGCB showed excellent performance for the ORR with the onset and half-way potentials at 0.96 V and 0.81 V (vs. RHE), respectively. It is significantly improved over that of the catalysts derived from only graphene (0.90 V and 0.76 V) or carbon nanosphere (0.82 V and 0.74 V). The enhanced catalytic activity on the NSGCB electrode could be attributed to the synergistic effect of N/Smore » co-doping and the enlarged interlayer space resulted from the insertion of carbon nanosphere into the graphene sheets. The four-electron selectivity and the limiting current density of the NSGCB nanocomposite are comparable to that of the commercially Pt/C catalyst. Furthermore, the NSGCB nanocomposite was superior to Pt/C in terms of long-term durability and tolerance to methanol poisoning.« less

  2. Investigation of the electrocatalysis for oxygen reduction reaction by Pt and binary Pt alloys: an XRD, XAS and electrochemical study

    SciTech Connect

    Mukerjee, S.; McBreen, J.; Srinivasan, S.

    1995-12-31

    Electrocatalysis for the oxygen reduction reaction (ORR) on five binary Pt alloy electrocatalysts (PtCr/C, PtMn/C, PtFe/C, PtCo/C and PtNi/C) supported on carbon have been investigated. The electrochemical characteristics for ORR in a proton conducting fuel cell environment has been correlated with the electronic and structural parameters determined under in situ conditions using XANES and EXAFS technique respectively. Results indicate that all the alloys possess higher Pt 5d band vacancies as compared to Pt/C. There is also evidence of lattice contraction in the alloys (supported by XRD results). Further, the Pt/C shows increase in Pt 5 d band vacancies during potential transitions from 0.54 to 0.84 V vs. RHE, which has been ration@ on the basis of OH type adsorption. In contrast to this, the alloys do not exhibit such an enhancement. Detailed EXAFS analysis supports the presence of OH species on Pt/C and its relative absence in the alloys. Correlation of the electrochemical results with bond distances and d-band vacancies show a volcano type behavior with the PtCr/C on top of the curve.

  3. Electrospun interconnected Fe-N/C nanofiber networks as efficient electrocatalysts for oxygen reduction reaction in acidic media

    PubMed Central

    Wu, Nan; Wang, Yingde; Lei, Yongpeng; Wang, Bing; Han, Cheng; Gou, Yanzi; Shi, Qi; Fang, Dong

    2015-01-01

    One-dimensional electrospun nanofibers have emerged as a potential candidate for high-performance oxygen reduction reaction (ORR) catalysts. However, contact resistance among the neighbouring nanofibers hinders the electron transport. Here, we report the preparation of interconnected Fe-N/C nanofiber networks (Fe-N/C NNs) with low electrical resistance via electrospinning followed by maturing and pyrolysis. The Fe-N/C NNs show excellent ORR activity with onset and half-wave potential of 55 and 108 mV less than those of Pt/C catalyst in 0.5 M H2SO4. Intriguingly, the resulting Fe-N/C NNs exhibit 34% higher peak current density and superior durability than generic Fe-N/C ones with similar microstructure and chemical compositions. Additionally, it also displays much better durability and methanol tolerance than Pt/C catalyst. The higher electroactivity is mainly due to the more effective electron transport between the interconnected nanofibers. Thus, our findings provide a novel insight into the design of functional electrospun nanofibers for the application in energy storage and conversion fields. PMID:26615799

  4. Synergistic enhancement of nitrogen and sulfur co-doped graphene with carbon nanospheres insertion for electrocatalytic oxygen reduction reaction

    SciTech Connect

    Wu, Min; Xin, Huolin L.; Wang, Jie; Wu, Zexing; Wang, Deli

    2015-03-13

    A nitrogen and sulfur co-doped graphene/carbon black (NSGCB) nanocomposite for the oxygen reduction reaction (ORR) was synthesized through a one-pot annealing of a precursor mixture containing graphene oxide, thiourea, and acidized carbon black (CB). The NSGCB showed excellent performance for the ORR with the onset and half-way potentials at 0.96 V and 0.81 V (vs. RHE), respectively. It is significantly improved over that of the catalysts derived from only graphene (0.90 V and 0.76 V) or carbon nanosphere (0.82 V and 0.74 V). The enhanced catalytic activity on the NSGCB electrode could be attributed to the synergistic effect of N/S co-doping and the enlarged interlayer space resulted from the insertion of carbon nanosphere into the graphene sheets. The four-electron selectivity and the limiting current density of the NSGCB nanocomposite are comparable to that of the commercially Pt/C catalyst. Furthermore, the NSGCB nanocomposite was superior to Pt/C in terms of long-term durability and tolerance to methanol poisoning.

  5. Electrospun interconnected Fe-N/C nanofiber networks as efficient electrocatalysts for oxygen reduction reaction in acidic media

    NASA Astrophysics Data System (ADS)

    Wu, Nan; Wang, Yingde; Lei, Yongpeng; Wang, Bing; Han, Cheng; Gou, Yanzi; Shi, Qi; Fang, Dong

    2015-11-01

    One-dimensional electrospun nanofibers have emerged as a potential candidate for high-performance oxygen reduction reaction (ORR) catalysts. However, contact resistance among the neighbouring nanofibers hinders the electron transport. Here, we report the preparation of interconnected Fe-N/C nanofiber networks (Fe-N/C NNs) with low electrical resistance via electrospinning followed by maturing and pyrolysis. The Fe-N/C NNs show excellent ORR activity with onset and half-wave potential of 55 and 108 mV less than those of Pt/C catalyst in 0.5 M H2SO4. Intriguingly, the resulting Fe-N/C NNs exhibit 34% higher peak current density and superior durability than generic Fe-N/C ones with similar microstructure and chemical compositions. Additionally, it also displays much better durability and methanol tolerance than Pt/C catalyst. The higher electroactivity is mainly due to the more effective electron transport between the interconnected nanofibers. Thus, our findings provide a novel insight into the design of functional electrospun nanofibers for the application in energy storage and conversion fields.

  6. Preparation and electrochemical properties of urchin-like La0.8Sr0.2MnO3 perovskite oxide as a bifunctional catalyst for oxygen reduction and oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Jin, Chao; Cao, Xuecheng; Zhang, Liya; Zhang, Cong; Yang, Ruizhi

    2013-11-01

    An urchin-like La0.8Sr0.2MnO3 (LSM) perovskite oxide has been synthesized through a co-precipitation method with urea as a precipitator, and characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET analysis. SEM results show that a micro/nanocomposite with an urchin-like morphology has been obtained. The as-synthesized LSM perovskite oxide has a high specific surface area of 48 m2 g-1. The catalytic activity of the oxide for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in 0.1 M KOH solution has been studied by using a rotating-ring-disk electrode (RRDE). In the ORR test, a maximum cathodic current density of 5.2 mA cm-2 at -1.0 V (vs. Ag/AgCl) with 2500 rpm was obtained, and the ORR mainly favors a direct four-electron pathway. The results of anodic linear scanning voltammograms indicate that the urchin-like LSM perovskite oxide exhibits an encouraging catalytic activity for the OER. All electrochemical measurements suggest that the urchin-like LSM perovskite oxide could be used as a bifunctional catalyst for the ORR and the OER.

  7. Oxidation and Reduction Reactions in Organic Chemistry

    ERIC Educational Resources Information Center

    Shibley, Ivan A., Jr.; Amaral, Katie E.; Aurentz, David J.; McCaully, Ronald J.

    2010-01-01

    A variety of approaches to the concept of oxidation and reduction appear in organic textbooks. The method proposed here is different than most published approaches. The oxidation state is calculated by totaling the number of heterogeneous atoms, [pi]-bonds, and rings. A comparison of the oxidation states of reactant and product determine what type…

  8. Spatially Resolved Mapping of Oxygen Reduction/evolution Reaction on Solid-Oxide Fuel Cell Cathodes with sub-10 nm Resolution

    SciTech Connect

    Kumar, Amit; Leonard, Donovan N; Jesse, Stephen; Ciucci, Francesco; Eliseev, Eugene; Morozovska, A. N.; Biegalski, Michael D; Christen, Hans M; Tselev, Alexander; Mutoro, Eva; Crumlin, Ethan; Morgan, Dane; Shao-Horn, Yang; Borisevich, Albina Y; Kalinin, Sergei

    2013-01-01

    Spatial localization of the oxygen reduction/evolution reactions (ORR/OER) on lanthanum strontium cobaltite (LSCO) surfaces with perovskite and layered perovskite structures is studied on the sub-10 nanometer level. Comparison between Electrochemical Strain Microscopy (ESM) and structural imaging by scanning transmission electron microscopy (STEM) suggest that small-angle grain boundaries act as regions with enhanced electrochemical activity. The ESM activity is compared across a family of LSCO samples, demonstrating excellent agreement with macroscopic behaviors. This study potentially paves the way for deciphering the mechanisms of electrochemical activity of solids on the level of single extended structural defects such as grain boundaries and dislocations.

  9. Core-shell Co@Co3O4 nanoparticle-embedded bamboo-like nitrogen-doped carbon nanotubes (BNCNTs) as a highly active electrocatalyst for the oxygen reduction reaction.

    PubMed

    Xiao, Junwu; Chen, Chen; Xi, Jiangbo; Xu, Yangyang; Xiao, Fei; Wang, Shuai; Yang, Shihe

    2015-04-28

    The current bottleneck for fuel cells and metal-air batteries lies in the sluggish oxygen reduction reaction (ORR) on the cathode side. Despite tremendous efforts, to develop a highly efficient ORR catalyst at low cost remains a great challenge. Herein, we have synthesized core-shell Co@Co3O4 nanoparticles embedded in the bamboo-like N-doped carbon tubes (BNCNTs) by a simple approach comprising thermal treatment of cobalt carbonate hydroxide and urea and oxidization. The ORR catalytic activities of the Co@Co3O4/BNCNT composites are closely dependent on the oxidization degree of the Co nanoparticles and the N content in the BNCNTs. When oxidized at 300 °C, the as-formed Co@Co3O4/BNCNTs-300 composite catalyst with an N/C molar ratio of ∼ 1.6% achieves the maximum ORR catalytic activity. The composite catalyst also exhibits a higher ORR catalytic activity than the Co3O4/carbon nanotube (CNT) catalyst. The tolerance for methanol molecules and the cycle stability performance of the composite catalyst are even superior to those of the highly efficient Pt/C catalyst. Such an excellent ORR catalytic activity can be ascribed to (1) the core-shell Co@Co3O4 nanoparticles embedded in BNCNTs, (2) the N-doping in BNCNTs, and (3) the synergetic effect of (1) and (2) on Co3O4 firmly attached to both Co nanoparticles and BNCNTs, resulting in accelerated electron transport and enhanced charge delocalization. PMID:25465620

  10. Oxygen reduction reaction increased tolerance and fuel cell performance of Pt and Ru xSe y onto oxide-carbon composites

    NASA Astrophysics Data System (ADS)

    Timperman, Laure; Gago, Aldo S.; Alonso-Vante, Nicolas

    Pt and Ru xSe y nanoparticles were selectively deposited onto oxide sites of oxide-carbon composite substrates using the photo-deposition process and compared to conventional carbon support materials. The oxide was essentially anatase phase. Cyclic voltammetry and rotating disk electrode measurements for the oxygen reduction reaction (ORR) in formic acid containing-electrolyte showed a tolerance improvement for ORR of Pt supported on composite substrates. This positive substrate effect on platinum, turned out not to be favorable for Ru xSe y catalyst centers. On the other hand, the methanol tolerance for ORR was increased for both nanostructured materials supported on the oxide-carbon composite. Single H 2/O 2 fuel cell results were in agreement with half-cell electrochemical measurements on Pt, showing an improvement of the power density when using the oxide-carbon as substrate for the cathode. The composites were evaluated as cathode catalysts of an HCOOH laminar-flow fuel cell (LFFC) in which commercial Pd/C was used as an anode catalyst. The cathodes with Ru xSe y and Pt supported on TiO 2/C improved the specific power density by 15% and 24%, respectively, with respect to carbon as support.

  11. Porous VO(x)N(y) nanoribbons supported on CNTs as efficient and stable non-noble electrocatalysts for the oxygen reduction reaction.

    PubMed

    Huang, K; Bi, K; Lu, Y K; Zhang, R; Liu, J; Wang, W J; Tang, H L; Wang, Y G; Lei, M

    2015-01-01

    Novel nanocomposites of carbon nanotubes supported porous VO(x)N(y) nonoribbons (VO(x)N(y)-CNTs) have been synthesized by the annealing of the sol-gel mixture of CNTs and V2O5 under NH3 atmosphere as well as the ageing process in air. Besides the morphological and structural characterizations revealed by TEM, SEAD, EDS, XRD and XPS measurements, typical electrochemical tests including cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry have been employed to determine the oxygen reduction reaction (ORR) performance of VO(x)N(y)-CNTs. Inspiringly, the results indicate that VO(x)N(y)-CNTs catalyst exhibits a 0.4 mA/cm(2) larger diffusion-limited current density, a 0.10  V smaller onset potential value, a 10.73% less of ORR current decay and an excellent methanol-tolerance compared with commercial Pt/C catalyst. Therefore, we have reasonable grounds to believe that this new VO(x)N(y)-CNTs nanocomposites can be regarded as a promising non-precious methanol-tolerant ORR catalyst candidate for alkaline fuel cells. PMID:26616719

  12. Porous VOxNy nanoribbons supported on CNTs as efficient and stable non-noble electrocatalysts for the oxygen reduction reaction

    PubMed Central

    Huang, K.; Bi, K.; Lu, Y. K.; Zhang, R.; Liu, J.; Wang, W. J.; Tang, H. L.; Wang, Y. G.; Lei, M.

    2015-01-01

    Novel nanocomposites of carbon nanotubes supported porous VOxNy nonoribbons (VOxNy-CNTs) have been synthesized by the annealing of the sol-gel mixture of CNTs and V2O5 under NH3 atmosphere as well as the ageing process in air. Besides the morphological and structural characterizations revealed by TEM, SEAD, EDS, XRD and XPS measurements, typical electrochemical tests including cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry have been employed to determine the oxygen reduction reaction (ORR) performance of VOxNy-CNTs. Inspiringly, the results indicate that VOxNy-CNTs catalyst exhibits a 0.4 mA/cm2 larger diffusion-limited current density, a 0.10  V smaller onset potential value, a 10.73% less of ORR current decay and an excellent methanol-tolerance compared with commercial Pt/C catalyst. Therefore, we have reasonable grounds to believe that this new VOxNy-CNTs nanocomposites can be regarded as a promising non-precious methanol-tolerant ORR catalyst candidate for alkaline fuel cells. PMID:26616719

  13. Effects of transition metal doping in Pt/M-TiO2 (M = V, Cr, and Nb) on oxygen reduction reaction activity

    NASA Astrophysics Data System (ADS)

    Kim, Jun-Hyuk; Kwon, Gihan; Lim, Hankwon; Zhu, Chenhui; You, Hoydoo; Kim, Yong-Tae

    2016-07-01

    High cost and low durability are unresolved issues that impede the commercialization of proton exchange membrane fuel cells (PEMFCs). To overcome these limitations, Pt/TiO2 is reported as an alternative electrocatalyst for enhancing the oxygen reduction reaction (ORR) activity and/or durability of the system. However, the low electrical conductivity of TiO2 is a drawback that may be addressed by doping. To date, most reports related to Pt/doped-TiO2 focus on changes in the catalyst activity caused by the Pt-TiO2 interaction (metal-support interaction), instead of the effect of doping itself; doping is merely considered to enhance the electrical conductivity of TiO2. In this study, we discuss the variation in the electronic fine structure of Pt caused by the dopant, and its correlation with the ORR activity. More extensive contraction of the Pt lattice in Pt/M-TiO2 (M = V, Cr, and Nb) relative to Pt/TiO2 and Pt/C leads to outstanding ORR specific activity of Pt/M-TiO2. Notably, a fourfold increase of the specific activity is achieved with Pt/V-TiO2 relative to Pt/C. Furthermore, an accelerated durability test (ADT) of Pt/V-TiO2 demonstrates that this system is three times more durable than conventional Pt/C due to the metal-support interaction.

  14. Synergistically Enhanced Electrocatalytic Activity of Sandwich-like N-Doped Graphene/Carbon Nanosheets Decorated by Fe and S for Oxygen Reduction Reaction.

    PubMed

    Men, Bao; Sun, Yanzhi; Liu, Jia; Tang, Yang; Chen, Yongmei; Wan, Pingyu; Pan, Junqing

    2016-08-01

    Although N-doped graphene-based electrocatalysts have shown good performance for oxygen reduction reaction (ORR), they still suffer from the single-type active site in the as-prepared catalyst, limited accessible active surface area because of easy aggregation of graphene, and harsh condition for preparation process of graphene. Therefore, further developing a novel type of graphene-based electrocatalyst by a facile and environmentally benign method is highly anticipated. Herein, we first fabricate a sandwich-like graphene/carbon hybrid using graphene oxide (GO) and nontoxic starch. Then the graphene/carbon hybrid undergoes postprocessing with iron(III) chloride (FeCl3) and potassium sulfocyanide (KSCN) to acquire N-doped graphene/carbon nanosheets decorated by Fe and S. The resultant displays the features of interpenetrated three-dimensional hierarchical architecture composed of abundant sandwich-like graphene/carbon nanosheets and low graphene content in as-prepared sample. Remarkably, the obtained catalyst possesses favorable kinetic activity due to the unique structure and synergistic effect of N, S, and Fe on ORR, showing high onset potential, low Tafel slope, and nearly four-electron pathway. Meanwhile, the catalyst exhibits strong methanol tolerance and excellent long-term durability. In view of the multiple active sites, unique hierarchical structure, low graphene content, and outstanding electrochemical activity of the as-prepared sample, this work could broaden the thinking to develop more highly efficient graphene/carbon electrocatalysts for ORR in fuel cells. PMID:27404342

  15. Experimental identification of the active sites in pyrolyzed carbon-supported cobalt-polypyrrole-4-toluenesulfinic acid as electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Sha, Hao-Dong; Yuan, Xianxia; Li, Lin; Ma, Zhong; Ma, Zi-Feng; Zhang, Lei; Zhang, Jiujun

    2014-06-01

    A series of carbon supported cobalt-polypyrrole-4-toluenesulfinic acid have been pyrolyzed in an argon atmosphere at 800 °C, then structurally characterized and electrochemically evaluated as oxygen reduction reaction (ORR) catalysts in aqueous 0.5 M sulfuric acid. The structures are cobalt bonded to nitrogen species (Co-Nx) along with metallic cobalt and cobalt oxide. When the cobalt loading in the compound is less than 1.0 wt%, the predominate form is Co-Nx, when the loading is higher than 1.0 wt%, metallic Co and Co oxide particles co-exist with the Co-Nx compound. At a Co loading of ∼1.0 wt%, the catalyst gives the best ORR activity. Both metallic Co and Co oxide are not active for catalyzing ORR, and block the catalytically active Co-Nx species from the surface and reduce the catalytic activity since the diffusion limiting current density on a rotating disk electrode (RDE) increases when the electrode blocking agents are washed away with acid.

  16. Porous VOxNy nanoribbons supported on CNTs as efficient and stable non-noble electrocatalysts for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Huang, K.; Bi, K.; Lu, Y. K.; Zhang, R.; Liu, J.; Wang, W. J.; Tang, H. L.; Wang, Y. G.; Lei, M.

    2015-11-01

    Novel nanocomposites of carbon nanotubes supported porous VOxNy nonoribbons (VOxNy-CNTs) have been synthesized by the annealing of the sol-gel mixture of CNTs and V2O5 under NH3 atmosphere as well as the ageing process in air. Besides the morphological and structural characterizations revealed by TEM, SEAD, EDS, XRD and XPS measurements, typical electrochemical tests including cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry have been employed to determine the oxygen reduction reaction (ORR) performance of VOxNy-CNTs. Inspiringly, the results indicate that VOxNy-CNTs catalyst exhibits a 0.4 mA/cm2 larger diffusion-limited current density, a 0.10  V smaller onset potential value, a 10.73% less of ORR current decay and an excellent methanol-tolerance compared with commercial Pt/C catalyst. Therefore, we have reasonable grounds to believe that this new VOxNy-CNTs nanocomposites can be regarded as a promising non-precious methanol-tolerant ORR catalyst candidate for alkaline fuel cells.

  17. Gas phase contributions to topochemical hydride reduction reactions

    SciTech Connect

    Kobayashi, Yoji; Li, Zhaofei; Hirai, Kei; Tassel, Cédric; Loyer, François; Ichikawa, Noriya; Abe, Naoyuki; Yamamoto, Takafumi; Shimakawa, Yuichi; and others

    2013-11-15

    Alkali and alkali earth hydrides have been used as solid state reductants recently to yield many interesting new oxygen-deficient transition metal oxides. These reactions have tacitly been assumed to be a solid phase reaction between the reductant and parent oxide. We have conducted a number of experiments with physical separation between the reductant and oxides, and find that in some cases reduction proceeds even when the reagents are physically separated, implying reactions with in-situ generated H{sub 2} and, to a lesser extent, getter mechanisms. Our findings change our understanding of these topochemical reactions, and should enhance the synthesis of additional new oxides and nanostructures. - Graphical abstract: Topochemical reductions with hydrides: Solid state or gas phase reaction? Display Omitted - Highlights: • SrFeO{sub 2} and LaNiO{sub 2} were prepared by topochemical reduction of oxides. • Separating the reducing agent (CaH{sub 2}, Mg metal) from the oxide still results in reduction. • Such topochemical reactions can occur in the gas phase.

  18. Highly Porous Carbon Derived from MOF-5 as a Support of ORR Electrocatalysts for Fuel Cells.

    PubMed

    Khan, Inayat Ali; Qian, Yuhong; Badshah, Amin; Nadeem, Muhammad Arif; Zhao, Dan

    2016-07-13

    The development of highly competent electrocatalysts for the sluggish oxygen reduction reaction (ORR) at cathodes of proton-exchange membrane fuel cells (PEMFCs) is extremely important for their long-term operation and wide applications. Herein, we present highly efficient ORR electrocatalysts based on Pt/Ni bimetallic nanoparticles dispersed on highly porous carbon obtained via pyrolysis of a metal-organic framework MOF-5. In comparison to the commercial Pt/C (20%), the electrocatalyst Pt-Ni/PC 950 (15:15%) in this study exhibits a pronounced positive shift of 90 mV in Eonset. In addition, it also demonstrates excellent long-term stability and durability during the 500-cycle continue-oxygen-supply (COS) accelerating durability tests (ADTs). The significantly improved activity and stability of Pt-Ni/PC 950 (15:15%) can be attributed to the Pt electron interaction with Ni and carbon support as has been proved in X-ray and microscopic analysis. PMID:27327655

  19. Three-dimensional N,B-doped graphene aerogel as a synergistically enhanced metal-free catalyst for the oxygen reduction reaction.

    PubMed

    Xu, Congcong; Su, Yan; Liu, Dajun; He, Xingquan

    2015-10-14

    Here, a novel N,B-doped graphene aerogel, abbreviated as N,B-GA, was obtained via a two-step approach and served as a metal-free catalyst for the oxygen reduction reaction (ORR). This two-step method involved a hydrothermal reaction and a pyrolysis procedure, guaranteeing the efficient insertion of the heteroatoms. The resulting three-dimensional (3D) N,B-GA obtained at pyrolysis temperature of 1000 °C exhibited outstanding catalytic activity for the oxygen reduction reaction (ORR), comparable to that of Pt/C. In addition, the catalytic activity of this 3D N,B-GA was obviously better than that of the nitrogen-doped graphene aerogel (N-GA) and boron-doped graphene aerogel (B-GA) in terms of the onset potential, half-wave potential and diffusion limiting current density. The superior catalytic reactivity arises from the synergistic coupling of the B and N dopants within the graphene domains. PMID:26364585

  20. Optimization of catalyst layer composition for PEMFC using graphene-based oxygen reduction reaction catalysts

    NASA Astrophysics Data System (ADS)

    Park, Jong Cheol; Park, Sung Hyeon; Chung, Min Wook; Choi, Chang Hyuck; Kho, Back Kyun; Woo, Seong Ihl

    2015-07-01

    The focus in recent years is on developing high performance non-precious metal catalysts (NPMCs) to reduce the catalyst cost in fuel cells. However, little attention has been paid to improve the utilization of NPMCs. Thus, this study focuses on the optimization of electrode component, particularly the Nafion content. With the synthesized graphene based oxygen reduction reaction (ORR) catalyst, the catalyst inks were prepared at various Nafion contents with suitable amounts of catalysts sprayed on the gas diffusion media. Twenty different single cells were assembled and measured for polarization, resistance and electrochemical impedance. Electrodes of 66.7 and 50.0% Nafion contents showed the highest performance for hydrogen/oxygen and hydrogen/air operation, respectively. These results were explained using the electrochemical impedance spectra, where the highest performance electrode resulted with the lowest charge transfer resistance. Moreover, negligible change in performance was observed during the 80 h of stability test. The optimization compositions of NPMC-based MEAs were very different to Pt-based MEAs, indicating the importance of optimization studies for the practical use of NPMCs.

  1. Three-Dimensionally Costabilized Metal Catalysts toward an Oxygen Reduction Reaction.

    PubMed

    Cheng, Kun; Jiang, Min; Ye, Bei; Amiinu, Ibrahim Saana; Liu, Xiaobo; Kou, Zongkui; Li, Wenqiang; Mu, Shichun

    2016-03-01

    Improving the long-term stability of metal catalysts is crucial to developing polymer electrolyte fuel cells (PEFCs). In this work, we first report an inorganic (TiO2)-organic (perfluorosulfonic acid, PFSA) costabilized Pt catalyst supported on graphene nanosheets (GNS) (Pt-PFSA-TiO2/GNS). Herein, TiO2, as a robust wall, impedes the collision between the metal nanoparticles (NPs) in plane along the horizontal x and y axes, while PFSA mainly anchors the metal NPs to constrain detachment along the vertical z axis. The resulting catalyst displays higher oxygen reduction reaction (ORR) activity in comparison to that of commercial Pt/C. Significantly, the stability is particularly better than that of only PFSA- or TiO2-decorated catalysts (Pt-PFSA/GNS or Pt-TiO2/GNS) and far better than that of Pt/C. After 6000 potential cycles, the half-wave potential (E1/2) of Pt-PFSA-TiO2/GNS decreases by only 16 mV, far less than that of Pt/C (56 mV). The excellent electrochemical property of Pt-PFSA-TiO2/GNS is predominantly attributed to the synergistic effect of PFSA and TiO2 in costabilizing the Pt NP by anchoring and blocking Pt NPs in all three spatial directions. The structural dynamics and mechanism of enhanced properties are also discussed. PMID:26866997

  2. Pyrolyzed binuclear-cobalt-phthalocyanine as electrocatalyst for oxygen reduction reaction in microbial fuel cells.

    PubMed

    Li, Baitao; Wang, Mian; Zhou, Xiuxiu; Wang, Xiujun; Liu, Bingchuan; Li, Baikun

    2015-10-01

    A novel platinum (Pt)-free cathodic materials binuclear-cobalt-phthalocyanine (Bi-CoPc) pyrolyzed at different temperatures (300-1000 °C) were examined as the oxygen reduction reaction (ORR) catalysts, and compared with unpyrolyzed Bi-CoPc/C and Pt cathode in single chamber microbial fuel cells (SCMFCs). The results showed that the pyrolysis process increased the nitrogen abundance on Bi-CoPc and changed the nitrogen types. The Bi-CoPc pyrolyzed at 800 °C contained a significant amount of pyrrolic-N, and exhibited a high electrochemical catalytic activity. The power density and current density increased with temperature: Bi-CoPc/C-800 > Bi-CoPc/C-1000 > Bi-CoPc/C-600 > Bi-CoPc/C-300 > Bi-CoPc/C. The SCMFC with Bi-CoPc/C-800 cathode had a maximum power density of 604 mW m(-2). The low cost Bi-CoPc compounds developed in this study showed a potential in air-breathing MFC systems, with the proper pyrolysis temperature being chosen. PMID:26142820

  3. Synthesis, characterization and electrochemical studies of nanostructured CaWO{sub 4} as platinum support for oxygen reduction reaction

    SciTech Connect

    Farsi, Hossein; Barzgari, Zahra

    2014-11-15

    Highlights: • Nanostructured CaWO{sub 4} was fabricated by co-precipitation method. • Platinum was electrodeposited onto the surface prepared nanostructured CaWO{sub 4}. • Pt/CaWO{sub 4}-graphite demonstrate good oxygen reduction reaction activity. - Abstract: In the present work, we employed nanostructured calcium tungstate as a supporting material for platinum, a well-known electrocatalyst for oxygen reduction. The co-precipitation method has been utilized to synthesize nanostructured calcium tungstate from aqueous solution. The structure and morphology of the obtained CaWO{sub 4} were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Preparation of the Pt/CaWO{sub 4}-graphite catalyst was carried out by electrodeposition of Pt onto the surface of CaWO{sub 4}/graphite electrode. The physical properties of the catalyst were determined by scanning electron microscopy analysis and energy dispersive X-ray (SEM/EDX). The electrochemical activity of the Pt/CaWO{sub 4}-graphite for the oxygen reduction reaction (ORR) was investigated in acid solution by cyclic voltammetry measurements, linear sweep voltammetry, and electrochemical impedance spectroscopy. The results revealed that the Pt/CaWO{sub 4}-graphite has higher electrocatalytic activity for oxygen reduction in comparison with Pt/graphite catalyst.

  4. Well-Combined Magnetically Separable Hybrid Cobalt Ferrite/Nitrogen-Doped Graphene as Efficient Catalyst with Superior Performance for Oxygen Reduction Reaction.

    PubMed

    Lu, Lei; Hao, Qingli; Lei, Wu; Xia, Xifeng; Liu, Peng; Sun, Dongping; Wang, Xin; Yang, Xujie

    2015-11-18

    Catalysts with low-cost, high activity and stability toward oxygen reduction reaction (ORR) are extremely desirable, but its development still remains a great challenge. Here, a novel magnetically separable hybrid of multimetal oxide, cobalt ferrite (CoFe2O4), anchored on nitrogen-doped reduced graphene oxide (CoFe2O4/NG) is prepared via a facile solvothermal method followed by calcination at 500 °C. The structure of CoFe2O4/NG and the interaction of both components are analyzed by several techniques. The possible formation of Co/Fe-N interaction in the CoFe2O4/NG catalyst is found. As a result, the well-combination of CoFe2O4 nanoparticles with NG and its improved crystallinity lead to a synergistic and efficient catalyst with high performance to ORR through a four-electron-transfer process in alkaline medium. The CoFe2O4/NG exhibits particularly comparable catalytic activity as commercial Pt/C catalyst, and superior stability against methanol oxidation and CO poisoning. Meanwhile, it has been proved that both nitrogen doping and the spinel structure of CoFe2O4 can have a significant contribution to the catalytic activity by contrast experiments. Multimetal oxide hybrid demonstrates better catalysis to ORR than a single metal oxide hybrid. All results make the low-cost and magnetically separable CoFe2O4/NG a promising alternative for costly platinum-based ORR catalyst in fuel cells and metal-air batteries. PMID:26390018

  5. Nanoporous PdZr surface alloy as highly active non-platinum electrocatalyst toward oxygen reduction reaction with unique structure stability and methanol-tolerance

    NASA Astrophysics Data System (ADS)

    Duan, Huimei; Xu, Caixia

    2016-06-01

    Nanoporous (NP) PdZr alloy with controllable bimetallic ratio is successfully fabricated by a simple dealloying method. By leaching out the more reactive Al from PdZrAl precursor alloy, NP-PdZr alloy with smaller ligament size was generated, characterized by the nanoscaled interconnected network skeleton and hollow channels extending in all three dimensions. Upon voltammetric scan in acid solution, the dissolution of surface Zr atoms generates the highly active Pd-Zr surface alloy with a nearly pure Pd surface and Pd-Zr alloy core. The NP-Pd80Zr20 surface alloy exhibits markedly enhanced specific and mass activities as well as higher catalytic stability toward oxygen reduction reaction (ORR) compared with NP-Pd and the state-of-the-art Pt/C catalysts. In addition, the NP-Pd80Zr20 surface alloy shows a better selectivity for ORR than methanol in the 0.1 M HClO4 and 0.1 M methanol mixed solution. X-ray photoelectron spectroscopy and density functional theory calculations both demonstrate that the weakened Pd-O bond and improved ORR performances in turn depend on the downshifted d-band center of Pd due to the alloying Pd with Zr (20 at.%). The as-made NP-PdZr alloy holds prospective applications as a cathode electrocatalyst in fuel-cell-related technologies with the advantages of superior overall ORR performances, unique structure stability, and easy preparation.

  6. Whole cell biotransformation for reductive amination reactions

    PubMed Central

    Klatte, Stephanie; Lorenz, Elisabeth; Wendisch, Volker F

    2014-01-01

    Whole cell biotransformation systems with enzyme cascading increasingly find application in biocatalysis to complement or replace established chemical synthetic routes for production of, e.g., fine chemicals. Recently, we established an Escherichia coli whole cell biotransformation system for reductive amination by coupling a transaminase and an amino acid dehydrogenase with glucose catabolism for cofactor recycling. Transformation of 2-keto-3-methylvalerate to l-isoleucine by E. coli cells was improved by genetic engineering of glucose metabolism for improved cofactor regeneration. Here, we compare this system with different strategies for cofactor regeneration such as cascading with alcohol dehydrogenases, with alternative production hosts such as Pseudomonas species or Corynebacterium glutamicum, and with improving whole cell biotransformation systems by metabolic engineering of NADPH regeneration. PMID:24406456

  7. Atomic Ordering Enhanced Electrocatalytic Activity of Nanoalloys for Oxygen Reduction Reaction

    SciTech Connect

    Loukrakpam, Rameshwori; Shan, Shiyao; Petkov, Valeri; Yang, Lefu; Luo, Jin; Zhong, Chuan-Jian

    2013-10-01

    For oxygen reduction reaction (ORR) over alloy electrocatalysts, the understanding of how the atomic arrangement of the metal species in the nanocatalysts is responsible for the catalytic enhancement is challenging for achieving better design and tailoring of nanoalloy catalysts. This paper reports results of an investigation of the atomic structures and the electrocatalytic activities of ternary and binary nanoalloys, aiming at revealing a fundamental insight into the unique atomic-scale structure-electrocatalytic activity relationship. PtIrCo catalyst and its binary counterparts (PtCo and PtIr) are chosen as a model system for this study. The effect of thermochemical treatment temperature on the atomic-scale structure of the catalysts was examined as a useful probe to the structure-activity correlation. The structural characterization of the binary and ternary nanoalloy catalysts was performed by combining surface sensitive techniques such as XPS and 3D atomic ordering sensitive techniques such as high-energy X-ray diffraction (HE-XRD) coupled to atomic pair distribution function (PDF) analysis (HE-XRD/PDFs) and computer simulations. The results show that the thermal treatment temperature tunes the nanoalloy’s atomic and chemical ordering in a different way depending on the chemical composition, leading to differences in the nanoalloy’s mass and specific activities. A unique structural tunability of the atomic ordering in a platinum-iridium-cobalt nanoalloy has been revealed for enhancing greatly the electrocatalytic activity toward oxygen reduction reaction, which has significant implication for rational design and nanoengineering of advanced catalysts for electrochemical energy conversion and storage.

  8. Nitrogen-doped carbon dots originating from unripe peach for fluorescent bioimaging and electrocatalytic oxygen reduction reaction.

    PubMed

    Atchudan, Raji; Edison, Thomas Nesakumar Jebakumar Immanuel; Lee, Yong Rok

    2016-11-15

    This paper reports the robust hydrothermal synthesis of nitrogen doped carbon dots (N-CDs) using the unripe fruit of Prunus persica (peach) as the carbon precursor and aqueous ammonia as the nitrogen source. The optical properties of synthesized N-CDs were characterized by ultraviolet visible (UV-Vis) and fluorescence spectroscopy techniques. The synthesized N-CDs were emitted blue light when excitated with a portable UV lamp. The materials with the optical properties were characterized further by high resolution transmission electron microscope (HRTEM), X-ray diffraction (XRD), Raman, Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). The mean size of the N-CDs was approximately 8nm, as calculated from the HRTEM image. The d-spacing of N-CDs, calculated using Bragg law, was approximately 0.21nm, which was consistent with the interlayer distance calculated from the HRTEM image. FT-IR spectroscopy and XPS revealed the presence of the phytoconstituents functionalities of peach fruit over the N-CDs surface and a high level of nitrogen doping on carbon dots (CDs) was confirmed by XPS studies. These results suggest that the unripe fruit extract of peach is an ideal candidate for the preparation of N-CDs. The resulting N-CDs showed excellent optical properties in water. The synthesized N-CDs exhibited a high fluorescence quantum yield and low cytotoxicity, and can be used as fluorescence imaging probes. In addition, the N-CDs were catalytically activite towards the oxygen reduction reaction (ORR). The N-CDs exhibited good catalytic activity in an alkaline medium (0.1M KOH) with a remarkable ORR of approximately 0.72V vs reversible hydrogen electrode (RHE), and O2 reduction follows mainly a 2 electron pathway by being reduced to hydrogen peroxide. The 2-electron reduction pathway is used in industry for H2O2 production. PMID:27479911

  9. Decoupling strain and ligand effects in ternary nanoparticles for improved ORR electrocatalysis.

    PubMed

    Jennings, Paul C; Lysgaard, Steen; Hansen, Heine A; Vegge, Tejs

    2016-09-21

    Ternary Pt-Au-M (M = 3d transition metal) nanoparticles show reduced OH adsorption energies and improved activity for the oxygen reduction reaction (ORR) compared to pure Pt nanoparticles, as obtained by density functional theory. The strain and ligand effects in nanoparticles are decoupled and correlated with the extended Pt(111) surface for benchmarking. The ternary metal in the core allows for tuning the catalytic activity through strain effects. Pt-Au-M for M = Cr, Mn, Co, Cu, Zn nanoparticles are of particular interest as they exhibit an optimal contribution of strain, ligand effects and stability. Good agreement is found with experimental studies showing increased activity of Pt-Au-Fe/Ni nanoparticles, and mid to late 3d transition metals are predicted to exhibit enhance activity and stability with respect to pure Pt nanoparticles. PMID:27550572

  10. Reproducibly creating hierarchical 3D carbon to study the effect of Si surface functionalization on the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zeng, Yuze; Flores, Jose F.; Shao, Yu-Cheng; Guo, Jinghua; Chuang, Yi-De; Lu, Jennifer Q.

    2016-06-01

    We report a new method to reproducibly fabricate functional 3D carbon structures directly on a current collector, e.g. stainless steel. The 3D carbon platform is formed by direct growth of upright arrays of carbon nanofiber bundles on a roughened surface of stainless steel via the seed-assisted approach. Each bundle consists of about 30 individual carbon nanofibers with a diameter of 18 nm on average. We have found that this new platform offers adequate structural integrity. As a result, no reduction of the surface area during downstream chemical functionalization was observed. With a fixed and reproducible 3D structure, the effect of the chemistry of the grafted species on the oxygen reduction reaction has been systematically investigated. This investigation reveals for the first time that non-conductive Si with an appropriate electronic structure distorts the carbon electronic structure and consequently enhances ORR electrocatalysis. The strong interface provides excellent electron connectivity according to electrochemical analysis. This highly reproducible and stable 3D platform can serve as a stepping-stone for the investigation of the effect of carbon surface functionalization on electrochemical reactions in general.We report a new method to reproducibly fabricate functional 3D carbon structures directly on a current collector, e.g. stainless steel. The 3D carbon platform is formed by direct growth of upright arrays of carbon nanofiber bundles on a roughened surface of stainless steel via the seed-assisted approach. Each bundle consists of about 30 individual carbon nanofibers with a diameter of 18 nm on average. We have found that this new platform offers adequate structural integrity. As a result, no reduction of the surface area during downstream chemical functionalization was observed. With a fixed and reproducible 3D structure, the effect of the chemistry of the grafted species on the oxygen reduction reaction has been systematically investigated. This

  11. Charge transfer induced activity of graphene for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Shen, Anli; Xia, Weijun; Zhang, Lipeng; Dou, Shuo; Xia, Zhenhai; Wang, Shuangyin

    2016-05-01

    Tetracyanoethylene (TCNE), with its strong electron-accepting ability, was used to dope graphene as a metal-free electrocatalyst for the oxygen reduction reaction (ORR). The charge transfer process was observed from graphene to TCNE by x-ray photoelectron spectroscopy and Raman characterizations. Our density functional theory calculations found that the charge transfer behavior led to an enhancement of the electrocatalytic activity for the ORR.

  12. A cobalt-nitrogen complex on N-doped three-dimensional graphene framework as a highly efficient electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Jiang, Yuanyuan; Lu, Yizhong; Wang, Xiaodan; Bao, Yu; Chen, Wei; Niu, Li

    2014-11-01

    The high cost and limited natural abundance of platinum hinder its widespread applications as the oxygen reduction reaction (ORR) electrocatalyst for fuel cells. Carbon-supported materials containing metals such as Fe or Co as well as nitrogen have been proposed to reduce the cost without obvious lowering the performance compared to Pt-based electrocatalysts. In this work, based on the pyrolyzed corrin structure of vitamin B12 on the simultaneously reduced graphene support (g-VB12), we construct an efficient oxygen reduction electrocatalyst with very positive half-wave potential (only ~30 mV deviation from Pt/C), high selectivity (electron transfer number close to 4) and excellent durability (only 11 mV shift of the half-wave potential after 10 000 potential cycles). The admirable performance of this electrocatalyst can be attributed to the homogeneous distribution of abundant Co-Nx active sites, and a well-defined three-dimensional mesoporous structure of the N-doped graphene support. The high activity and long-term stability of the low cost g-VB12 make it a promising ORR electrocatalyst in alkaline fuel cells.The high cost and limited natural abundance of platinum hinder its widespread applications as the oxygen reduction reaction (ORR) electrocatalyst for fuel cells. Carbon-supported materials containing metals such as Fe or Co as well as nitrogen have been proposed to reduce the cost without obvious lowering the performance compared to Pt-based electrocatalysts. In this work, based on the pyrolyzed corrin structure of vitamin B12 on the simultaneously reduced graphene support (g-VB12), we construct an efficient oxygen reduction electrocatalyst with very positive half-wave potential (only ~30 mV deviation from Pt/C), high selectivity (electron transfer number close to 4) and excellent durability (only 11 mV shift of the half-wave potential after 10 000 potential cycles). The admirable performance of this electrocatalyst can be attributed to the homogeneous

  13. CuCo2O4 ORR/OER Bi-functional catalyst: Influence of synthetic approach on performance

    SciTech Connect

    Serov, Alexey; Andersen, Nalin I.; Roy, Aaron J.; Matanovic, Ivana; Artyushkova, Kateryna; Atanassov, Plamen

    2015-02-07

    A series of CuCo2O4 catalysts were synthesized by pore forming, sol-gel, spray pyrolysis and sacrificial support methods. Catalysts were characterized by XRD, SEM, XPS and BET techniques. The electrochemical activity for the oxygen reduction and oxygen evolution reactions (ORR and OER) was evaluated in alkaline media by RRDE. Density Functional Theory was used to identify two different types of active sites responsible for ORR/OER activity of CuCo2O4 and it was found that CuCo2O4 can activate the O-O bond by binding molecular oxygen in bridging positions between Co or Co and Cu atoms. It was found that the sacrificial support method (SSM) catalyst has the highest performance in both ORR and OER and has the highest content of phase-pure CuCo2O4. It was shown that the presence of CuO significantly decreases the activity in oxygen reduction and oxygen evolution reactions. As a result, the half-wave potential (E1/2) of CuCo2O4-SSM was found as 0.8 V, making this material a state-of-the-art, unsupported oxide catalyst.

  14. Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

    DOE PAGESBeta

    Zhang, Lulu; Su, Dong; Zhu, Shangqian; Chang, Qiaowan; Yue, Jeffrey; Du, Zheng; Shao, Minhua

    2016-04-26

    Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

  15. Synthesis of PtM (M=Co, Ni)/Reduced Graphene Oxide Nanocomposites as Electrocatalysts for the Oxygen Reduction Reaction.

    PubMed

    Li, Jialiang; Fu, Xinning; Mao, Zhou; Yang, Yushi; Qiu, Tong; Wu, Qingzhi

    2016-12-01

    A series of PtM (M=Co, Ni)/reduced graphene oxide (rG-O) nanocomposites were successfully synthesized through a facile hydrothermal method. The as-synthesized nanocomposites were characterized using transmission electron microscopy and high-resolution transmission electron microscopy, X-ray diffraction, inductively coupled plasma-atomic emission spectrometer, and X-ray photoelectron spectroscopy. The electrochemical performance and oxygen reduction reaction (ORR) activity of PtM/rG-O nanocomposites were evaluated using cyclic voltammetry and the rotating disk electrode method. The results show that the addition of the reductant (1,2-hexadecanediol, HAD) in the reaction system slightly improved the ORR activity of PtM/rG-O nanocomposites with a negligible influence on the size and morphology of alloy NPs. Furthermore, PtNi/rG-O nanocomposites displayed the higher electrochemical stability than PtCo/rG-O nanocomposites. These results provide a facile strategy for the synthesis of Pt-based alloy NPs/rG-O nanocomposites for applications in catalysis and energy-related processes. PMID:26732276

  16. Hybrid of porous cobalt oxide nanospheres and nitrogen-doped graphene for applications in lithium-ion batteries and oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Mengmeng; Li, Rong; Chang, Xiaoxuan; Xue, Chao; Gou, Xinglong

    2015-09-01

    A new single-source precursor has been developed from the hydrothermal reaction of graphite oxide (GO), melamine resin (MR) monomers, and CoCl2 to prepare a sandwich-like hybrid of ultrathin nitrogen-doped graphene (NG) sheets and porous Co3O4 nanospheres (Co3O4/NG). This unique structure endows the Co3O4/NG hybrid with large surface area and enhanced electrochemical performances as both anode material for Li-ion batteries and electrocatalyst for oxygen reduction reaction (ORR). As an anode material, it exhibits high reversible capacity, excellent cycling stability and rate performance (1236 and 489 mAh g-1 over 200 cycles at 0.1C and 2C, respectively; 371 mAh g-1 at 5C). As an ORR electrocatalyst, it shows superior catalytic activity and high selectivity for the four-electron reduction pathway compared to the bare Co3O4 and NG alone. Moreover, the Co3O4/NG hybrid is insensitive to methanol, and is much more stable than Pt/C catalyst over long term operation.

  17. Cumulative effect of transition metals on nitrogen and fluorine co-doped graphite nanofibers: an efficient and highly durable non-precious metal catalyst for the oxygen reduction reaction.

    PubMed

    Peera, S Gouse; Arunchander, A; Sahu, A K

    2016-08-14

    Nitrogen and fluorine co-doped graphite nanofibers (N/F-GNF) and their cumulative effect with Fe and Co have been developed as an alternative non-precious metal catalyst for efficient oxygen reduction reaction (ORR) in acidic media. The synergistic effect between the doped hetero atoms and the co-ordinated Fe and Co towards ORR activity and durability of the catalyst is deeply investigated. A high ORR onset potential comparable with commercial Pt/C catalyst is observed with the Fe-Co/NF-GNF catalyst, which indicates that this catalyst is a potential alternative to Pt/C. A fivefold increase in mass activity is achieved by the Fe-Co/NF-GNF catalyst compared to the simple N/F-GNF catalyst, which endorses the significant role of transition metal atoms in enhancing ORR activity. The advanced Fe-Co/NF-GNF catalyst also exhibits complete tolerance to CH3OH and CO. The Fe-Co/NF-GNF catalyst also exhibits excellent durability towards the ORR with only a 10 mV negative shift in its half wave potential after a 10 000 repeated potential cycling test, whereas in the case of a commercial Pt/C catalyst there was an ∼110 mV negative shift under similar environmental conditions. More stringent corrosive test cycles were also performed by maintaining the cell as high as 1.4 V with a later decrease to 0.6 V vs. RHE for 300 cycles, which showed the excellent durability of the Fe-Co/NF-GNF catalyst in comparison with the Pt/C catalyst. XPS analysis of the Fe-Co/NF-GNF catalyst presents the ORR active chemical states of N (pyridinic-N and graphitic-N) and F (semi-ionic-F) and the co-ordinated sites of Fe and Co species with the dopants. The excellent performance and durability of the Fe-Co/NF-GNF catalyst is due to the synergistic effect between the hetero atoms dopants (N and F) and strong co-ordinating bonds of M-N-C, which protect the graphene layers around the metallic species and greatly mitigates the leaching of Co and Fe during the long term cycling test. The high activity

  18. Molecular catalysis of the oxygen reduction reaction by iron porphyrin catalysts tethered into Nafion layers: An electrochemical study in solution and a membrane-electrode-assembly study in fuel cells

    NASA Astrophysics Data System (ADS)

    He, Qinggang; Mugadza, Tawanda; Kang, Xiongwu; Zhu, Xiaobing; Chen, Shaowei; Kerr, John; Nyokong, Tebello

    2012-10-01

    This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV-Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.

  19. Pt skin on Pd-Co-Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR

    NASA Astrophysics Data System (ADS)

    Xiao, Weiping; Zhu, Jing; Han, Lili; Liu, Sufen; Wang, Jie; Wu, Zexing; Lei, Wen; Xuan, Cuijuan; Xin, Huolin L.; Wang, Deli

    2016-08-01

    Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a highly active, durable, carbon supported, and monolayer Pt coated Pd-Co-Zn nanoparticle is synthesized via a simple impregnation-reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition-activity volcano curve for the Pd-Co-Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd8CoZn/C nanoparticles show a substantial enhancement in both the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd8CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N2-saturated 0.1 M HClO4 solution, Pd8CoZn@Pt/C shows improved mass activity (2.62 A mg-1Pt) and specific activity (4.76 A m-2total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O2-saturated 0.1 M HClO4 solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. The results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation.Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a highly active, durable, carbon supported, and monolayer Pt coated Pd-Co-Zn nanoparticle is synthesized via a simple impregnation-reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition-activity volcano curve for the Pd-Co-Zn nanoparticles and determined that Pd : Co : Zn = 8

  20. Reduction of chemical reaction networks through delay distributions

    NASA Astrophysics Data System (ADS)

    Barrio, Manuel; Leier, André; Marquez-Lago, Tatiana T.

    2013-03-01

    Accurate modelling and simulation of dynamic cellular events require two main ingredients: an adequate description of key chemical reactions and simulation of such chemical events in reasonable time spans. Quite logically, posing the right model is a crucial step for any endeavour in Computational Biology. However, more often than not, it is the associated computational costs which actually limit our capabilities of representing complex cellular behaviour. In this paper, we propose a methodology aimed at representing chains of chemical reactions by much simpler, reduced models. The abridgement is achieved by generation of model-specific delay distribution functions, consecutively fed to a delay stochastic simulation algorithm. We show how such delay distributions can be analytically described whenever the system is solely composed of consecutive first-order reactions, with or without additional "backward" bypass reactions, yielding an exact reduction. For models including other types of monomolecular reactions (constitutive synthesis, degradation, or "forward" bypass reactions), we discuss why one must adopt a numerical approach for its accurate stochastic representation, and propose two alternatives for this. In these cases, the accuracy depends on the respective numerical sample size. Our model reduction methodology yields significantly lower computational costs while retaining accuracy. Quite naturally, computational costs increase alongside network size and separation of time scales. Thus, we expect our model reduction methodologies to significantly decrease computational costs in these instances. We anticipate the use of delays in model reduction will greatly alleviate some of the current restrictions in simulating large sets of chemical reactions, largely applicable in pharmaceutical and biological research.

  1. Pt skin on Pd-Co-Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR.

    PubMed

    Xiao, Weiping; Zhu, Jing; Han, Lili; Liu, Sufen; Wang, Jie; Wu, Zexing; Lei, Wen; Xuan, Cuijuan; Xin, Huolin L; Wang, Deli

    2016-08-21

    Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a highly active, durable, carbon supported, and monolayer Pt coated Pd-Co-Zn nanoparticle is synthesized via a simple impregnation-reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition-activity volcano curve for the Pd-Co-Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd8CoZn/C nanoparticles show a substantial enhancement in both the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd8CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N2-saturated 0.1 M HClO4 solution, Pd8CoZn@Pt/C shows improved mass activity (2.62 A mg(-1)Pt) and specific activity (4.76 A m(-2)total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O2-saturated 0.1 M HClO4 solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. The results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation. PMID:27445114

  2. Reproducibly creating hierarchical 3D carbon to study the effect of Si surface functionalization on the oxygen reduction reaction.

    PubMed

    Zeng, Yuze; Flores, Jose F; Shao, Yu-Cheng; Guo, Jinghua; Chuang, Yi-De; Lu, Jennifer Q

    2016-06-01

    We report a new method to reproducibly fabricate functional 3D carbon structures directly on a current collector, e.g. stainless steel. The 3D carbon platform is formed by direct growth of upright arrays of carbon nanofiber bundles on a roughened surface of stainless steel via the seed-assisted approach. Each bundle consists of about 30 individual carbon nanofibers with a diameter of 18 nm on average. We have found that this new platform offers adequate structural integrity. As a result, no reduction of the surface area during downstream chemical functionalization was observed. With a fixed and reproducible 3D structure, the effect of the chemistry of the grafted species on the oxygen reduction reaction has been systematically investigated. This investigation reveals for the first time that non-conductive Si with an appropriate electronic structure distorts the carbon electronic structure and consequently enhances ORR electrocatalysis. The strong interface provides excellent electron connectivity according to electrochemical analysis. This highly reproducible and stable 3D platform can serve as a stepping-stone for the investigation of the effect of carbon surface functionalization on electrochemical reactions in general. PMID:27217228

  3. New mechanistic insight into the oxygen reduction reaction on Ruddlesden–Popper cathodes for intermediate-temperature solid oxide fuel cells

    DOE PAGESBeta

    Li, Wenyuan; Guan, Bo; Zhang, Xinxin; Yan, Jianhua; Zhou, Yue; Liu, Xingbo

    2016-01-01

    Ruddlesden–Popper (R–P) phase materials have been investigated widely as cathode candidates for IT-SOFCs. However, widespread application of R–P phase cathodes demands further improvement in electrode activity whose progress is hindered by the limited information in the oxygen reduction reaction (ORR). The ORR mechanism for the R–P phase is therefore investigated in this paper using (LaSr)2NiO4d as an example. Accurate characterization of the surface oxygen exchange process is realized by developing thin and dense polycrystalline LSNO layers via a versatile spray-modified pressing method we invented before to avoid perceptible bulk diffusion contribution, surface enrichment and geometry complication. The governing factors ofmore » the ORR are identified as oxygen adsorption and incorporation based on the findings in reaction orders from electrochemical impedance spectroscopy (EIS), stoichiometryrelated chemical capacitance and intrinsic anisotropic properties. The incorporation rate is proven to drastically depend on the amount of interstitial oxygen O00 i . Since the unfilled interstitial sites V i in the R–P phase serve to accommodate the adsorbed oxygen during incorporation, like vacancies in the perovskite structure V O , moreO00 i would seem to suppress the kinetics of this process. In regards to this, for the first time, a physical model is proposed to reconcile the discrepancy between the experimental results and intuitive reasoning. Based on supporting evidence, this model illustrates a possibility of how O00 i works to regulate the exchange rate, and how the contradiction between V O and O00 i is harmonized so that the latter in the R–P structure also positively promotes the incorporation rate in the ORR« less

  4. Facile synthesis of Rh-Pd alloy nanodendrites as highly active and durable electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Qi, Yue; Wu, Jianbo; Zhang, Hui; Jiang, Yingying; Jin, Chuanhong; Fu, Maoshen; Yang, Hong; Yang, Deren

    2014-05-01

    In addition to activity, durability of Pd-based catalysts in a highly corrosive medium has become one of the most important barriers to limit their industrial applications such as low-temperature fuel cell technologies. Here, Rh with a unique capability to resist against oxidation etching was incorporated into Pd-based catalysts to enhance both their activity and durability for oxygen reduction reaction (ORR). This idea was achieved through the synthesis of the Rh-Pd alloy nanodendrites by co-reducing Rh and Pd salt precursors in oleylamine (OAm) containing cetyltrimethylammonium bromide (CTAB). In this synthesis, Rh-Pd alloy nanostructures with Rh-Pd atomic ratios from 19 : 1 to 1 : 4 were generated by varying the molar ratios of Rh and Pd salt precursors. Interestingly, this variation of the molar ratios of the precursors from Rh rich to Pd rich would lead to the shape evolution of Rh-Pd alloy from dendritic nanostructures to spherical aggregations. We found that Br- ions derived from CTAB were also indispensible to the production of Rh-Pd alloy nanodendrites. Owing to the addition of highly stable Rh as well as the radical structure with a large number of low-coordinated sites on the arms, Rh-Pd alloy nanodendrites with a Rh-Pd atomic ratio of 4 : 1 (Rh80Pd20) exhibited a substantially enhanced electrocatalytic performance towards ORR with a 5% loss of mass activity during the accelerated stability test for 10 000 cycles compared to ~50% loss of the commercial Pt/C (E-TEK).In addition to activity, durability of Pd-based catalysts in a highly corrosive medium has become one of the most important barriers to limit their industrial applications such as low-temperature fuel cell technologies. Here, Rh with a unique capability to resist against oxidation etching was incorporated into Pd-based catalysts to enhance both their activity and durability for oxygen reduction reaction (ORR). This idea was achieved through the synthesis of the Rh-Pd alloy nanodendrites by co

  5. A highly efficient electrocatalyst for oxygen reduction reaction: phosphorus and nitrogen co-doped hierarchically ordered porous carbon derived from an iron-functionalized polymer

    NASA Astrophysics Data System (ADS)

    Deng, Chengwei; Zhong, Hexiang; Li, Xianfeng; Yao, Lan; Zhang, Huamin

    2016-01-01

    Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated.Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic

  6. Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials

    NASA Astrophysics Data System (ADS)

    Chen, Xi'an; Chen, Xiaohua; Xu, Xin; Yang, Zhi; Liu, Zheng; Zhang, Lijie; Xu, Xiangju; Chen, Ying; Huang, Shaoming

    2014-10-01

    Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g-1, good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and

  7. A comparative study of composition and morphology effect of Ni(x)Co(1-x)(OH)2 on oxygen evolution/reduction reaction.

    PubMed

    Wang, Lei; Lin, Chong; Huang, Dekang; Zhang, Fengxing; Wang, Mingkui; Jin, Jian

    2014-07-01

    Oxygen electrochemistry has been intensely studied in the pursuit of sustainable and efficient energy conversion and storage solutions. Over the years, developing oxygen electrode catalysts with high activity and low cost remains a great challenge, despite tremendous efforts. Here, NixCo1-x(OH)2 is used as a bifunctional electrocatalyst for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). The effect of its compositions (x = 1, 0.55, 0) and morphologies (including both multilayer and single-layer NixCo1-x(OH)2) on catalytic activity is studied systematically in order to optimize the oxygen-electrochemical performance of 3d-M (M = Ni and Co) metal hydroxides. Our results show that the compositions of NixCo1-x(OH)2 has a great influence on overpotentials by comparing multilayer Co(OH)2, Ni0.55Co0.45(OH)2, and Ni(OH)2 for OER. Multilayer Ni(OH)2 exhibits the lowest overpotential of 324 mV at the current density of 5 mA/cm(2). Moreover, the overpotential could be greatly lowered by using single-layer NixCo1-x(OH)2. Single-layer Ni(OH)2 nanosheet manifests 71 mV overpotential decrease (5 mA/cm(2)) and a factor of 14 turnover frequency increase as compared to multilayer Co(OH)2 for OER. As for ORR, multilayer Co(OH)2 shows the best activity among multilayer NixCo1-x(OH)2. Similar to OER, single-layer NixCo1-x(OH)2 demonstrates enhanced ORR activity over multilayer NixCo1-x(OH)2. Single-layer Co(OH)2 exhibits the best catalytic activity and 3.7 electrons are transferred during oxygen reduction process. The successful identification of the composition and morphology effect of 3d metal hydroxides on electrocatalytic performance provides the foundation for rational design of active sites for high-performance catalyst for both OER and ORR. PMID:24915609

  8. A nitrogen-doped mesoporous carbon containing an embedded network of carbon nanotubes as a highly efficient catalyst for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Li, Jin-Cheng; Zhao, Shi-Yong; Hou, Peng-Xiang; Fang, Ruo-Pian; Liu, Chang; Liang, Ji; Luan, Jian; Shan, Xu-Yi; Cheng, Hui-Ming

    2015-11-01

    A nitrogen-doped mesoporous carbon containing a network of carbon nanotubes (CNTs) was produced for use as a catalyst for the oxygen reduction reaction (ORR). SiO2 nanoparticles were decorated with clusters of Fe atoms to act as catalyst seeds for CNT growth, after which the material was impregnated with aniline. After polymerization of the aniline, the material was pyrolysed and the SiO2 was removed by acid treatment. The resulting carbon-based hybrid also contained some Fe from the CNT growth catalyst and was doped with N from the aniline. The Fe-N species act as active catalytic sites and the CNT network enables efficient electron transport in the material. Mesopores left by the removal of the SiO2 template provide short transport pathways and easy access to ions. As a result, the catalyst showed not only excellent ORR activity, with 59 mV more positive onset potential and 30 mV more positive half-wave potential than a Pt/C catalyst, but also much longer durability and stronger tolerance to methanol crossover than a Pt/C catalyst.A nitrogen-doped mesoporous carbon containing a network of carbon nanotubes (CNTs) was produced for use as a catalyst for the oxygen reduction reaction (ORR). SiO2 nanoparticles were decorated with clusters of Fe atoms to act as catalyst seeds for CNT growth, after which the material was impregnated with aniline. After polymerization of the aniline, the material was pyrolysed and the SiO2 was removed by acid treatment. The resulting carbon-based hybrid also contained some Fe from the CNT growth catalyst and was doped with N from the aniline. The Fe-N species act as active catalytic sites and the CNT network enables efficient electron transport in the material. Mesopores left by the removal of the SiO2 template provide short transport pathways and easy access to ions. As a result, the catalyst showed not only excellent ORR activity, with 59 mV more positive onset potential and 30 mV more positive half-wave potential than a Pt/C catalyst

  9. Role of silver current collector on the operational stability of selected cobalt-containing oxide electrodes for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Chen, Yubo; Wang, Fucun; Chen, Dengjie; Dong, Feifei; Park, Hee Jung; Kwak, Chan; Shao, Zongping

    2012-07-01

    The long-term stability for oxygen reduction reaction (ORR) of two typical perovskite cathode materials of SOFCs, i.e., Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) and Sm0.5Sr0.5CoO3-δ (SSC), is investigated in a symmetric cell configuration under air condition at 700 °C using Sm0.2Ce0.8O1.9 (SDC) electrolyte substrate and silver current collectors. Moreover, two different methods of silver current collection are tested, i.e., whole electrode surface deposited with a diluted silver paste (CC-01) and a mesh-like current collector using concentrated silver paste (CC-02). Electrochemical impedance spectra are applied for stability investigations. With the CC-01 current collector, the performance of the electrode deteriorates significantly, although the initial performance is good. By contrast, fairly stable performance is obtained from symmetric cells with either BSCF or SSC + SDC electrodes using the CC-02 current collector, even though a phase transition is observed for BSCF. For instance, after approximately 800 h of continuous stability testing, the area-specific resistance of the BSCF electrode retains a value of approximately 0.065 Ω cm2, except for a slight fluctuation within the range of 0.06-0.07 Ω cm2. These findings reveal that both BSCF and SSC can be stably operated for ORR under symmetric cell conditions; however, an appropriate current collection method is crucial to achieving stable performance.

  10. Metal-support interaction in platinum and palladium nanoparticles loaded on nitrogen-doped mesoporous carbon for oxygen reduction reaction.

    PubMed

    Perini, Lorenzo; Durante, Christian; Favaro, Marco; Perazzolo, Valentina; Agnoli, Stefano; Schneider, Oliver; Granozzi, Gaetano; Gennaro, Armando

    2015-01-21

    Mesoporous carbons are highly porous materials, which show large surface area, chemical inertness and electrochemical performances superior to traditional carbon material. In this study, we report the preparation of nitrogen-doped and undoped mesoporous carbons by an optimized hard template procedure employing silica as template, sucrose and ammonia as carbon and nitrogen source, respectively. Surface area measurements assert a value of 900 and 600 m(2) g(-1) for the best doped and undoped samples, respectively. Such supports were then thoroughly characterized by surface science and electron microscopy tools. Afterward, they were decorated with Pt and Pd nanoparticles, and it was found that the presence of nitrogen defects plays a significant role in improving the metal particles dimension and dispersion. In fact, when doped supports are used, the resulting metal nanoparticles are smaller (2-4 nm) and less prone to aggregation. Photoemission measurements give evidence of a binding energy shift, which is consistent with the presence of an electronic interaction between nitrogen atoms and the metal nanoparticles, especially in the case of Pd. The catalytic properties of electrodes decorated with such catalyst/support systems were investigated by linear sweep voltammetry and by rotating disk electrode measurements, revealing excellent stability and good activity toward oxygen reduction reaction (ORR). In particular, although Pd nanoparticles always result in lower activity than Pt ones, both Pt and Pd electrodes based on the N-doped supports show an increased activity toward ORR with respect to the undoped ones. At the same mass loading, the Tafel slope and the stability test of the Pt@N-doped electrocatalysts indicate superior performances to that of a commercial Pt@C catalysts (30 wt % Pt on Vulcan XC-72, Johnson Matthey). PMID:25525718

  11. Core/shell face-centered tetragonal FePd/Pd nanoparticles as an efficient non-Pt catalyst for the oxygen reduction reaction

    SciTech Connect

    Zhu, Huiyuan; Jiang, Guangming; Zhang, Xu; Shen, Bo; Wu, Liheng; Zhang, Sen; Lu, Gang; Wu, Zhongbiao; Sun, Shouheng

    2015-10-04

    We report the synthesis of core/shell face-centered tetragonal (fct)-FePd/Pd nanoparticles (NPs) via reductive annealing of core/shell Pd/Fe3O4 NPs followed by temperature-controlled Fe etching in acetic acid. Among three different kinds of core/shell FePd/Pd NPs studied (FePd core at similar to 8 nm and Pd shell at 0.27, 0.65, or 0.81 nm), the fct-FePd/Pd-0.65 NPs are the most efficient catalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO4 with Pt-like activity and durability. This enhanced ORR catalysis arises from the desired Pd lattice compression in the 0.65 nm Pd shell induced by the fct-FePd core. Lastly, our study offers a general approach to enhance Pd catalysis in acid for ORB.

  12. Core/shell face-centered tetragonal FePd/Pd nanoparticles as an efficient non-Pt catalyst for the oxygen reduction reaction

    DOE PAGESBeta

    Zhu, Huiyuan; Jiang, Guangming; Zhang, Xu; Shen, Bo; Wu, Liheng; Zhang, Sen; Lu, Gang; Wu, Zhongbiao; Sun, Shouheng

    2015-10-04

    We report the synthesis of core/shell face-centered tetragonal (fct)-FePd/Pd nanoparticles (NPs) via reductive annealing of core/shell Pd/Fe3O4 NPs followed by temperature-controlled Fe etching in acetic acid. Among three different kinds of core/shell FePd/Pd NPs studied (FePd core at similar to 8 nm and Pd shell at 0.27, 0.65, or 0.81 nm), the fct-FePd/Pd-0.65 NPs are the most efficient catalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO4 with Pt-like activity and durability. This enhanced ORR catalysis arises from the desired Pd lattice compression in the 0.65 nm Pd shell induced by the fct-FePd core. Lastly, our study offersmore » a general approach to enhance Pd catalysis in acid for ORB.« less

  13. Effect of cationic molecules on the oxygen reduction reaction on fuel cell grade Pt/C (20 wt%) catalyst in potassium hydroxide (aq, 1 mol dm(-3)).

    PubMed

    Ong, Ai Lien; Inglis, Kenneth K; Whelligan, Daniel K; Murphy, Sam; Varcoe, John R

    2015-05-14

    This study investigates the effect of 1 mmol dm(-3) concentrations of a selection of small cationic molecules on the performance of a fuel cell grade oxygen reduction reaction (ORR) catalyst (Johnson Matthey HiSPEC 3000, 20 mass% Pt/C) in aqueous KOH (1 mol dm(-3)). The cationic molecules studied include quaternary ammonium (including those based on bicyclic systems) and imidazolium types as well as a phosphonium example: these serve as fully solubilised models for the commonly encountered head-groups in alkaline anion-exchange membranes (AAEM) and anion-exchange ionomers (AEI) that are being developed for application in alkaline polymer electrolyte fuel cells (APEFCs), batteries and electrolysers. Both cyclic and hydrodynamic linear sweep rotating disk electrode voltammetry techniques were used. The resulting voltammograms and subsequently derived data (e.g. apparent electrochemical active surface areas, Tafel plots, and number of [reduction] electrons transferred per O2) were compared. The results show that the imidazolium examples produced the highest level of interference towards the ORR on the Pt/C catalyst under the experimental conditions used. PMID:25877304

  14. Computerized reduction of elementary reaction sets for combustion modeling

    NASA Technical Reports Server (NTRS)

    Wikstrom, Carl V.

    1991-01-01

    If the entire set of elementary reactions is to be solved in the modeling of chemistry in computational fluid dynamics, a set of stiff ordinary differential equations must be integrated. Some of the reactions take place at very high rates, requiring short time steps, while others take place more slowly and make little progress in the short time step integration. The goal is to develop a procedure to automatically obtain sets of finite rate equations, consistent with a partial equilibrium assumptions, from an elementary set appropriate to local conditions. The possibility of computerized reaction reduction was demonstrated. However, the ability to use the reduced reaction set depends on the ability of the CFD approach in incorporate partial equilibrium calculations into the computer code. Therefore, the results should be tested on a code with partial equilibrium capability.

  15. First-Principles Design of Graphene-Based Active Catalysts for Oxygen Reduction and Evolution Reactions in the Aprotic Li-O2 Battery.

    PubMed

    Kang, Joonhee; Yu, Jong-Sung; Han, Byungchan

    2016-07-21

    Using first-principles density functional theory (DFT) calculations, we demonstrate that catalytic activities toward oxygen reduction and evolution reactions (ORR and OER) in a Li-O2 battery can be substantially improved with graphene-based materials. We accomplish the goal by calculating free energy diagrams for the redox reactions of oxygen to identify a rate-determining step controlling the overpotentials. We unveil that the catalytic performance is well described by the adsorption energies of the intermediates LiO2 and Li2O2 and propose that graphene-based materials can be substantially optimized through either by N doping or encapsulating Cu(111) single crystals. Furthermore, our systematic approach with DFT calculations applied to design of optimum catalysts enables screening of promising candidates for the oxygen electrochemistry leading to considerable improvement of efficiency of a range of renewable energy devices. PMID:27392527

  16. Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table.

    PubMed

    Toh, Rou Jun; Sofer, Zdeněk; Pumera, Martin

    2015-11-16

    Electrocatalysts have been developed to meet the needs and requirements of renewable energy applications. Metal oxides have been well explored and are promising for this purpose, however, many reports focus on only one or a few metal oxides at once. Herein, thirty metal oxides, which were either commercially available or synthesized by a simple and scalable method, were screened for comparison with regards to their electrocatalytic activity towards the oxygen reduction reaction (ORR). We show that although manganese, iron, cobalt, and nickel oxides generally displayed the ability to enhance the kinetics of oxygen reduction under alkaline conditions compared with bare glassy carbon, there is no significant correlation between the position of a metal on the periodic table and the electrocatalytic performance of its respective metal oxides. Moreover, it was also observed that mixed valent (+2, +3) oxides performed the poorest, compared with their respective pure metal oxides. These findings may be of paramount importance in the field of renewable energy. PMID:26351175

  17. Activity and Stability of Ruddlesden-Popper-Type La(n+1) Ni(n) O(3n+1) (n=1, 2, 3, and ∞) Electrocatalysts for Oxygen Reduction and Evolution Reactions in Alkaline Media.

    PubMed

    Yu, Jie; Sunarso, Jaka; Zhu, Yinlong; Xu, Xiaomin; Ran, Ran; Zhou, Wei; Shao, Zongping

    2016-02-18

    Increasing energy demands have stimulated intense research activity on cleaner energy conversion such as regenerative fuel cells and reversible metal-air batteries. It is highly challenging but desirable to develop low-cost bifunctional catalysts for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), the lack of which is currently one of the major limiting components towards commercialization of these technologies. Here, we have conducted a systematic study on the OER and ORR performances of the Ruddlesden-Popper family of La(n+1)Ni(n) O(3n+1) (n=1, 2, 3, and ∞) in an alkaline medium for the first time. It is apparent that the Ni-O bond lengths and the hyperstoichiometric oxides in the rock-salt layers correlate with the ORR activities, whereas the OER activities appear to be influenced by the OH(-) content on the surface of the compounds. In our case, the electronic configuration fails to predict the electrocatalytic activity of these compounds. This work provides guidelines to develop new electrocatalysts with improved performances. PMID:26788934

  18. Surprisingly high activity for oxygen reduction reaction of selected oxides lacking long oxygen-ion diffusion paths at intermediate temperatures: a case study of cobalt-free BaFeO(3-δ).

    PubMed

    Dong, Feifei; Chen, Yubo; Chen, Dengjie; Shao, Zongping

    2014-07-23

    The widespread application of solid oxide fuel cell technology requires the development of innovative electrodes with high activity for oxygen reduction reaction (ORR) at intermediate temperatures. Here, we demonstrate that a cobalt-free parent oxide BaFeO(3-δ) (BF), which lacks long-range oxygen-ion diffusion paths, has surprisingly high electrocatalytic activity for ORR. Both in situ high-temperature X-ray diffraction analysis on room-temperature powder and transmission electron microscopy on quenched powder are applied to investigate the crystal structure of BF. Despite the lack of long oxygen-ion diffusion paths, the easy redox of iron cations as demonstrated by thermal gravimetric analysis (TGA) and oxygen temperature-programmed desorption and the high oxygen vacancy concentration as supported by iodometric titration and TGA benefit the reduction of oxygen to oxygen ions. Moreover, the electrical conductivity relaxation technique in conjunction with a transient thermogravimetric study reveals very high surface exchange kinetics of BF oxide. At 700 °C, the area specific resistance of BF cathode, as expressed by a symmetrical cell configuration, is only ∼0.021 Ω cm(2), and the derived single fuel cell achieves high power output with a peak power density of 870 mW cm(-2). It suggests that an undoped BF parent oxide can be used as a high-efficiency catalyst for ORR. PMID:24978102

  19. One Dimensional Graphitic Carbon Nitrides as Effective Metal-Free Oxygen Reduction Catalysts

    PubMed Central

    Tahir, Muhammad; Mahmood, Nasir; Zhu, Jinghan; Mahmood, Asif; Butt, Faheem K.; Rizwan, Syed; Aslam, Imran; Tanveer, M.; Idrees, Faryal; Shakir, Imran; Cao, Chuanbao; Hou, Yanglong

    2015-01-01

    To explore the effect of morphology on catalytic properties of graphitic carbon nitride (GCN), we have studied oxygen reduction reaction (ORR) performance of two different morphologies of GCN in alkaline media. Among both, tubular GCN react with dissolved oxygen in the ORR with an onset potential close to commercial Pt/C. Furthermore, the higher stability and excellent methanol tolerance of tubular GCN compared to Pt/C emphasizes its suitability for fuel cells. PMID:26201998

  20. Heterogeneous Electrocatalyst of Palladium-Cobalt-Phosphorus on Carbon Support for Oxygen Reduction Reaction in High Temperature Proton Exchange Membrane Fuel Cells.

    PubMed

    You, Dae Jong; Pak, Chanho; Jin, Seon-Ah; Lee, Kang Hee; Kwon, Kyungjung; Choi, Kyoung Hwan; Heo, Pil Won; Jang, Hongchul; Kim, Jun Young; Kim, Ji Man

    2016-05-01

    Palladium-cobalt-phosphorus (PdCoP) catalysts supported on carbon (Ketjen Black) were investigated as a cathode catalyst for oxygen reduction reaction (ORR) in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The PdCoP catalyst was synthesized via a modified polyol process in teflon-sealed reactor by microwave-heating. From X-ray diffraction and transmission electron microscopic analysis, the PdCoP catalyst exhibits a face-centered cubic structure, similar to palladium (Pd), which is attributed to form a good solid solution of Co atoms and P atoms in the Pd lattice. The PdCoP nanoparticles with average diameter of 2.3 nm were uniformly distributed on the carbon support. The electrochemical surface area (ECSA) and ORR activity of PdP, PdCo and PdCoP catalysts were measured using a rotating disk electrode technique with cyclic voltammetry and the linear sweep method. The PdCoP catalysts showed the highest performances for ECSA and ORR, which might be attributed both to formation of small nanoparticle by phosphorus atom and to change in lattice constant of Pd by cobalt atom. Furthermore, The HT-PEMFCs single cell performance employing PdCoP catalyst exhibited an enhanced cell performance compared to a single cell using the PdP and PdCo catalysts. This result indicates the importance of electric and geometric control of Pd alloy nanoparticles that can improve the catalytic activity. This synergistic combination of Co and P with Pd could provide the direction of development of non-Pt catalyst for fuel cell system. PMID:27483757

  1. Cumulative effect of transition metals on nitrogen and fluorine co-doped graphite nanofibers: an efficient and highly durable non-precious metal catalyst for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Peera, S. Gouse; Arunchander, A.; Sahu, A. K.

    2016-07-01

    Nitrogen and fluorine co-doped graphite nanofibers (N/F-GNF) and their cumulative effect with Fe and Co have been developed as an alternative non-precious metal catalyst for efficient oxygen reduction reaction (ORR) in acidic media. The synergistic effect between the doped hetero atoms and the co-ordinated Fe and Co towards ORR activity and durability of the catalyst is deeply investigated. A high ORR onset potential comparable with commercial Pt/C catalyst is observed with the Fe-Co/NF-GNF catalyst, which indicates that this catalyst is a potential alternative to Pt/C. A fivefold increase in mass activity is achieved by the Fe-Co/NF-GNF catalyst compared to the simple N/F-GNF catalyst, which endorses the significant role of transition metal atoms in enhancing ORR activity. The advanced Fe-Co/NF-GNF catalyst also exhibits complete tolerance to CH3OH and CO. The Fe-Co/NF-GNF catalyst also exhibits excellent durability towards the ORR with only a 10 mV negative shift in its half wave potential after a 10 000 repeated potential cycling test, whereas in the case of a commercial Pt/C catalyst there was an ~110 mV negative shift under similar environmental conditions. More stringent corrosive test cycles were also performed by maintaining the cell as high as 1.4 V with a later decrease to 0.6 V vs. RHE for 300 cycles, which showed the excellent durability of the Fe-Co/NF-GNF catalyst in comparison with the Pt/C catalyst. XPS analysis of the Fe-Co/NF-GNF catalyst presents the ORR active chemical states of N (pyridinic-N and graphitic-N) and F (semi-ionic-F) and the co-ordinated sites of Fe and Co species with the dopants. The excellent performance and durability of the Fe-Co/NF-GNF catalyst is due to the synergistic effect between the hetero atoms dopants (N and F) and strong co-ordinating bonds of M-N-C, which protect the graphene layers around the metallic species and greatly mitigates the leaching of Co and Fe during the long term cycling test. The high activity and

  2. A simple synthesis method of sulfur-free Fe-N-C catalyst witih high ORR activity

    SciTech Connect

    Ding, Zhongfen; Johnston, Christina M; Zelenay, Piotr

    2010-01-01

    To try to deconvolute which factors affect the activity and durability of metal-nitrogen-carbon (M-N-C) type non-precious catalysts for oxygen reduction reaction (ORR), M-N-C catalysts based on ion chloride, polyaniline (PANI) and Ketjen Black carbon support were synthesized using different synthetic conditions. The catalysts were characterized electrochemically and tested as cathodes for Hydrogen fuel cells. PANI is usually chemically oxidative polymerized using ammonium persulfate (APS) as oxidant. To eliminate sulfur in the synthesized catalysts, a simple synthesis method using ion chloride as oxidant for aniline polymerization was developed. Two different aniline polymerization conditions led to very different product morphologies. Synthesized at low initial proton concentration, the final product was composed of dense micrometer sized particles. A decomposable salt was found to be able to prohibit PANI cross linking during the drying and annealing process and thus led to porous product. The porous catalyst has much higher ORR activity than the dense product due to more accessible active sites. Synthesized at high proton concentration, the catalyst appeared to be porous. The decomposable salt treatment did not make too much improvement in the porous structure and electrochemical activity. However, fuel cell testing using air as cathode feeder indicates that the salt treatment improves mass transfer in the cathode layer. Catalyst synthesized using this simple method has performance comparable to our state-of-the art catalyst synthesized in a much more complicated procedure. The factor that sulfur sources are completely eliminated in the synthesis suggests that sulfur is not necessary for the ORR catalysis activity.

  3. Mechanisms of Enhanced Electrocatalytic Activity for Oxygen Reduction Reaction on High-Index Platinum n(111)-(111) Surfaces.

    PubMed

    Yue, Jeffrey; Du, Zheng; Shao, Minhua

    2015-09-01

    Oxygen reduction reactions (ORRs) on high-index planes of Pt n(111)-(111) were studied by density functional theory (DFT). The stepped surfaces, where n = 2, 3, and 4, showed that O2, O, and OH exhibited higher binding energies along the step compared to the terrace plane. The Pt atoms along the step can become distorted through the binding of the O and OH, where the shift in position of the Pt atoms is the largest along the stepped sites, hence forming stronger bonds with O atoms. One of the two O atoms produced from the bond dissociation of O2 will push the other one down a step with lower binding energies, consequently reducing the energy required for the protonation reaction (O + H(+) → OH, and OH + H(+) → H2O). The quicker recovery back to the clean Pt surface would therefore improve the catalytic properties of Pt nanoparticles, especially those with exposure to high-indexed facets. PMID:26267316

  4. Role of Cu-Ion Doping in Cu-α-MnO2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction

    DOE PAGESBeta

    Davis, Danae J.; Lambert, Timothy N.; Vigil, Julian A.; Rodriguez, Mark A.; Brumbach, Michael T.; Coker, Eric N.; Limmer, Steven J.

    2014-07-09

    The role of Cu-ion doping in α-MnO2 electrocatalysts for the oxygen reduction reaction in alkaline electrolyte was investigated. Copper doped α-MnO2 nanowires (Cu-α-MnO2) were prepared with varying amounts of Cu2+ using a solvothermal method. The electrocatalytic dataindicates that Cu-α-MnO2 nanowires have higher terminal current densities, enhanced kinetic rate constants, and improved charge transfer resistances that trend with Cu-content, exceeding values attained by α-MnO2 alone. The observed improvement in catalytic behavior correlates with an increase in Mn3+ content for the Cu-α-MnO2 nanowires. The Mn3+/Mn4+ couple is themediator for the rate-limiting redox driven O2-/OH- exchange. It is proposed that O2 adsorbs viaanmore » axial site (the eg orbital on the Mn3+ d4 ion) at the surface, or at edge defects, of the nanowireand that the increase in covalent nature of the nanowire with Cu-ion doping leads to stabilization of O2 adsorbates and faster rates of reduction. This work is applicable to other manganese oxide electrocatalysts and shows for the first time there is a correlation for manganese oxides between electrocatalytic activity for the ORR in alkaline electrolyte and an increase in Mn3+ character of the oxide.« less

  5. Influence of water on the reaction path of the oxygen reduction reaction in fuel cells

    NASA Astrophysics Data System (ADS)

    Malardier-Jugroot, Cecile; Groves, Michael; Jugroot, Manish

    2015-04-01

    The development of fuel cell technology has been limited in part due to the cost of the catalyst used in the cell and the rate limiting oxygen reduction reaction. We will present a molecular modelling study focus toward the prediction of improved durability and catalytic efficiency of the Platinum catalyst using doped graphene and doped single walled carbon nanotube surface. The most promising carbon supports - active centre systems were then studied in the gas phase and with explicit water molecules to model the oxygen reduction reaction and tailor the catalytic centres to improve the efficiency of this reaction while reducing the probability of occurrence of side reactions. Two major conclusions have been drawn from this analysis of the oxygen reduction reaction with and without water present. The doping of the carbon surface leads to a stronger platinum-surface interaction and does help the breaking of the oxygen-oxygen bond. These two are interrelated since the stronger surface-platinum bond allows for the same orbitals to interact with the oxygen-oxygen orbital. In addition, the dopants could make the surfaces more polar thus retaining water which might help catalyze the reaction, this property could be very promising to increase the effectiveness of fuel cell cathodes.

  6. Nitrogen and fluorine dual-doped mesoporous graphene: a high-performance metal-free ORR electrocatalyst with a super-low HO2(-) yield.

    PubMed

    Jiang, Shu; Sun, Yujing; Dai, Haichao; Hu, Jingting; Ni, Pengjuan; Wang, Yilin; Li, Zhen; Li, Zhuang

    2015-06-28

    In this study, we successfully, for the first time, prepared nitrogen and fluorine dual-doped mesoporous graphene (NF-MG) via the thermal treatment of graphene oxide/polyaniline composites (GO/PANI) and NH4F. Benefiting from the synergistic effect of N and F co-doping into the G framework, the oxygen reduction reaction performance of the optimal catalyst (NF-MG3) is comparable with the-state-of-the-art Pt/C catalyst in an alkaline medium, which makes it an ideal candidate as an efficient metal-free ORR electrocatalyst in fuel cells. PMID:26032909

  7. Chemical reactions occurring during direct solar reduction of CO2.

    PubMed

    Lyma, J L; Jensen, R J

    2001-09-28

    At high temperatures carbon dioxide may absorb solar radiation and react to form carbon monoxide and molecular oxygen. The CO, so produced, may be converted by well-established means to a combustible fuel, such as methanol. We intend to make a future demonstration of the solar reduction of CO2 based on these processes. This paper, however, addresses only the problem of preserving, or even enhancing, the initial photolytic CO by quenching the hot gas with colder H2O or CO2. We present model calculations with a reaction mechanism used extensively in other calculations. If a CO2 gas stream is heated and photolyzed by intense solar radiation and then allowed to cool slowly, it will react back to the initial CO2 by a series of elementary chemical reactions. The back reaction to CO2 can be terminated with the rapid addition of CO2, water, or a mixture. Calculations show that a three-fold quench with pure CO2 will stop the reactions and preserve over 90% of the initial photolytic CO. We find that water has one of two effects. It can either increase the CO level, or it can catalyze the recombination of O and CO to CO2. The gas temperature is the determining factor. If the quench gas is not sufficient to keep the temperature below approximately 1100 K, a chain-branching reaction dominates and the reaction to CO2 occurs. If the temperature stays below that level a chain terminating reaction dominates and the CO is increased. The former case occurs below approximately a fourfold quench with a water/CO2 mixture. The later case occurs when the quench is greater than fourfold. We conclude that CO2, H2O, or a mixture may quench the hot gas stream photolyzed by solar radiation and preserve the photolytic CO. PMID:11589409

  8. A review of the stability and durability of non-precious metal catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Banham, Dustin; Ye, Siyu; Pei, Katie; Ozaki, Jun-ichi; Kishimoto, Takeaki; Imashiro, Yasuo

    2015-07-01

    A major hurdle to the widespread commercialization of proton exchange membrane fuel cells (PEMFCs) is the high loading of noble metal (Pt/Pt-alloy) catalyst at the cathode, which is necessary to facilitate the inherently sluggish oxygen reduction reaction (ORR). To eliminate the use of Pt/Pt-alloy catalysts at the cathode of PEMFCs and thus significantly reduce the cost, extensive research on non-precious metal catalysts (NPMCs) has been carried out over the past decade. Major advances in improving the ORR activity of NPMCs, particularly Fe- and Co-based NPMCs, have elevated these materials to a level at which they can start to be considered as potential alternatives to Pt/Pt-alloy catalysts. Unfortunately, the stability (performance loss following galvanostatic experiments) of these materials is currently unacceptably low and the durability (performance loss following voltage cycling) remains uncertain. The three primary mechanisms of instability are: (a) Leaching of the metal site, (b) Oxidative attack by H2O2, and (c) Protonation followed by possible anion adsorption of the active site. While (a) has largely been solved, further work is required to understand and prevent losses from (b) and/or (c). Thus, this review is focused on historical progress in (and possible future strategies for) improving the stability/durability of NPMCs.

  9. Facile synthesis of N-rich carbon quantum dots by spontaneous polymerization and incision of solvents as efficient bioimaging probes and advanced electrocatalysts for oxygen reduction reaction.

    PubMed

    Lei, Zhouyue; Xu, Shengjie; Wan, Jiaxun; Wu, Peiyi

    2016-01-28

    In this study, uniform nitrogen-doped carbon quantum dots (N-CDs) were synthesized through a one-step solvothermal process of cyclic and nitrogen-rich solvents, such as N-methyl-2-pyrrolidone (NMP) and dimethyl-imidazolidinone (DMEU), under mild conditions. The products exhibited strong light blue fluorescence, good cell permeability and low cytotoxicity. Moreover, after a facile post-thermal treatment, it developed a lotus seedpod surface-like structure of seed-like N-CDs decorating on the surface of carbon layers with a high proportion of quaternary nitrogen moieties that exhibited excellent electrocatalytic activity and long-term durability towards the oxygen reduction reaction (ORR). The peak potential was -160 mV, which was comparable to or even lower than commercial Pt/C catalysts. Therefore, this study provides an alternative facile approach to the synthesis of versatile carbon quantum dots (CDs) with widespread commercial application prospects, not only as bioimaging probes but also as promising electrocatalysts for the metal-free ORR. PMID:26739885

  10. Porous Core-Shell Fe3C Embedded N-doped Carbon Nanofibers as an Effective Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Ren, Guangyuan; Lu, Xianyong; Li, Yunan; Zhu, Ying; Dai, Liming; Jiang, Lei

    2016-02-17

    The development of nonprecious-metal-based electrocatalysts with high oxygen reduction reaction (ORR) activity, low cost, and good durability in both alkaline and acidic media is very important for application of full cells. Herein, we developed a facile and economical strategy to obtain porous core-shell Fe3C embedded nitrogen-doped carbon nanofibers (Fe3C@NCNF-X, where X denotes pyrolysis temperature) by electrospinning of polyvinylidene fluoride (PVDF) and FeCl3 mixture, chemical vapor phase polymerization of pyrrole, and followed by pyrolysis of composite nanofibers at high temperatures. Note that the FeCl3 and polypyrrole acts as precursor for Fe3C core and N-doped carbon shell, respectively. Moreover, PVDF not only plays a role as carbon resources, but also provides porous structures due to hydrogen fluoride exposure originated from thermal decomposition of PVDF. The resultant Fe3C@NCNF-X catalysts, particularly Fe3C@NCNF-900, showed efficient electrocatalytic performance for ORR in both alkaline and acidic solutions, which are attributed to the synergistic effect between Fe3C and N-doped carbon as catalytic active sites, and carbon shell protects Fe3C from leaching out. In addition, the Fe3C@NCNF-X catalyst displayed a better long-term stability, free from methanol crossover and CO-poisoning effects than those of Pt/C, which is of great significance for the design and development of advanced electrocatalysts based on nonprecious metals. PMID:26808226

  11. Fabrication of PdCo Bimetallic Nanoparticles Anchored on Three-Dimensional Ordered N-Doped Porous Carbon as an Efficient Catalyst for Oxygen Reduction Reaction.

    PubMed

    Xue, Hairong; Tang, Jing; Gong, Hao; Guo, Hu; Fan, Xiaoli; Wang, Tao; He, Jianping; Yamauchi, Yusuke

    2016-08-17

    PdCo bimetallic nanoparticles (NPs) anchored on three-dimensional (3D) ordered N-doped porous carbon (PdCo/NPC) were fabricated by an in situ synthesis. Within this composite, N-doped porous carbon (NPC) with an ordered mesoporous structure possesses a high surface area (659.6 m(2) g(-1)), which can facilitate electrolyte infiltration. NPC also acts as a perfect 3D conductive network, guaranteeing fast electron transport. In addition, homogeneously distributed PdCo alloy NPs (∼15 nm) combined with the doping of the N element can significantly improve the electrocatalytic activity for the oxygen reduction reaction (ORR). Due to the structural and material superiority, although the weight percentage of PdCo NPs (∼8 wt%) is much smaller than that of commercial Pt/C (20 wt%), the PdCo/NPC catalyst exhibits similar excellent electrocatalytic activity; however, its superior durability and methanol-tolerance ability of the ORR are as great as those of commercial Pt/C in alkaline media. PMID:27441490

  12. High Performance and Cost-Effective Direct Methanol Fuel Cells: Fe-N-C Methanol-Tolerant Oxygen Reduction Reaction Catalysts.

    PubMed

    Sebastián, David; Serov, Alexey; Artyushkova, Kateryna; Gordon, Jonathan; Atanassov, Plamen; Aricò, Antonino S; Baglio, Vincenzo

    2016-08-01

    Direct methanol fuel cells (DMFCs) offer great advantages for the supply of power with high efficiency and large energy density. The search for a cost-effective, active, stable and methanol-tolerant catalyst for the oxygen reduction reaction (ORR) is still a great challenge. In this work, platinum group metal-free (PGM-free) catalysts based on Fe-N-C are investigated in acidic medium. Post-treatment of the catalyst improves the ORR activity compared with previously published PGM-free formulations and shows an excellent tolerance to the presence of methanol. The feasibility for application in DMFC under a wide range of operating conditions is demonstrated, with a maximum power density of approximately 50 mW cm(-2) and a negligible methanol crossover effect on the performance. A review of the most recent PGM-free cathode formulations for DMFC indicates that this formulation leads to the highest performance at a low membrane-electrode assembly (MEA) cost. Moreover, a 100 h durability test in DMFC shows suitable applicability, with a similar performance-time behavior compared to common MEAs based on Pt cathodes. PMID:27376964

  13. Co@Co3 O4 @PPD Core@bishell Nanoparticle-Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction.

    PubMed

    Wang, Zhijuan; Li, Bing; Ge, Xiaoming; Goh, F W Thomas; Zhang, Xiao; Du, Guojun; Wuu, Delvin; Liu, Zhaolin; Andy Hor, T S; Zhang, Hua; Zong, Yun

    2016-05-01

    Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high-performance primary zinc-air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co3 O4 core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co3 O4 @PPD core@bishell structure, obtained via a three-step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co3 O4 NPs encapsulated by ultrathin highly graphitized N-doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N-doped graphitic carbon outer shell and ultrathin nanocrystalline Co3 O4 inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co3 O4 @PPD in air-cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm(-2) . PMID:27031907

  14. Influence of sp(3)-sp(2) Carbon Nanodomains on Metal/Support Interaction, Catalyst Durability, and Catalytic Activity for the Oxygen Reduction Reaction.

    PubMed

    Campos-Roldán, Carlos A; Ramos-Sánchez, Guadalupe; Gonzalez-Huerta, Rosa G; Vargas García, Jorge R; Balbuena, Perla B; Alonso-Vante, Nicolas

    2016-09-01

    In this work, platinum nanoparticles were impregnated by two different techniques, namely the carbonyl chemical route and photodeposition, onto systematically surface-modified multiwalled carbon nanotubes. The different interactions between platinum nanoparticles with sp(2)-sp(3) carbon nanodomains were investigated. The oxidation of an adsorbed monolayer of carbon monoxide, used to probe electronic catalytic modification, suggests a selective nucleation of platinum nanoparticles onto sp(2) carbon nanodomains when photodeposition synthesis is carried out. XPS attests the catalytic center electronic modification obtained by photodeposition. DFT calculations were used to determine the interaction energy of a Pt cluster with sp(2) and sp(3) carbon surfaces as well as with oxidized ones. The interaction energy and electronic structure of the platinum cluster presents dramatic changes as a function of the support surface chemistry, which also modifies its catalytic properties evaluated by the interaction with CO. The interaction energy was calculated to be 8-fold higher on sp(3) and oxidized surfaces in comparison to sp(2) domains. Accelerated Stability Test (AST) was applied only on the electronic-modified materials to evaluate the active phase degradation and their activity toward oxygen reduction reaction (ORR). The stability of photodeposited materials is correlated with the surface chemical nature of supports indicating that platinum nanoparticles supported onto multiwalled carbon nanotubes with the highest sp(2) character show the higher stability and activity toward ORR. PMID:27494283

  15. Gram-level synthesis of core-shell structured catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Luo, Mingchuan; Wei, Lingli; Wang, Fanghui; Han, Kefei; Zhu, Hong

    2014-12-01

    Over the past decade, Pt based core-shell structured alloys have been studied extensively as oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs) because of their distinctive electrochemical performance and low Pt loading. In this paper, a facile route based on microwave-assisted polyol method and chemical dealloying process is proposed to synthesize carbon supported core-shell structured nanoparticles (NPs) in gram-level for ORR electrocatalysis in PEMFCs. The obtained samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). These physical characterization indicate that the final synthesized NPs are highly dispersed on the carbon support, and in a core-shell structure with CuPt alloy as the core and Pt as the shell. Electrochemical measurements, conducted by cyclic voltammetry (CV) and rotating disk electrode (RDE) tests, show the core-shell structured catalyst exhibit a 3× increase in mass activity and a 2× increase in specific activity over the commercial Pt/C catalyst, respectively. These results demonstrate that this route can be a reliable way to synthesize low-Pt catalyst in large-scale for PEMFCs.

  16. A highly efficient electrocatalyst for oxygen reduction reaction: phosphorus and nitrogen co-doped hierarchically ordered porous carbon derived from an iron-functionalized polymer.

    PubMed

    Deng, Chengwei; Zhong, Hexiang; Li, Xianfeng; Yao, Lan; Zhang, Huamin

    2016-01-21

    Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm(2) g(-1)) and a pore volume of 1.14 cm(3) g(-1). Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated. PMID:26692228

  17. A model reduction method for biochemical reaction networks

    PubMed Central

    2014-01-01

    Background In this paper we propose a model reduction method for biochemical reaction networks governed by a variety of reversible and irreversible enzyme kinetic rate laws, including reversible Michaelis-Menten and Hill kinetics. The method proceeds by a stepwise reduction in the number of complexes, defined as the left and right-hand sides of the reactions in the network. It is based on the Kron reduction of the weighted Laplacian matrix, which describes the graph structure of the complexes and reactions in the network. It does not rely on prior knowledge of the dynamic behaviour of the network and hence can be automated, as we demonstrate. The reduced network has fewer complexes, reactions, variables and parameters as compared to the original network, and yet the behaviour of a preselected set of significant metabolites in the reduced network resembles that of the original network. Moreover the reduced network largely retains the structure and kinetics of the original model. Results We apply our method to a yeast glycolysis model and a rat liver fatty acid beta-oxidation model. When the number of state variables in the yeast model is reduced from 12 to 7, the difference between metabolite concentrations in the reduced and the full model, averaged over time and species, is only 8%. Likewise, when the number of state variables in the rat-liver beta-oxidation model is reduced from 42 to 29, the difference between the reduced model and the full model is 7.5%. Conclusions The method has improved our understanding of the dynamics of the two networks. We found that, contrary to the general disposition, the first few metabolites which were deleted from the network during our stepwise reduction approach, are not those with the shortest convergence times. It shows that our reduction approach performs differently from other approaches that are based on time-scale separation. The method can be used to facilitate fitting of the parameters or to embed a detailed model of

  18. Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

    NASA Astrophysics Data System (ADS)

    O'Laoire, Cormac Micheal

    Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li

  19. La2O2CO3 Encapsulated La2O3 Nanoparticles Supported on Carbon as Superior Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Gu, Weiwei; Liu, Jingjun; Hu, Mingan; Wang, Feng; Song, Ye

    2015-12-01

    Constructing nanoscale hybrid materials with unique interfacial structures by using various metal oxides and carbon supports as building blocks are of great importance to develop highly active, economical hybrid catalysts for oxygen reduction reaction (ORR). In this work, La2O2CO3 encapsulated La2O3 nanoparticles on a carbon black (La2O2CO3@La2O3/C) were fabricated via chemical precipitation in an aqueous solution containing different concentrations of cetyltrimethyl ammonium bromide (CTAB), followed by calcination at 750 °C. At a given CTAB concentration 24.8 mmol/L, the obtained lanthanum compound nanoparticles reach the smallest particle size (7.1 nm) and are well-dispersed on the carbon surface. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results demonstrate the formation of La2O2CO3 located on the surface of La2O3 nanoparticles in the hybrid. The synthesized La2O2CO3@La2O3/C hybrid exhibits a significantly enhanced electrocatalytic activity in electrocatalysis experiments relative to pure La2O3, La2O2CO3, and carbon in an alkaline environment, by using the R(R)DE technique. Moreover, its long-term stability also outperforms that obtained by commercial Pt/C catalysts (E-TEK). The exact origin of the fast ORR kinetics is mainly ascribed to the La2O2CO3 layer sandwiched at the interface of carbon and La2O3, which contributes favorable surface-adsorbed hydroxide (-OH(-)(ad)) substitution and promotes active oxygen adsorption at the interfaces. The unique covalent -C-O-C(═O)-O-La-O- bonds, formed at the interfaces between La2O2CO3 and carbon, can act as active sites for the improved ORR kinetics over this hybrid catalyst. Therefore, the fabrication of lanthanum compound-based hybrid material with an unique interfacial structure maybe open a new way to develop carbon-supported metal oxides as next-generation of ORR catalysts. PMID:26619261

  20. Nitrogen and sulfur co-doped carbon with three-dimensional ordered macroporosity: An efficient metal-free oxygen reduction catalyst derived from ionic liquid

    NASA Astrophysics Data System (ADS)

    Wu, Hui; Shi, Liang; Lei, Jiaheng; Liu, Dan; Qu, Deyu; Xie, Zhizhong; Du, Xiaodi; Yang, Peng; Hu, Xiaosong; Li, Junsheng; Tang, Haolin

    2016-08-01

    The development of efficient and durable catalyst for oxygen reduction reaction (ORR) is critical for the practical application of proton exchange membrane fuel cell (PEMFC). A novel imidazole based ionic liquid is synthesized in this study and used subsequently for the preparation of a N and S co-doped metal-free catalyst with three dimensional ordered microstructure. The catalyst prepared at 1100 °C showed improved ORR catalytic performance and stability compared to commercial Pt/C catalyst. We demonstrate that the high graphitic N content and high degree of graphitization of the synthesized catalyst is responsible for its superb ORR activity. Our results suggest that the N and S co-doped metal-free catalyst reported here is a promising alternative to traditional ORR catalyst based on noble metal. Furthermore, the current study also demonstrate that importance of morphology engineering in the development of high performance ORR catalyst.

  1. Nitrogen-doped nanoporous carbon derived from waste pomelo peel as a metal-free electrocatalyst for the oxygen reduction reaction.

    PubMed

    Yuan, Wenjing; Feng, Yi; Xie, Anjian; Zhang, Xiuzhen; Huang, Fangzhi; Li, Shikuo; Zhang, Xing; Shen, Yuhua

    2016-04-21

    The development of a new catalyst for the low-cost, environmentally friendly and highly efficient oxygen reduction reaction (ORR) is important for the commercialization of fuel cells. Herein, a smart strategy was proposed for the preparation of a novel nitrogen-doped nanoporous carbon (N-PC) using resource-rich pomelo peel, a type of waste, as starting material. The typical product (N-PC-1000) possesses a high BET surface area (up to 1444.9 m(2) g(-1)), porous structure and high graphitic N content. In alkaline and acidic media, the N-PC-1000 shows not only decent catalytic activities in terms of onset potential and current density, but also has excellent tolerance to methanol poisoning effects and durability. This study provides worthy inspiration for using other environmental wastes to prepare related functional carbon materials with a variety of promising practical applications such as supercapacitors and lithium-ion batteries. PMID:27055724

  2. Diversity of Contaminant Reduction Reactions by Zero-Valent Iron: Role of the Reductate

    SciTech Connect

    Miehr, R; Tratnyek, Paul G.; Bandstra, J; Scherer, Michelle; Alowitz, M; Bylaska, Eric J.

    2004-01-01

    The reactions of 8 model contaminants with 9 types of granular Fe(0) were studied in batch experiments using consistent experimental conditions. The model contaminants (herein referred to as reductates because they were reduced by the iron metal) included cations (Cu2+), anions (CrO42-; NO3-; and 5,5,7,7-indigotetrasulfonate), and neutral species (2-chloroacetophenone; 2,4,6-trinitrotoluene; carbon tetrachloride; and trichloroethene). The diversity of this range of reductates offers a uniquely broad perspective on the reactivity of Fe(0). Rate constants for disappearance of the reductates vary over as much as 4 orders of magnitude for particular reductates (due to differences in the 9 types of iron) but differences among the reductates were even larger, ranging over almost 7 orders of magnitude. Various ways of summarizing the data all suggest that relative reactivities with Fe(0) varies in the order: Cu2, I4S > 2CAP, TNT > CT, Cr6 > TCE > NO3. Although the reductate h as the largest effect on disappearance kinetics, more subtle differences in reactivity due to the type of Fe(0) suggests that removal of Cr6 and NO3 (the inorganic anions) involves adsorption to oxides on the Fe(0), whereas the disappearance kinetics of all other types of reductants is favored by reduction on comparatively oxide-free metal. Correlation analysis of the disappearance rate constants using descriptors of the reductates calculated by molecular modeling (energies of the lowest unoccupied molecular orbitals, LUMO, highest occupied molecular orbitals, HOMO, and HOMO-LUMO gaps) showed that reactivities generally increase with decreasing ELUMO and increasing EGAP (and, therefore, increasing chemical hardness h).

  3. Nitrogen-doped nanoporous carbon derived from waste pomelo peel as a metal-free electrocatalyst for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yuan, Wenjing; Feng, Yi; Xie, Anjian; Zhang, Xiuzhen; Huang, Fangzhi; Li, Shikuo; Zhang, Xing; Shen, Yuhua

    2016-04-01

    The development of a new catalyst for the low-cost, environmentally friendly and highly efficient oxygen reduction reaction (ORR) is important for the commercialization of fuel cells. Herein, a smart strategy was proposed for the preparation of a novel nitrogen-doped nanoporous carbon (N-PC) using resource-rich pomelo peel, a type of waste, as starting material. The typical product (N-PC-1000) possesses a high BET surface area (up to 1444.9 m2 g-1), porous structure and high graphitic N content. In alkaline and acidic media, the N-PC-1000 shows not only decent catalytic activities in terms of onset potential and current density, but also has excellent tolerance to methanol poisoning effects and durability. This study provides worthy inspiration for using other environmental wastes to prepare related functional carbon materials with a variety of promising practical applications such as supercapacitors and lithium-ion batteries.The development of a new catalyst for the low-cost, environmentally friendly and highly efficient oxygen reduction reaction (ORR) is important for the commercialization of fuel cells. Herein, a smart strategy was proposed for the preparation of a novel nitrogen-doped nanoporous carbon (N-PC) using resource-rich pomelo peel, a type of waste, as starting material. The typical product (N-PC-1000) possesses a high BET surface area (up to 1444.9 m2 g-1), porous structure and high graphitic N content. In alkaline and acidic media, the N-PC-1000 shows not only decent catalytic activities in terms of onset potential and current density, but also has excellent tolerance to methanol poisoning effects and durability. This study provides worthy inspiration for using other environmental wastes to prepare related functional carbon materials with a variety of promising practical applications such as supercapacitors and lithium-ion batteries. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00764c

  4. Cumulative effect of transition metals on nitrogen and fluorine co-doped graphite nanofibers: an efficient and highly durable non-precious metal catalyst for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Peera, S. Gouse; Arunchander, A.; Sahu, A. K.

    2016-07-01

    Nitrogen and fluorine co-doped graphite nanofibers (N/F-GNF) and their cumulative effect with Fe and Co have been developed as an alternative non-precious metal catalyst for efficient oxygen reduction reaction (ORR) in acidic media. The synergistic effect between the doped hetero atoms and the co-ordinated Fe and Co towards ORR activity and durability of the catalyst is deeply investigated. A high ORR onset potential comparable with commercial Pt/C catalyst is observed with the Fe-Co/NF-GNF catalyst, which indicates that this catalyst is a potential alternative to Pt/C. A fivefold increase in mass activity is achieved by the Fe-Co/NF-GNF catalyst compared to the simple N/F-GNF catalyst, which endorses the significant role of transition metal atoms in enhancing ORR activity. The advanced Fe-Co/NF-GNF catalyst also exhibits complete tolerance to CH3OH and CO. The Fe-Co/NF-GNF catalyst also exhibits excellent durability towards the ORR with only a 10 mV negative shift in its half wave potential after a 10 000 repeated potential cycling test, whereas in the case of a commercial Pt/C catalyst there was an ~110 mV negative shift under similar environmental conditions. More stringent corrosive test cycles were also performed by maintaining the cell as high as 1.4 V with a later decrease to 0.6 V vs. RHE for 300 cycles, which showed the excellent durability of the Fe-Co/NF-GNF catalyst in comparison with the Pt/C catalyst. XPS analysis of the Fe-Co/NF-GNF catalyst presents the ORR active chemical states of N (pyridinic-N and graphitic-N) and F (semi-ionic-F) and the co-ordinated sites of Fe and Co species with the dopants. The excellent performance and durability of the Fe-Co/NF-GNF catalyst is due to the synergistic effect between the hetero atoms dopants (N and F) and strong co-ordinating bonds of M-N-C, which protect the graphene layers around the metallic species and greatly mitigates the leaching of Co and Fe during the long term cycling test. The high activity and

  5. Comparison of iridium- and ruthenium-based, Pt-surface-enriched, nanosize catalysts for the oxygen-reduction reaction

    NASA Astrophysics Data System (ADS)

    Kaplan, D.; Goor, M.; Alon, M.; Tsizin, S.; Burstein, L.; Rosenberg, Y.; Popov, I.; Peled, E.

    2016-02-01

    Pt-surface-enriched nanosize catalysts (Pt-SENS catalysts) with ruthenium and iridium cores, supported on XC72, were synthesized and characterized. The structure and composition of the catalysts are determined by Energy-Dispersive X-ray Spectroscopy (EDS), X-ray Photoelectron Spectroscopy (XPS), Scanning Transmission Electron Microscopy (STEM) and X-Ray Diffraction (XRD). Electrochemical characterization tests, including oxygen-reduction-catalysis activity and durability studies of catalysts are performed with the use of cyclic-voltammetry and rotating-disk-electrode (RDE) techniques at room temperature. The ORR activity of the homemade catalysts is also compared to ORR activity of commercial 50%Pt/C catalyst. It is determined that the Ir-based catalyst (Pt/Ir/XC72) shows higher ORR activity in terms of A g-1 of Pt (at 0.85 V vs. RHE) than the Ru-based catalyst (Pt/Ru/XC72) and the commercial 50%Pt/C. The Ru-based catalyst shows similar ORR activity in terms of A g-1 of Pt, to that of the commercial 50%Pt/C, but with much lower durability.

  6. Nitrogen-doped hierarchically porous carbon spheres as efficient metal-free electrocatalysts for an oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, You-Lin; Shi, Cheng-Xiang; Xu, Xue-Yan; Sun, Ping-Chuan; Chen, Tie-Hong

    2015-06-01

    Using hierarchically mesoporous silica spheres as a hard template and methyl violet as carbon and nitrogen source, nitrogen-doped hierarchically porous carbon spheres (N-HCS) are successfully prepared via a nanocasting method. The nitrogen-doped carbon spheres obtained after carbonization at 1000 °C (N-HCS-1000) exhibit a hierarchically micro-meso-macroporous structure with a relatively high surface area (BET) of 1413 m2 g-1 and a notably large pore volume of 2.96 cm3 g-1. In an oxygen reduction reaction (ORR) in alkaline media, the N-HCS-1000 material exhibits excellent activity with high current density, and its onset potential is notably close to that of the commercial Pt/C catalyst. The efficient catalytic activity of this catalyst could be attributed to the high electrical conductivity of the nitrogen-doped carbon matrix as well as the hierarchically porous framework. This catalyst also exhibits better methanol crossover resistance and higher stability than the commercial Pt/C catalyst.

  7. Hollow mesoporous carbon nitride nanosphere/three-dimensional graphene composite as high efficient electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Qin, Yong; Li, Juan; Yuan, Jie; Kong, Yong; Tao, Yongxin; Lin, Furong; Li, Shan

    2014-12-01

    Hollow mesoporous carbon nitride nanosphere (HMCN) is firstly prepared via an etching route using hollow mesoporous silica as a sacrificial template. The as-obtained HMCN is a uniform spherical particle with a diameter of ∼300 nm,and possesses a high specific surface area up to 439 m2 g-1. Hollow mesoporous carbon nitride nanosphere/three-dimensional (3D) graphene composite (HMCN-G) is subsequently fabricated via a hydrothermal treatment of HMCN with graphene oxide. As an electrocatalyst for oxygen reduction reaction (ORR), the HMCN-G shows significantly enhanced electrocatalytic activity compared to bulk graphitic carbon nitride (g-C3N4) and HMCN in terms of the electron-transfer number, current density and onset potential. Increased density of catalytically active sites and improved accessibility to electrolyte enabled by the hollow and mesoporous architecture of HMCN, and high conductivity induced from graphene are considered to contribute to the remarkable electrocatalytic performance of the HMCN-G. Furthermore, HMCN-G exhibits superior methanol tolerance to Pt/C catalyst, suggesting that it is a promising metal-free electrocatalyst for polymer electrolyte membrane fuel cell (PEMFC).

  8. In-situ synchrotron x-ray spectroscopy of ruthenium nanoparticles modified with selenium for oxygen reduction reaction.

    SciTech Connect

    Inukai, J.; Cao, D.; Wieckowski, A.; Chang, K.-C.; Menzel, A.; Komanicky, V.; You, H.; Materials Science Division; Univ. of Illinois; Univ. of Yamanashi

    2007-11-15

    We used in situ Se K-edge X-ray spectroscopy to characterize Ru nanoparticles chemically modified with submonolayers of selenium (Se/Ru) [Cao et al. J. Electrochem. Soc. 2006, 153, A869]. X-ray powder diffraction verified that the Se/Ru catalyst had metallic Ru cores. The in situ X-ray absorption near edge structure taken at the open circuit potential showed that there were both elemental and oxidized selenium on the as-prepared Se/Ru samples. All selenium oxide was reduced to the elemental form of selenium by applying negative potentials. By applying positive potentials, selenium was subsequently reoxidized. The analysis of the extended X-ray absorption fine structure shows the appearance of selenium hydration (Se-OH{sub 2}) in a deaerated solution, which was not observed during the oxygen reduction reaction. We present evidence that Se-free Ru atoms play an important role in the ORR activity of the Se/Ru catalyst studied in this paper.

  9. In situ synchrotron x-ray spectroscopy of ruthenium nanoparticles modified with selenium for an oxygen reduction reaction.

    SciTech Connect

    Inukai, J.; Cao, D.; Wieckowski, A.; Chang, K.-C.; Menzel, A.; Komanicky, V.; You, H.; Univ. Illinois; Univ. Yamanashi

    2007-11-15

    We used in situ Se K-edge X-ray spectroscopy to characterize Ru nanoparticles chemically modified with submonolayers of selenium (Se/Ru) [Cao et al. J. Electrochem. Soc. 2006, 153, A869]. X-ray powder diffraction verified that the Se/Ru catalyst had metallic Ru cores. The in situ X-ray absorption near edge structure taken at the open circuit potential showed that there were both elemental and oxidized selenium on the as-prepared Se/Ru samples. All selenium oxide was reduced to the elemental form of selenium by applying negative potentials. By applying positive potentials, selenium was subsequently reoxidized. The analysis of the extended X-ray absorption fine structure shows the appearance of selenium hydration (Se-OH{sub 2}) in a deaerated solution, which was not observed during the oxygen reduction reaction. We present evidence that Se-free Ru atoms play an important role in the ORR activity of the Se/Ru catalyst studied in this paper.

  10. Activity of Co-N multi walled carbon nanotubes electrocatalysts for oxygen reduction reaction in acid conditions

    NASA Astrophysics Data System (ADS)

    Osmieri, Luigi; Monteverde Videla, Alessandro H. A.; Specchia, Stefania

    2015-03-01

    Two catalysts are synthesized by wet impregnation of multi walled carbon nanotubes (MWCNT) with a complex formed between Co(II) ions and the nitrogen-containing molecule 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ), followed by one or two identical heat treatments in N2 atmosphere at 800 °C for 3 h. Catalysts are fully characterized by FESEM, EDX, BET, XRD, FTIR, TGA, XPS analyses, and electrochemical techniques. The electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalysts in acid conditions is assessed by means of a rotating disk electrode (RDE) apparatus and a specific type of cell equipped with a gas diffusion working electrode (GDE). In both testing approaches, the catalyst heat-treated twice (Co-N/MWCNT-2) exhibits higher electroactivity than the catalyst heat-treated once (Co-N/MWCNT-1). Chronoamperometries both in RDE and GDE cell are also performed, showing less electroactivity decay and better current performance for the catalyst heat-treated twice.

  11. Examination of the electroactive composites containing cobalt nanoclusters and nitrogen-doped nanostructured carbon as electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Pacuła, Aleksandra; Ikeda, Katsuyoshi; Masuda, Takuya; Uosaki, Kohei

    2012-12-01

    A series of electroactive composites containing cobalt nanoclusters and N-doped graphite-like carbon is obtained by catalytic chemical vapour deposition (CCVD) using Mg-Co-Al layered double hydroxides and acetonitrile. The influence of synthesis temperature, e.g. 600, 700 and 800 °C on their physicochemical properties is examined by means of X-ray diffraction, elemental analysis, thermal analysis, nitrogen sorption, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy. N-doped graphite-like carbon in the catalysts shows various morphologies. The composite prepared at 600 °C contains plate-like particles, whereas those synthesized at 700 and 800 °C, contain not only plate-like particles but also multi-walled carbon nanotubes. The concentration of nitrogen uniformly incorporated in the carbon framework is ca. 2 wt %. The electrocatalytic properties of the catalysts for oxygen reduction reaction (ORR) are evaluated in alkaline media by cyclic voltammetry and rotating disk electrode (RDE) measurement. The composites are proved to have the ability to reduce oxygen according to 2-electron pathway.

  12. Facile, scalable synthesis of edge-halogenated graphene nanoplatelets as efficient metal-free eletrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Jeon, In-Yup; Choi, Hyun-Jung; Choi, Min; Seo, Jeong-Min; Jung, Sun-Min; Kim, Min-Jung; Zhang, Sheng; Zhang, Lipeng; Xia, Zhenhai; Dai, Liming; Park, Noejung; Baek, Jong-Beom

    2013-06-01

    A series of edge-selectively halogenated (X = Cl, Br, I) graphene nanoplatelets (XGnPs = ClGnP, BrGnP, IGnP) were prepared simply by ball-milling graphite in the presence of Cl2, Br2 and I2, respectively. High BET surface areas of 471, 579 and 662 m2/g were observed for ClGnP, BrGnP and IGnP, respectively, indicating a significant extent of delamination during the ball-milling and subsequent workup processes. The newly-developed XGnPs can be well dispersed in various solvents, and hence are solution processable. Furthermore, XGnPs showed remarkable electrocatalytic activities toward oxygen reduction reaction (ORR) with a high selectivity, good tolerance to methanol crossover/CO poisoning effects, and excellent long-term cycle stability. First-principle density-functional calculations revealed that halogenated graphene edges could provide decent adsorption sites for oxygen molecules, in a good agreement with the experimental observations.

  13. Facile synthesis of N-rich carbon quantum dots by spontaneous polymerization and incision of solvents as efficient bioimaging probes and advanced electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Lei, Zhouyue; Xu, Shengjie; Wan, Jiaxun; Wu, Peiyi

    2016-01-01

    In this study, uniform nitrogen-doped carbon quantum dots (N-CDs) were synthesized through a one-step solvothermal process of cyclic and nitrogen-rich solvents, such as N-methyl-2-pyrrolidone (NMP) and dimethyl-imidazolidinone (DMEU), under mild conditions. The products exhibited strong light blue fluorescence, good cell permeability and low cytotoxicity. Moreover, after a facile post-thermal treatment, it developed a lotus seedpod surface-like structure of seed-like N-CDs decorating on the surface of carbon layers with a high proportion of quaternary nitrogen moieties that exhibited excellent electrocatalytic activity and long-term durability towards the oxygen reduction reaction (ORR). The peak potential was -160 mV, which was comparable to or even lower than commercial Pt/C catalysts. Therefore, this study provides an alternative facile approach to the synthesis of versatile carbon quantum dots (CDs) with widespread commercial application prospects, not only as bioimaging probes but also as promising electrocatalysts for the metal-free ORR.In this study, uniform nitrogen-doped carbon quantum dots (N-CDs) were synthesized through a one-step solvothermal process of cyclic and nitrogen-rich solvents, such as N-methyl-2-pyrrolidone (NMP) and dimethyl-imidazolidinone (DMEU), under mild conditions. The products exhibited strong light blue fluorescence, good cell permeability and low cytotoxicity. Moreover, after a facile post-thermal treatment, it developed a lotus seedpod surface-like structure of seed-like N-CDs decorating on the surface of carbon layers with a high proportion of quaternary nitrogen moieties that exhibited excellent electrocatalytic activity and long-term durability towards the oxygen reduction reaction (ORR). The peak potential was -160 mV, which was comparable to or even lower than commercial Pt/C catalysts. Therefore, this study provides an alternative facile approach to the synthesis of versatile carbon quantum dots (CDs) with widespread

  14. Reduction of dynamical biochemical reactions networks in computational biology

    PubMed Central

    Radulescu, O.; Gorban, A. N.; Zinovyev, A.; Noel, V.

    2012-01-01

    Biochemical networks are used in computational biology, to model mechanistic details of systems involved in cell signaling, metabolism, and regulation of gene expression. Parametric and structural uncertainty, as well as combinatorial explosion are strong obstacles against analyzing the dynamics of large models of this type. Multiscaleness, an important property of these networks, can be used to get past some of these obstacles. Networks with many well separated time scales, can be reduced to simpler models, in a way that depends only on the orders of magnitude and not on the exact values of the kinetic parameters. The main idea used for such robust simplifications of networks is the concept of dominance among model elements, allowing hierarchical organization of these elements according to their effects on the network dynamics. This concept finds a natural formulation in tropical geometry. We revisit, in the light of these new ideas, the main approaches to model reduction of reaction networks, such as quasi-steady state (QSS) and quasi-equilibrium approximations (QE), and provide practical recipes for model reduction of linear and non-linear networks. We also discuss the application of model reduction to the problem of parameter identification, via backward pruning machine learning techniques. PMID:22833754

  15. Nitrogen and fluorine dual-doped mesoporous graphene: a high-performance metal-free ORR electrocatalyst with a super-low HO2- yield

    NASA Astrophysics Data System (ADS)

    Jiang, Shu; Sun, Yujing; Dai, Haichao; Hu, Jingting; Ni, Pengjuan; Wang, Yilin; Li, Zhen; Li, Zhuang

    2015-06-01

    In this study, we successfully, for the first time, prepared nitrogen and fluorine dual-doped mesoporous graphene (NF-MG) via the thermal treatment of graphene oxide/polyaniline composites (GO/PANI) and NH4F. Benefiting from the synergistic effect of N and F co-doping into the G framework, the oxygen reduction reaction performance of the optimal catalyst (NF-MG3) is comparable with the-state-of-the-art Pt/C catalyst in an alkaline medium, which makes it an ideal candidate as an efficient metal-free ORR electrocatalyst in fuel cells.In this study, we successfully, for the first time, prepared nitrogen and fluorine dual-doped mesoporous graphene (NF-MG) via the thermal treatment of graphene oxide/polyaniline composites (GO/PANI) and NH4F. Benefiting from the synergistic effect of N and F co-doping into the G framework, the oxygen reduction reaction performance of the optimal catalyst (NF-MG3) is comparable with the-state-of-the-art Pt/C catalyst in an alkaline medium, which makes it an ideal candidate as an efficient metal-free ORR electrocatalyst in fuel cells. Electronic supplementary information (ESI) available: Experimental details (Scheme S1), optimization and morphology of NF-MGs catalysts (Fig. S1-S2), Fig. S3-S9, and Tables S1-S2. See DOI: 10.1039/c5nr01793a

  16. Enhanced electrocatalytic activity and stability of Pd3V/C nanoparticles with a trace amount of Pt decoration for the oxygen reduction reaction

    DOE PAGESBeta

    Liu, Sufen; Han, Lili; Zhu, Jing; Xiao, Weiping; Wang, Jie; Liu, Hongfang; Xin, Huolin; Wang, Deli

    2015-09-14

    In this study, carbon supported Pd3V bimetallic alloy nanoparticles (Pd3V/C) have been successfully synthesized via a simple impregnation–reduction method, followed by high temperature treatment under a H2 atmosphere. Electrochemical tests reveal that the half-wave potential of Pd3V/C-500 shifts positively 40 mV compared with Pd/C. However, the catalytic activity of Pd3V/C-500 suffers from serious degradation after 1k cycles. By a spontaneous displacement reaction or co-reduction method, a trace amount of Pt was decorated on the surface or inside of the Pd3V/C nanoparticles. The catalytic activity and stability of the Pd3V@Pt/C and Pt-Pd3V/C catalysts for the oxygen reduction reaction (ORR) are enhancedmore » significantly, and are comparable to commercial Pt/C. In addition, the Pt mass activity of Pd3V@Pt/C and Pt-Pd3V/C improves by factors of 10.9 and 6.5 at 0.80 V relative to Pt/C. Moreover, Pt-decorated Pd3V/C nanoparticles show almost no obvious morphology change after durability tests, because the Pt-rich shell plays an important role in preventing degradation.« less

  17. Earth-Abundant Nanomaterials for Oxygen Reduction.

    PubMed

    Xia, Wei; Mahmood, Asif; Liang, Zibin; Zou, Ruqiang; Guo, Shaojun

    2016-02-18

    Replacing the rare and precious platinum (Pt) electrocatalysts with earth-abundant materials for promoting the oxygen reduction reaction (ORR) at the cathode of fuel cells is of great interest in developing high-performance sustainable energy devices. However, the challenging issues associated with non-Pt materials are still their low intrinsic catalytic activity, limited active sites, and the poor mass transport properties. Recent advances in material sciences and nanotechnology enable rational design of new earth-abundant materials with optimized composition and fine nanostructure, providing new opportunities for enhancing ORR performance at the molecular level. This Review highlights recent breakthroughs in engineering nanocatalysts based on the earth-abundant materials for boosting ORR. PMID:26663778

  18. Multicopper models for the laccase active site: effect of nuclearity on electrocatalytic oxygen reduction.

    PubMed

    Tse, Edmund C M; Schilter, David; Gray, Danielle L; Rauchfuss, Thomas B; Gewirth, Andrew A

    2014-08-18

    Cu complexes of 2,2'-dipicolylamine (DPA) were prepared and tested as electrocatalysts for the oxygen reduction reaction (ORR). To study the effect of multinuclearity on the ORR, two Cu-DPA units were connected with a flexible linker, and a third metal-binding pocket was installed in the ligand framework. ORR onset potentials and the diffusion-limited current densities of di- and tricopper complexes of DPA derivatives were found to be comparable to those of the simpler Cu-DPA system. Electrochemical analyses, crystallographic data, and metal-substitution studies suggested that Cu complexes of DPA derivatives reacted with O2 via a binuclear intermolecular pathway but that the Cu center in the third binding site did not participate in the ORR process. This study highlights the viability of Cu-DPA complexes to mimic the T3-site of laccase, and serves as a guide for designing future laccase models. PMID:25072935

  19. Shrimp-shell derived carbon nanodots as carbon and nitrogen sources to fabricate three-dimensional N-doped porous carbon electrocatalysts for the oxygen reduction reaction.

    PubMed

    Liu, Rongrong; Zhang, Haimin; Liu, Shengwen; Zhang, Xian; Wu, Tianxing; Ge, Xiao; Zang, Yipeng; Zhao, Huijun; Wang, Guozhong

    2016-02-01

    Development of cheap, abundant and metal-free N-doped carbon materials as high efficiency oxygen reduction electrocatalysts is crucial for their practical applications in future fuel cell devices. Here, three-dimensional (3D) N-doped porous carbon (NPC) materials have been successfully developed by a simple template-assisted (e.g., SiO2 spheres) high temperature pyrolysis approach using shrimp-shell derived N-doped carbon nanodots (N-CNs) as carbon and nitrogen sources obtained through a facile hydrothermal method. The shrimp-shell derived N-CNs with a product yield of ∼ 5% possess rich surface O- and N-containing functional groups and small nanodot sizes of 1.5-5.0 nm, which are mixed with surface acidification treated SiO2 spheres with an average diameter of ∼ 200 nm in aqueous solution to form a N-CNs@SiO2 composite subjected to a thermal evaporation treatment. The resultant N-CNs@SiO2 composite is further thermally treated in a N2 atmosphere at different pyrolysis temperatures, followed by acid etching, to obtain 3D N-doped porous carbon (NPC) materials. As electrocatalysts for oxygen reduction reaction (ORR) in alkaline media, the experimental results demonstrate that 3D NPC obtained at 800 °C (NPC-800) with a surface area of 360.2 m(2) g(-1) exhibits the best ORR catalytic activity with an onset potential of -0.06 V, a half wave potential of -0.21 V and a large limiting current density of 5.3 mA cm(-2) (at -0.4 V, vs. Ag/AgCl) among all NPC materials investigated, comparable to that of the commercial Pt/C catalyst with an onset potential of -0.03 V, a half wave potential of -0.17 V and a limiting current density of 5.5 mA cm(-2) at -0.4 V. Such a 3D porous carbon ORR electrocatalyst also displays superior durability and high methanol tolerance in alkaline media, apparently better than the commercial Pt/C catalyst. The findings of this work would be valuable for the development of low-cost and abundant N-doped carbon materials from biomass as high

  20. Phosphorus/sulfur Co-doped porous carbon with enhanced specific capacitance for supercapacitor and improved catalytic activity for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhou, Yao; Ma, Ruguang; Candelaria, Stephanie L.; Wang, Jiacheng; Liu, Qian; Uchaker, Evan; Li, Pengxi; Chen, Yongfang; Cao, Guozhong

    2016-05-01

    Phosphorus (P)/sulfur (S) co-doped porous carbon derived from resorcinol and furaldehyde are synthesized through one-step sol-gel processing with the addition of phosphorus pentasulfide as P and S source followed with freeze-drying and pyrolysis in nitrogen. The P/S co-doping strategy facilitates the pore size widening both in micropore and mesopore regions, together with the positive effect on the degree of graphitization of porous carbon through elimination of amorphous carbon through the formation and evaporation of carbon disulfide. As an electrode for supercapacitor application, P/S co-doped porous carbon demonstrates 43.5% improvement on specific capacitance of the single electrode compared to pristine porous carbon in organic electrolyte at a current of 0.5 mA due to the P-induced pseudocapacitive reactions. As for electrocatalytic use, promoted electrocatalytic activity and high resistance to crossover effects of oxygen reduction reaction (ORR) in alkaline media are observed after the introduction of P and S into porous carbon. After air activation, the specific capacitance of the single electrode of sample PS-pC reaches up to 103.5 F g-1 and an improved oxygen reduction current density.

  1. Facile Synthesis of Quasi-One-Dimensional Au/PtAu Heterojunction Nanotubes and Their Application as Catalysts in an Oxygen-Reduction Reaction.

    PubMed

    Cai, Kai; Liu, Jiawei; Zhang, Huan; Huang, Zhao; Lu, Zhicheng; Foda, Mohamed F; Li, Tingting; Han, Heyou

    2015-05-11

    An intermediate-template-directed method has been developed for the synthesis of quasi-one-dimensional Au/PtAu heterojunction nanotubes by the heterogeneous nucleation and growth of Au on Te/Pt core-shell nanostructures in aqueous solution. The synthesized porous Au/PtAu bimetallic nanotubes (PABNTs) consist of porous tubular framework and attached Au nanoparticles (AuNPs). The reaction intermediates played an important role in the preparation, which fabricated the framework and provided a localized reducing agent for the reduction of the Au and Pt precursors. The Pt7 Au PABNTs showed higher electrocatalytic activity and durability in the oxygen-reduction reaction (ORR) in 0.1 M HClO4 than porous Pt nanotubes (PtNTs) and commercially available Pt/C. The mass activity of PABNTs was 218 % that of commercial Pt/C after an accelerated durability test. This study demonstrates the potential of PABNTs as highly efficient electrocatalysts. In addition, this method provides a facile strategy for the synthesis of desirable hetero-nanostructures with controlled size and shape by utilizing an intermediate template. PMID:25833689

  2. Fundamentals of several reactions for the carbothermic reduction of alumina

    NASA Astrophysics Data System (ADS)

    Walker, Matthew S.

    The current process used for primary aluminum production, the Hall-Heroult process, is reliable, but it also is expensive, consumes large amounts of energy, and generates significant quantities of greenhouse gas emissions. One possible alternative process is the carbothermic reduction of alumina, wherein aluminum is formed by reducing alumina with carbon at high temperatures. This process, if successful, has the potential for substantial reductions in energy consumption, capital costs, and greenhouse gas emissions. One critical component to making this process successful involves obtaining a better understanding of the thermodynamics. Specifically, the key thermodynamic data are the free energies of the reactions and the thermodynamic activities of the metal (Al-C) and slag systems (Al2O3-Al4C3). These are critical for evaluating and controlling the carbothermic process, but experimental data is extremely limited and much of it was measured many years ago when the experimental techniques available may not have been adequate. The overall objective for this research was to assess the validity of the thermodynamic data for this process, as well as its suitability for predicting the behavior of the process. This was done through experimental investigations into both the slag (carbide) making reaction and the binary Al2O 3-Al4C3 phase diagram. The comparison of these results, to those expected based on the current understanding for the process thermodynamics (using FactSage along with the ALCO database), assesses the validity of the thermodynamic data. In this document, the experimental results for investigating the reactions of Al2O3 with carbon are presented. This work involved measuring the operating line for the first step of the carbothermic aluminum process, slag making. This was done using two experimental methods. One involved measuring the evolution of CO from the reactions using a mass spectrometer. The other involved using a vacuum thermobalance (TGA) to

  3. Pd@Pt core-shell concave decahedra: A class of catalysts for the oxygen reduction reaction with enhanced activity and durability

    DOE PAGESBeta

    Wang, Xue; Vera, Madeline; Chi, Miaofang; Xia, Younan; Luo, Ming; Huang, Hongwen; Ruditskiy, Aleksey; Park, Jinho; Bao, Shixiong; Liu, Jingyue; et al

    2015-11-13

    Here, we report a facile synthesis of multiply twinned Pd@Pt core shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200 degrees C, naturally generating a core shell structure covered by concave facets. The nonuniformity inmore » the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm2pt) and mass (1.60 A/mg/2pt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm2pt and 0.32 A/mgpt, respectively). After 10 000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgpt, more than twice that of the pristine Pt/C catalyst.« less

  4. Pd@Pt core-shell concave decahedra: A class of catalysts for the oxygen reduction reaction with enhanced activity and durability

    SciTech Connect

    Wang, Xue; Vera, Madeline; Chi, Miaofang; Xia, Younan; Luo, Ming; Huang, Hongwen; Ruditskiy, Aleksey; Park, Jinho; Bao, Shixiong; Liu, Jingyue; Howe, Jane; Xie, Zhaoxiong

    2015-11-13

    Here, we report a facile synthesis of multiply twinned Pd@Pt core shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200 degrees C, naturally generating a core shell structure covered by concave facets. The nonuniformity in the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm2pt) and mass (1.60 A/mg/2pt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm2pt and 0.32 A/mgpt, respectively). After 10 000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgpt, more than twice that of the pristine Pt/C catalyst.

  5. Metal-free Ketjenblack incorporated nitrogen-doped carbon sheets derived from gelatin as oxygen reduction catalysts.

    PubMed

    Nam, Gyutae; Park, Joohyuk; Kim, Sun Tai; Shin, Dong-bin; Park, Noejung; Kim, Youngsik; Lee, Jang-Soo; Cho, Jaephil

    2014-01-01

    Electrocatalysts facilitating oxygen reduction reaction (ORR) are vital components in advanced fuel cells and metal-air batteries. Here we report Ketjenblack incorporated nitrogen-doped carbon sheets derived from gelatin and apply these easily scalable materials as metal-free electrocatalysts for ORR. These carbon nanosheets demonstrate highly comparable catalytic activity for ORR as well as better durability than commercial Vulcan carbon supported Pt catalysts in alkaline media. Physico-chemical characterization and theoretical calculations suggest that proper combination of graphitic and pyridinic nitrogen species with more exposed edge sites effectively facilitates a formation of superoxide, [O2(ad)](-), via one-electron transfer, thus increasing catalytic activities for ORR. Our results demonstrate a novel strategy to expose more nitrogen doped edge sites by irregular stacked small sheets in developing better electrocatalysts for Zn-air batteries. These desirable architectures are embodied by an amphiphlilic gelatin mediated compatible synthetic strategy between hydrophobic carbon and aqueous water. PMID:24635744

  6. Facile synthesis of platinum-gold alloyed string-bead nanochain networks with the assistance of allantoin and their enhanced electrocatalytic performance for oxygen reduction and methanol oxidation reactions

    NASA Astrophysics Data System (ADS)

    He, Li-Li; Zheng, Jie-Ning; Song, Pei; Zhong, Shu-Xian; Wang, Ai-Jun; Chen, Zhaojiang; Feng, Jiu-Ju

    2015-02-01

    In this work, a facile one-pot wet-chemical method is developed for preparation of bimetallic platinum-gold (Pt-Au) alloyed string-bead nanochain networks, using allantoin as a structure-directing agent, without any template, surfactant, or seed. The characterization experiments are mainly performed by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) spectroscopy. The as-prepared Pt-Au nanocrystals show enhanced electrocatalytic performance toward oxygen reduction reaction (ORR) mainly predominated by a four-electron pathway, and display improved catalytic activity and high stability for methanol oxidation reaction (MOR) over commercial Pt black and Pt-Ru black.

  7. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts.

    PubMed

    Greeley, J; Stephens, I E L; Bondarenko, A S; Johansson, T P; Hansen, H A; Jaramillo, T F; Rossmeisl, J; Chorkendorff, I; Nørskov, J K

    2009-10-01

    The widespread use of low-temperature polymer electrolyte membrane fuel cells for mobile applications will require significant reductions in the amount of expensive Pt contained within their cathodes, which drive the oxygen reduction reaction (ORR). Although progress has been made in this respect, further reductions through the development of more active and stable electrocatalysts are still necessary. Here we describe a new set of ORR electrocatalysts consisting of Pd or Pt alloyed with early transition metals such as Sc or Y. They were identified using density functional theory calculations as being the most stable Pt- and Pd-based binary alloys with ORR activity likely to be better than Pt. Electrochemical measurements show that the activity of polycrystalline Pt(3)Sc and Pt(3)Y electrodes is enhanced relative to pure Pt by a factor of 1.5-1.8 and 6-10, respectively, in the range 0.9-0.87 V. PMID:21378936

  8. Oxygen Reduction Catalysis at a Dicobalt Center: The Relationship of Faradaic Efficiency to Overpotential.

    PubMed

    Passard, Guillaume; Ullman, Andrew M; Brodsky, Casey N; Nocera, Daniel G

    2016-03-01

    The selective four electron, four proton, electrochemical reduction of O2 to H2O in the presence of a strong acid (TFA) is catalyzed at a dicobalt center. The faradaic efficiency of the oxygen reduction reaction (ORR) is furnished from a systematic electrochemical study by using rotating ring disk electrode (RRDE) methods over a wide potential range. We derive a thermodynamic cycle that gives access to the standard potential of O2 reduction to H2O in organic solvents, taking into account the presence of an exogenous proton donor. The difference in ORR selectivity for H2O vs H2O2 depends on the thermodynamic standard potential as dictated by the pKa of the proton donor. The model is general and rationalizes the faradaic efficiencies reported for many ORR catalytic systems. PMID:26876226

  9. Oxygen Reduction Reaction Kinetics in Sr-Doped La2NiO4+  Ruddlesden-Popper Phase as Cathode for Solid Oxide Fuel Cells

    DOE PAGESBeta

    Guan, B.; Li, W.; Zhang, H.; Liu, X.

    2015-01-01

    In this paper, electro-catalytic reduction of oxygen in Sr-doped lanthanum nickelates, La2-xSrxNiO4+δ (0 ≤ x ≤ 0.4) RuddlesdenPopper(R-P)phase,hasbeeninvestigated.Theoxygenreductionreaction(ORR)kineticsisevaluatedviaelectrochemicalimpedance spectroscopy (EIS) with the symmetric cell configuration. The maximum performance is achieved with the un-doped La2NiO4+δ, ∼0.13 cm2 at 800◦C. Sr doping decreases the electrode performance progressively. Further detailed analysis indicates that bulk ionicdiffusionandsurfaceoxygenexchangeco-limittheORRofthosecathodes.Srsubstitutionleadstobothloweredbulkdiffusion and surface exchange rates. With high Sr content (x = 0.3, 0.4), oxygen ion transfer resistance between nickelate/electrolyte is observed. As for the surface exchange process, oxygen adsorption is suggested to be the main rate-limiting step (RLS) according to the reaction orders, which is retarded further by themore » oxidation of Ni2+ to Ni3+ as Sr content increases. The possible role of incorporation process in determining the overall reaction rate is also discussed.« less

  10. Nitrogen-doped graphene aerogel-supported spinel CoMn2O4 nanoparticles as an efficient catalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, Yisi; Li, Jie; Li, Wenzhang; Li, Yaomin; Chen, Qiyuan; Zhan, Faqi

    2015-12-01

    Spinel CoMn2O4 (CMO) nanoparticles grown on three-dimensional (3D) nitrogen-doped graphene areogel (NGA) is prepared by a facile two-step hydrothermal method. The NGA not only possesses the intrinsic property of graphene, but also has abundant pore conformations for supporting spinel metal oxide nanoparticles, thus would be suitable as a good electrocatalysts' support for oxygen reduction reaction (ORR). The structure, morphology, porous properties, and chemical composition of CMO/NGA are investigated by X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, nitrogen adsorption-desorption measurements, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of catalysts is discussed by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and rotating disk electrode (RDE) measurements in O2-saturated 0.1 M KOH electrolyte. The CMO/NGA hybrid exhibits more positive onset potential and half-wave potential, faster charge transfer than that of CMO and NGA, and its electrocatalytic performance is comparable with the commercial 20 wt.% Pt/C. Furthermore, it mainly favors a direct 4e- reaction pathway, and has excellent ethanol tolerance and high durability, which is attributed to the unique 3D crumpled porous nanostructure of NGA with large specific area and fast electron transport, and the synergic covalent coupling between the CoMn2O4 nanoparticles and NGA.

  11. Oxygen Reduction Reaction Kinetics in Sr-Doped La2NiO4+  Ruddlesden-Popper Phase as Cathode for Solid Oxide Fuel Cells

    SciTech Connect

    Guan, B.; Li, W.; Zhang, H.; Liu, X.

    2015-01-01

    In this paper, electro-catalytic reduction of oxygen in Sr-doped lanthanum nickelates, La2-xSrxNiO4+δ (0 ≤ x ≤ 0.4) RuddlesdenPopper(R-P)phase,hasbeeninvestigated.Theoxygenreductionreaction(ORR)kineticsisevaluatedviaelectrochemicalimpedance spectroscopy (EIS) with the symmetric cell configuration. The maximum performance is achieved with the un-doped La2NiO4+δ, ∼0.13 #2;cm2 at 800◦C. Sr doping decreases the electrode performance progressively. Further detailed analysis indicates that bulk ionicdiffusionandsurfaceoxygenexchangeco-limittheORRofthosecathodes.Srsubstitutionleadstobothloweredbulkdiffusion and surface exchange rates. With high Sr content (x = 0.3, 0.4), oxygen ion transfer resistance between nickelate/electrolyte is observed. As for the surface exchange process, oxygen adsorption is suggested to be the main rate-limiting step (RLS) according to the reaction orders, which is retarded further by the oxidation of Ni2+ to Ni3+ as Sr content increases. The possible role of incorporation process in determining the overall reaction rate is also discussed.

  12. Hybrid binuclear-cobalt-phthalocyanine as oxygen reduction reaction catalyst in single chamber microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Li, Baitao; Zhou, Xiuxiu; Wang, Xiujun; Liu, Bingchuan; Li, Baikun

    2014-12-01

    A novel hybrid binuclear-cobalt-phthalocyanine (Bi-CoPc) is developed as the cathode catalyst to replace the costly platinum (Pt) in single chamber microbial fuel cells (SCMFCs). Bi-CoPc/C is integrated with metal oxides (NiO and CoO) to form macrocyclic complex for enhanced oxygen reduction rate (ORR). The characteristics of hybrid catalysts (Bi-CoPc/C-CoO and Bi-CoPc/C-NiO) are compared with Co-contained catalysts (CoPc/C and Bi-CoPc/C) and metal oxide catalysts (NiO and CoO). The increase in O and N functional groups indicates the benefits of NiO and CoO to the cathode catalysts. The cyclic voltammetry (CV) shows the reduction peak for Bi-CoPc/C-NiO and Bi-CoPc/C-CoO at -0.12 V and -0.22 V, respectively. The power densities (368 mW m-2 and 400 mW m-2) of SCMFCs with Bi-CoPc/C-CoO and Bi-CoPc-NiO/C are the highest among the cathodes tested, and close to that of Pt (450 mW m-2). This study demonstrates that hybrid Bi-CoPc/C with metal oxides has a great potential as a cost-effective catalyst in MFCs.

  13. Effects of ionomer morphology on oxygen reduction on Pt

    SciTech Connect

    Chlistunoff, Jerzy; Pivovar, Bryan

    2015-05-21

    In this paper, the oxygen reduction reaction (ORR) at the interface between platinum and Nafion 1100 equivalent weight was studied as a function of temperature (20–80 °C), humidity (10–100%), scan rate, the manner in which Nafion film was deposited, and the state of the Pt surface using ultramicroelectrodes employing cyclic voltammetry and chronoamperometry. ORR on smooth electrodes was strongly inhibited under specific conditions dependent on temperature, humidity, and scan rate. From the data presented, we postulate that dynamic changes in the molecular structure of the ionomer at the platinum interface result in differences in ORR voltammetry for films prepared and equilibrated under different conditions. The lack of similar changes for rough, platinized electrodes has been attributed to differences in initial ionomer structure and a higher energy barrier for ionomer restructuring. Finally, these model system studies yield insight into the ionomer-catalyst interface of particular interest for polymer electrolyte fuel cells.

  14. Controlled synthesis of La{sub 1−x}Sr{sub x}CrO{sub 3} nanoparticles by hydrothermal method with nonionic surfactant and their ORR activity in alkaline medium

    SciTech Connect

    Choi, Bo Hyun; Park, Shin-Ae; Park, Bong Kyu; Chun, Ho Hwan; Kim, Yong-Tae

    2013-10-15

    Graphical abstract: We demonstrate that Sr-doped LaCrO{sub 3} nanoparticles were successfully prepared by the hydrothermal synthesis method using the nonionic surfactant Triton X-100 and the applicability of La{sub 1−x}Sr{sub x}CrO{sub 3} to oxygen reduction reaction (ORR) electrocatalysis in an alkaline medium. Compared with the nanoparticles synthesized by the coprecipitation method, they showed enhanced ORR activity. - Highlights: • Sr-doped LaCrO{sub 3} nanoparticles were successfully prepared by the hydrothermal method using the nonionic surfactant. • Homogeneously shaped and sized Sr-doped LaCrO{sub 3} nanoparticles were readily obtained. • Compared with the nanoparticles synthesized by the coprecipitation method, they showed an enhanced ORR activity. • The main origin was revealed to be the decreased particle size due to the nonionic surfactant. - Abstract: Sr-doped LaCrO{sub 3} nanoparticles were prepared by the hydrothermal method with the nonionic surfactant Triton X-100 followed by heat treatment at 1000 °C for 10 h. The obtained perovskite nanoparticles had smaller particle size (about 100 nm) and more uniform size distribution than those synthesized by the conventional coprecipitation method. On the other hand, it was identified with the material simulation that the electronic structure change by Sr doping was negligible, because the initially unfilled e{sub g}-band was not affected by the p-type doping. Finally, the perovskite nanoparticles synthesized by hydrothermal method showed much higher ORR activity by over 200% at 0.8 V vs. RHE than those by coprecipitation method.

  15. A CoFe2O4/graphene nanohybrid as an efficient bi-functional electrocatalyst for oxygen reduction and oxygen evolution

    NASA Astrophysics Data System (ADS)

    Bian, Weiyong; Yang, Zhenrong; Strasser, Peter; Yang, Ruizhi

    2014-03-01

    Development of efficient electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) remain key issues for the commercialization of fuel cells and metal-air batteries. In this study, A CoFe2O4/graphene nanohybrid is facilely synthesized via a two-step process and applied as an electrocatalyst for the ORR and the OER. The as-prepared CoFe2O4/graphene nanohybrid demonstrates excellent catalytic activity for the ORR. At the same mass loading, the Tafel slope of CoFe2O4/graphene electrocatalyst for the ORR is comparable to that of the commercial Pt/C (20 wt% Pt on Vulcan XC-72, Johnson Matthey). The ORR on CoFe2O4/graphene mainly favours a direct 4e- reaction pathway. The CoFe2O4/graphene nanohybrid also affords high catalytic activity for the OER. The chronoamperometric tests show that CoFe2O4/graphene catalyst exhibits excellent stability for both the ORR and the OER, outperforming the commercial Pt/C. The high electrocatalytic activity and durability of CoFe2O4/graphene nanohybrid are attributed to the strong coupling between CoFe2O4 nanoparticles and graphene.

  16. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction

    PubMed Central

    Parnell, Charlette M.; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A.; Mudalige, Thilak K.; Biris, Alexandru S.; Ghosh, Anindya

    2016-01-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material’s −0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 106 mol−1s−1 was observed for the polydopamine-coated material–over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells. PMID:27528439

  17. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction.

    PubMed

    Parnell, Charlette M; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A; Mudalige, Thilak K; Biris, Alexandru S; Ghosh, Anindya

    2016-01-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material's -0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 10(6) mol(-1)s(-1) was observed for the polydopamine-coated material-over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells. PMID:27528439

  18. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    PubMed Central

    2015-01-01

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NOx species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. PMID:27162977

  19. Investigation of oxygen reduction reaction kinetics on Sm 0.5Sr 0.5CoO 3- δ cathode supported on Ce 0.85Sm 0.075Nd 0.075O 2- δ electrolyte

    NASA Astrophysics Data System (ADS)

    Gao, Zhan; Liu, Xingmin; Bergman, Bill; Zhao, Zhe

    Sm 0.5Sr 0.5CoO 3- δ (SSC) cathode prepared by a glycine-nitrate process (GNP) is investigated for solid oxide fuel cells (SOFCs) based on Ce 0.85Sm 0.075Nd 0.075O 2- δ (SNDC) electrolyte. SSC forms cubic perovskite structure after being annealed at 1100 °C for 5 h. SSC cathode and SNDC electrolyte can retain their own structure and there is no reaction between the two compositions. The microstructure of the cathode and the interfaces between cathodes and SNDC electrolytes are studied by scanning electron microscopy (SEM) after sintering at various temperatures. Impedance spectroscopy measurements reveal that area specific resistances (ASRs) of SSC-SNDC30 cathode are much lower than those of SSC cathode. Kinetics of oxygen reduction reaction (ORR) on porous SSC cathode is investigated by analysis of impedance spectra. Medium-frequency conductivities show no dependency on oxygen partial pressure (PO2) , which can be attributed to the oxygen ions transfer across the electrode/electrolyte interface. The dependencies of low-frequency conductivities on oxygen partial pressure (PO2) vary in the range from ca. 0.31 to ca. 0.34 and increase with the increasing temperatures. The low-frequency electrode process is a mixing process involving oxygen reduction reaction related to atomic oxygen and oxygen ions conduction step together with total charge-transfer step. IR-compensated current density (i)-overpotential (η) relationship is established and the exchange current densities i o originated from high-field approximations are much higher than those of low-field approximations and a.c. impedance data under OCV state. It demonstrates the polarization overpotential has great effect on the kinetics of ORR. The polarization current is observed to increase with time in the long-term stability measurement, which can be ascribed to the propagation process of oxygen vacancies.

  20. Probing the influence of the center atom coordination structure in iron phthalocyanine multi-walled carbon nanotube-based oxygen reduction reaction catalysts by X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Peng, Yingxiang; Li, Zhipan; Xia, Dingguo; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia

    2015-09-01

    Three different pentacoordinate iron phthalocyanine (FePc) electrocatalysts with an axial ligand (pyridyl group, Py) anchored to multi-walled carbon nanotubes (MWCNTs) are prepared by a microwave method as high performance composite electrocatalysts (FePc-Py/MWCNTs) for the oxygen reduction reaction (ORR). For comparison, tetracoordinate FePc electrocatalysts without an axial ligand anchored to MWCNTs (FePc/MWCNTs) are assembled in the same way. Ultraviolet-visible spectrophotometry (UV-Vis), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HRTEM) are used to characterize the obtained electrocatalysts. The electrocatalytic activity of the samples is measured by linear sweep voltammetry (LSV), and the onset potential of all of the FePc-Py/MWCNTs electrocatalysts is found to be more positive than that of their FePc/MWCNTs counterparts. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy are employed to elucidate the relationship between molecular structure and electrocatalytic activity. XPS indicates that higher concentrations of Fe3+ and pyridine-type nitrogen play critical roles in determining the electrocatalytic ORR activity of the samples. XAFS spectroscopy reveals that the FePc-Py/MWCNTs electrocatalysts have a coordination geometry around Fe that is closer to the square pyramidal structure, a higher concentration of Fe3+, and a smaller phthalocyanine ring radius compared with those of FePc/MWCNTs.

  1. One-pot synthesis of nitrogen and sulfur co-doped onion-like mesoporous carbon vesicle as an efficient metal-free catalyst for oxygen reduction reaction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Han, Ce; Bo, Xiangjie; Zhang, Yufan; Li, Mian; Guo, Liping

    2014-12-01

    Nitrogen and sulfur co-doped onion-like mesoporous carbon vesicle (NS-MCV) with multilayer lamellar structure is synthesized as a metal-free catalyst through a convenient and economical procedure. The synthesized materials are systematically characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, nitrogen adsorption-desorption, and X-ray photoelectron spectroscopy (XPS). The characterization results demonstrate that N and S atoms can be successfully doped into the framework of MCV with little impact on the morphology and structure. The NS-MCV manifests a remarkably high electrocatalytic activity as a metal-free electrocatalyst for the oxygen reduction reaction (ORR) with mainly a four-electron transfer pathway. Moreover, in contrast to the commercially available Pt/C catalyst, the NS-MCV shows much better long-term stability and tolerance toward methanol crossover in an alkaline medium. Such excellent performances can be mainly attributed to the synergistic effect arising from the addition of N and S heteroatom, optimized S content and high surface area. The NS-MCV with a simple synthesis method may further exploited as potentially efficient and inexpensive metal-free ORR catalyst materials.

  2. Cobalt Molybdenum Oxynitrides: Synthesis, Structural, Characterization, and Catalytic Activity for the Oxygen Reduction Reaction

    SciTech Connect

    Cao, Bingfei; Veith, Gabriel M; Diaz, Rosa; Liu, Jue; Stach, Eric; Adzic, Radoslav R.; Khalifah, P.

    2013-01-01

    Here, we report the synthesis and characterization of CoxMo1 xOyNz compounds supported on carbon black as potential cathode catalysts for ORR. They were prepared by a conventional impregnation method. Their ORR activities in both acid and alkaline electrolytes were evaluated via half-cell measurements. The synthesis temperature and sample composition both strongly impacted their physical and chemical properties. Factors influencing their crystal structures, morphologies and ORR activities will be discussed based on the results of structural and spectroscopic studies.

  3. Enhanced electrocatalytic activity and stability of Pd3V/C nanoparticles with a trace amount of Pt decoration for the oxygen reduction reaction

    SciTech Connect

    Liu, Sufen; Han, Lili; Zhu, Jing; Xiao, Weiping; Wang, Jie; Liu, Hongfang; Xin, Huolin; Wang, Deli

    2015-09-14

    In this study, carbon supported Pd3V bimetallic alloy nanoparticles (Pd3V/C) have been successfully synthesized via a simple impregnation–reduction method, followed by high temperature treatment under a H2 atmosphere. Electrochemical tests reveal that the half-wave potential of Pd3V/C-500 shifts positively 40 mV compared with Pd/C. However, the catalytic activity of Pd3V/C-500 suffers from serious degradation after 1k cycles. By a spontaneous displacement reaction or co-reduction method, a trace amount of Pt was decorated on the surface or inside of the Pd3V/C nanoparticles. The catalytic activity and stability of the Pd3V@Pt/C and Pt-Pd3V/C catalysts for the oxygen reduction reaction (ORR) are enhanced significantly, and are comparable to commercial Pt/C. In addition, the Pt mass activity of Pd3V@Pt/C and Pt-Pd3V/C improves by factors of 10.9 and 6.5 at 0.80 V relative to Pt/C. Moreover, Pt-decorated Pd3V/C nanoparticles show almost no obvious morphology change after durability tests, because the Pt-rich shell plays an important role in preventing degradation.

  4. Planning and conduct of operational readiness reviews (ORR)

    SciTech Connect

    Not Available

    1993-11-01

    The purpose of this Standard is to establish a uniform process for when an ORR (1) of a new nuclear facility is to be started, (2) a previously operated facility is to be restarted, or (3) any new operating phase that results in a significant increase in existing hazards, or could introduce significant hazards not previously encountered is planned. This Standard describes a method to verify that the facility is physically ready to startup, that the managers and operators are prepared to manage and operate the facility in the proposed phase, and that the necessary infrastructure are in place. It also provides a methodology for determining the breadth and depth of the ORR so as to be consistent with the hazards and complexity of the proposed facility transition. This Standard provides procedures for the conduct of an ORR when required by the circumstances of the startup as specified in DOE 5480.31. The Standard also discusses principles and criteria for Readiness Assessments incident to the facility startup process when an ORR in not required.

  5. Reduction of a phosphorus oxide and acid reaction set

    SciTech Connect

    Twarowski, A.

    1995-07-01

    It has been predicted for some time that hypersonic aircraft will suffer from diminished fuel efficiency due to the slow speed of radical recombination in the nozzle of the aircraft and the consequent expulsion of high-energy fragments during high Mach number flight. The addition of small amounts of phosphine combustion products (phosphorus oxides and acids) to water vapor has been found to result in a faster relaxation rate of OH to its equilibrium density following H{sub 2}O photolysis. This article describes the systematic construction of a reaction model of 162 phosphorus reactions among 17 phosphorus-containing species. Those reactions that contribute to the reestablishment of equilibrium following the perturbation of the system by H{sub 2}O photolysis or by an increase in temperature are identified. A thermodynamic free energy function is used to quantify the rate of system relaxation back to equilibrium for a series of 36 reaction conditions covering a temperature range of 1,500 to 3,000 K, a gas density range of 5 {times} 10{sup {minus}7} to 5 {times} 10{sup {minus}5} mol/cm{sup 3} and a fuel equivalence ratio of 0.8 to 1.2.

  6. Nanocrystalline Fe-Fe2O3 particle-deposited N-doped graphene as an activity-modulated Pt-free electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Dhavale, Vishal M.; Singh, Santosh K.; Nadeema, Ayasha; Gaikwad, Sachin S.; Kurungot, Sreekumar

    2015-11-01

    The size-controlled growth of nanocrystalline Fe-Fe2O3 particles (2-3 nm) and their concomitant dispersion on N-doped graphene (Fe-Fe2O3/NGr) could be attained when the mutually assisted redox reaction between NGr and Fe3+ ions could be controlled within the aqueous droplets of a water-in-oil emulsion. The synergistic interaction existing between Fe-Fe2O3 and NGr helped the system to narrow down the overpotential for the oxygen reduction reaction (ORR) by bringing a significant positive shift to the reduction onset potential, which is just 15 mV higher than its Pt-counterpart. In addition, the half-wave potential (E1/2) of Fe-Fe2O3/NGr is found to be improved by a considerable amount of 135 mV in comparison to the system formed by dispersing Fe-Fe2O3 nanoparticles on reduced graphene oxide (Fe-Fe2O3/RGO), which indicates the presence of a higher number of active sites in Fe-Fe2O3/NGr. Despite this, the ORR kinetics of Fe-Fe2O3/NGr are found to be shifted significantly to the preferred 4-electron-transfer pathway compared to NGr and Fe-Fe2O3/RGO. Consequently, the H2O2% was found to be reduced by 78.3% for Fe-Fe2O3/NGr (13.0%) in comparison to Fe-Fe2O3/RGO (51.2%) and NGr (41.0%) at -0.30 V (vs. Hg/HgO). This difference in the yield of H2O2 formed between the systems along with the improvements observed in terms of the oxygen reduction onset and E1/2 in the case of Fe-Fe2O3/NGr reveals the activity modulation achieved for the latter is due to the coexistence of factors such as the presence of the mixed valancies of iron nanoparticles, small size and homogeneous distribution of Fe-Fe2O3 nanoparticles and the electronic modifications induced by the doped nitrogen in NGr. A controlled interplay of these factors looks like worked favorably in the case of Fe-Fe2O3/NGr. As a realistic system level validation, Fe-Fe2O3/NGr was employed as the cathode electrode of a single cell in a solid alkaline electrolyte membrane fuel cell (AEMFC). The system could display an open

  7. Copper-modified covalent triazine frameworks as non-noble-metal electrocatalysts for oxygen reduction.

    PubMed

    Iwase, Kazuyuki; Yoshioka, Tatsuro; Nakanishi, Shuji; Hashimoto, Kazuhito; Kamiya, Kazuhide

    2015-09-14

    The electrochemical oxygen reduction reaction (ORR) is an important cathode reaction of various types of fuel cells. The development of electrocatalysts composed only of abundant elements is a key goal because currently only platinum is a suitable catalyst for ORR. Herein, we synthesized copper-modified covalent triazine frameworks (CTF) hybridized with carbon nanoparticles (Cu-CTF/CPs) as efficient electrocatalysts for the ORR in neutral solutions. The ORR onset potential of the synthesized Cu-CTF/CP was 810 mV versus the reversible hydrogen electrode (RHE; pH 7), the highest reported value at neutral pH for synthetic Cu-based electrocatalysts. Cu-CTF/CP also displayed higher stability than a Cu-based molecular complex at neutral pH during the ORR, a property that was likely as a result of the covalently cross-linked structure of CTF. This work may provide a new platform for the synthesis of durable non-noble-metal electrocatalysts for various target reactions. PMID:26227987

  8. Role of LiCoO2 Surface Terminations in Oxygen Reduction and Evolution Kinetics.

    PubMed

    Han, Binghong; Qian, Danna; Risch, Marcel; Chen, Hailong; Chi, Miaofang; Meng, Ying Shirley; Shao-Horn, Yang

    2015-04-16

    Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of LiCoO2 nanorods with sizes in the range from 9 to 40 nm were studied in alkaline solution. The sides of these nanorods were terminated with low-index surfaces such as (003), while the tips were terminated largely with high-index surfaces such as (104), as revealed by high-resolution transmission electron microscopy. Electron energy loss spectroscopy demonstrated that low-spin Co(3+) prevailed on the sides, while the tips exhibited predominantly high- or intermediate-spin Co(3+). We correlated the electronic and atomic structure to higher specific ORR and OER activities at the tips as compared to the sides, which was accompanied by more facile redox of Co(2+/3+) and higher charge transferred per unit area. These findings highlight the critical role of surface terminations and electronic structures of transition-metal oxides on the ORR and OER activity. PMID:26263135

  9. Study on kinetics of cathodic reduction of dissolved oxygen in 3.5% sodium chloride solution

    NASA Astrophysics Data System (ADS)

    Li, Yongjuan; Zhang, Dun; Wu, Jiajia

    2010-09-01

    Electrochemical reduction of dissolved oxygen in seawater on metals is of great importance for corrosion studies. The present paper studied cathodic reduction of dissolved oxygen on Q235 carbon steel in 3.5% sodium chloride (NaCl) solutions by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE). The cyclic voltammetric results demonstrated the cathodic process on Q235 carbon steel in O2-saturated 3.5% NaCl solution contains three reactions: dissolved oxygen reduction, iron oxides reduction and hydrogen evolution. The peak potential of oxygen reduction reaction (ORR) is -0.85 V vs Ag/AgCl, 3 molL-1 KCl. The EIS results indicated that the ORR occurring on Q235 carbon steel is a 4-electron process and that no finite diffusion is caused by the intermediate of H2O2 produced by ORR. The RDE and RRDE voltammograms confirmed the EIS results and it was found that the number of transferred electrons for ORR was nearly 4, i.e., dissolved oxygen reduced to water.

  10. Opening gates to oxygen reduction reactions on Cu(111) surface

    NASA Astrophysics Data System (ADS)

    Sumer, Aslihan; Chaudhuri, Santanu

    2015-03-01

    Electrocatalytic reduction of oxygen is composed of multiple steps, including the diffusion-adsorption-dissociation of molecular oxygen. This study explores the role of electrical double layer in aqueous medium in quantifying the rate of these coupled electrochemical processes at the electrode interface during oxygen reduction. The electronic, energetic, and configurational aspects of molecular oxygen diffusion and adsorption onto Cu(111) in water are identified through density functional theory based computations. The liquid phase on Cu(111) is modeled with hexagonal-ordered water bilayers, at two slightly different structures, with O-H bonds either facing the vacuum or the metal surface. The results indicate that the energetically preferred structure of water bilayers and adsorption configuration of O2 are different in cathodic and anodic potentials. The diffusion of O2 is found to be heavily hindered at the water/metal interface because of the ordering of water molecules in bilayers as compared to the bulk liquid. The unique correlations of diffusion and adsorption kinetics with water structure identified in this work can provide clues for improving oxygen reduction efficiency.

  11. Opening gates to oxygen reduction reactions on Cu(111) surface.

    PubMed

    Sumer, Aslihan; Chaudhuri, Santanu

    2015-03-28

    Electrocatalytic reduction of oxygen is composed of multiple steps, including the diffusion-adsorption-dissociation of molecular oxygen. This study explores the role of electrical double layer in aqueous medium in quantifying the rate of these coupled electrochemical processes at the electrode interface during oxygen reduction. The electronic, energetic, and configurational aspects of molecular oxygen diffusion and adsorption onto Cu(111) in water are identified through density functional theory based computations. The liquid phase on Cu(111) is modeled with hexagonal-ordered water bilayers, at two slightly different structures, with O-H bonds either facing the vacuum or the metal surface. The results indicate that the energetically preferred structure of water bilayers and adsorption configuration of O2 are different in cathodic and anodic potentials. The diffusion of O2 is found to be heavily hindered at the water/metal interface because of the ordering of water molecules in bilayers as compared to the bulk liquid. The unique correlations of diffusion and adsorption kinetics with water structure identified in this work can provide clues for improving oxygen reduction efficiency. PMID:25833599

  12. Opening gates to oxygen reduction reactions on Cu(111) surface

    SciTech Connect

    Sumer, Aslihan; Chaudhuri, Santanu

    2015-03-28

    Electrocatalytic reduction of oxygen is composed of multiple steps, including the diffusion-adsorption-dissociation of molecular oxygen. This study explores the role of electrical double layer in aqueous medium in quantifying the rate of these coupled electrochemical processes at the electrode interface during oxygen reduction. The electronic, energetic, and configurational aspects of molecular oxygen diffusion and adsorption onto Cu(111) in water are identified through density functional theory based computations. The liquid phase on Cu(111) is modeled with hexagonal-ordered water bilayers, at two slightly different structures, with O–H bonds either facing the vacuum or the metal surface. The results indicate that the energetically preferred structure of water bilayers and adsorption configuration of O{sub 2} are different in cathodic and anodic potentials. The diffusion of O{sub 2} is found to be heavily hindered at the water/metal interface because of the ordering of water molecules in bilayers as compared to the bulk liquid. The unique correlations of diffusion and adsorption kinetics with water structure identified in this work can provide clues for improving oxygen reduction efficiency.

  13. Studies of reductive elimination reactions to form carbon-oxygen bonds from Pt(IV) complexes.

    PubMed

    Williams, B S; Goldberg, K I

    2001-03-21

    The platinum(IV) complexes fac-L(2)PtMe(3)(OR) (L(2) = bis(diphenylphosphino)ethane, o-bis(diphenylphosphino)benzene, R = carboxyl, aryl; L = PMe(3), R = aryl) undergo reductive elimination reactions to form carbon-oxygen bonds and/or carbon-carbon bonds. The carbon-oxygen reductive elimination reaction produces either methyl esters or methyl aryl ethers (anisoles) and L(2)PtMe(2), while the carbon-carbon reductive elimination reaction affords ethane and L(2)PtMe(OR). Choice of reaction conditions allows the selection of either type of coupling over the other. A detailed mechanistic study of the reductive elimination reactions supports dissociation of the OR(-) ligand as the initial step for the C-O bond formation reaction. This is followed by a nucleophilic attack of OR(-) upon a methyl group bound to the Pt(IV) cation to produce the products MeOR and L(2)PtMe(2). C-C reductive elimination proceeds from L(2)PtMe(3)(OR) by initial L (L = PMe(3)) or OR(-) (L(2) = dppe, dppbz) dissociation, followed by C-C coupling from the resulting five-coordinate intermediate. Our studies demonstrate that both C-C and C-O reductive elimination reactions from Pt(IV) are more facile in polar solvents, in the presence of Lewis acids, and for OR(-) groups that contain electron withdrawing substituents. PMID:11456927

  14. Platinum Monolayer on IrFe Core-Shell Nanoparticle Electrocatalysts for the Oxygen Reduction Reaction

    SciTech Connect

    K Sasaki; K Kuttiyiel; D Su; R Adzic

    2011-12-31

    We synthesized high activity and stability platinum monolayer on IrFe core-shell nanoparticle electrocatalysts. Carbon-supported IrFe core-shell nanoparticles were synthesized by chemical reduction and subsequent thermal annealing. The formation of Ir shells on IrFe solid-solution alloy cores has been verified by scanning transmission electron microscopy coupled with energy-loss spectroscopy (EELS) and in situ X-ray absorption spectroscopy. The Pt monolayers were deposited on IrFe core-shell nanoparticles by galvanic replacement of underpotentially deposited Cu adatoms on the Ir shell surfaces. The specific and Pt mass activities for the ORR on the Pt monolayer on IrFe core-shell nanoparticle electrocatalyst are 0.46 mA/cm{sup 2} and 1.1 A/mg{sub Pt}, which are much higher than those on a commercial Pt/C electrocatalyst. High durability of Pt{sub ML}/IrFe/C has also been demonstrated by potential cycling tests. These high activity and durability observed can be ascribed to the structural and electronic interaction between the Pt monolayer and the IrFe core-shell nanoparticles.

  15. Platinum Monolayer on IrFe Core–Shell Nanoparticle Electrocatalysts for the Oxygen Reduction Reaction

    SciTech Connect

    Sasaki K.; Kuttiyiel, K.A.; Su, D.; Adzic, R.R.

    2012-04-19

    We synthesized high activity and stability platinum monolayer on IrFe core-shell nanoparticle electrocatalysts. Carbon-supported IrFe core-shell nanoparticles were synthesized by chemical reduction and subsequent thermal annealing. The formation of Ir shells on IrFe solid-solution alloy cores has been verified by scanning transmission electron microscopy coupled with energy-loss spectroscopy (EELS) and in situ X-ray absorption spectroscopy. The Pt monolayers were deposited on IrFe core-shell nanoparticles by galvanic replacement of underpotentially deposited Cu adatoms on the Ir shell surfaces. The specific and Pt mass activities for the ORR on the Pt monolayer on IrFe core-shell nanoparticle electrocatalyst are 0.46 mA/cm{sup 2} and 1.1 A/mg{sub Pt}, which are much higher than those on a commercial Pt/C electrocatalyst. High durability of Pt{sub ML}/IrFe/C has also been demonstrated by potential cycling tests. These high activity and durability observed can be ascribed to the structural and electronic interaction between the Pt monolayer and the IrFe core-shell nanoparticles.

  16. Sex Discrimination and the Equal Protection Clause: An Analysis of Kahn v. Shevin and Orr v. Orr.

    ERIC Educational Resources Information Center

    Hull, E. A.

    1979-01-01

    Argues that "Kahn" continues stereotypic thinking toward women whereas "Orr" may call sex-based dispensations into question. Calls for declaring sex a suspect classification. Available from the Syracuse Law Review, Syracuse University, Syracuse, NY 13210; sc $3.50. (IRT)

  17. Platinum-cobalt catalysts for the oxygen reduction reaction in high temperature proton exchange membrane fuel cells - Long term behavior under ex-situ and in-situ conditions

    NASA Astrophysics Data System (ADS)

    Schenk, Alexander; Grimmer, Christoph; Perchthaler, Markus; Weinberger, Stephan; Pichler, Birgit; Heinzl, Christoph; Scheu, Christina; Mautner, Franz-Andreas; Bitschnau, Brigitte; Hacker, Viktor

    2014-11-01

    Platinum cobalt catalysts (Pt-Co) have attracted much interest as cathode catalysts for proton exchange membrane fuel cells (PEMFCs) due to their high activity toward oxygen reduction reaction (ORR). Many of the reported catalysts show outstanding performance in ex-situ experiments. However, the laborious synthesis protocols of these Pt-Co catalysts disable an efficient and economic production of membrane electrode assemblies (MEAs). We present an economic, flexible and continuous Pt-M/C catalyst preparation method as part of a large scale membrane electrode assembly manufacturing. In comparison, the as-prepared Pt-Co/C based high temperature (HT)-PEM MEA showed an equal performance to a commercially available HT-PEM MEA during 600 h of operation under constant load, although the commercial one had a significantly higher Pt loading at the cathode.

  18. Enhanced electrocatalysis of the oxygen reduction reaction based on pattering of platinum surfaces with cyanide.

    SciTech Connect

    Strmcnik, D.; Escudero-Escribano, M.; Kodama, K.; Stamenkovic, V. R.; Cuesta, A.; Markovic, N. M.; Materials Science Division; Inst. de Quimica Fisica; Toyota Central R&D Labs., Inc.

    2010-08-15

    The slow rate of the oxygen reduction reaction in the phosphoric acid fuel cell is the main factor limiting its wide application. Here, we present an approach that can be used for the rational design of cathode catalysts with potential use in phosphoric acid fuel cells, or in any environments containing strongly adsorbing tetrahedral anions. This approach is based on molecular patterning of platinum surfaces with cyanide adsorbates that can efficiently block the sites for adsorption of spectator anions while the oxygen reduction reaction proceeds unhindered. We also demonstrate that, depending on the supporting electrolyte anions and cations, on the same CN-covered Pt(111) surface, the oxygen reduction reaction activities can range from a 25-fold increase to a 50-fold decrease. This behaviour is discussed in the light of the role of covalent and non-covalent interactions in controlling the ensemble of platinum active sites required for high turn over rates of the oxygen reduction reaction.

  19. Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide

    SciTech Connect

    Strmcnik, D.; Escudero, M.; Kodama, K.; Stamenkovic, V. R.; Cuesta, A.; Markovic, N. M.

    2010-10-01

    The slow rate of the oxygen reduction reaction in the phosphoric acid fuel cell is the main factor limiting its wide application. Here, we present an approach that can be used for the rational design of cathode catalysts with potential use in phosphoric acid fuel cells, or in any environments containing strongly adsorbing tetrahedral anions. This approach is based on molecular patterning of platinum surfaces with cyanide adsorbates that can efficiently block the sites for adsorption of spectator anions while the oxygen reduction reaction proceeds unhindered. We also demonstrate that, depending on the supporting electrolyte anions and cations, on the same CN-covered Pt(111) surface, the oxygen reduction reaction activities can range from a 25-fold increase to a 50-fold decrease. This behaviour is discussed in the light of the role of covalent and non-covalent interactions in controlling the ensemble of platinum active sites required for high turn over rates of the oxygen reduction reaction.

  20. Method of reduction of nitroaromatics by enzymatic reaction with redox enzymes

    DOEpatents

    Shah, Manish M.

    2000-01-01

    A method for the controlled reduction of nitroaromatic compounds such as nitrobenzene and 2,4,6-trinitrotoluene by enzymatic reaction with redox enzymes, such as Oxyrase (Trademark of Oxyrase, Inc., Mansfield, Ohio).

  1. Method of controlled reduction of nitroaromatics by enzymatic reaction with oxygen sensitive nitroreductase enzymes

    DOEpatents

    Shah, M.M.; Campbell, J.A.

    1998-07-07

    A method is described for the controlled reduction of nitroaromatic compounds such as nitrobenzene and 2,4,6-trinitrotoluene by enzymatic reaction with oxygen sensitive nitroreductase enzymes, such as ferredoxin NADP oxidoreductase. 6 figs.

  2. Method of controlled reduction of nitroaromatics by enzymatic reaction with oxygen sensitive nitroreductase enzymes

    DOEpatents

    Shah, Manish M.; Campbell, James A.

    1998-01-01

    A method for the controlled reduction of nitroaromatic compounds such as nitrobenzene and 2,4,6-trinitrotoluene by enzymatic reaction with oxygen sensitive nitroreductase enzymes, such as ferredoxin NADP oxidoreductase.

  3. Organic radicals for the enhancement of oxygen reduction reaction in Li-O2 batteries.

    PubMed

    Tesio, A Y; Blasi, D; Olivares-Marín, M; Ratera, I; Tonti, D; Veciana, J

    2015-12-25

    We examine for the first time the ability of inert carbon free-radicals as soluble redox mediators to catalyze and enhance the oxygen reduction reaction in a (TEGDME)-based electrolyte. We demonstrate that the tris(2,4,6-trichlorophenyl)methyl (TTM) radical is capable of chemically favoring the oxygen reduction reaction improving significantly the Li-O2 battery performance. PMID:26488114

  4. Transition Metal Nitride Coated with Atomic Layers of Pt as a Low-Cost, Highly Stable Electrocatalyst for the Oxygen Reduction Reaction.

    PubMed

    Tian, Xinlong; Luo, Junming; Nan, Haoxiong; Zou, Haobin; Chen, Rong; Shu, Ting; Li, Xiuhua; Li, Yingwei; Song, Huiyu; Liao, Shijun; Adzic, Radoslav R

    2016-02-10

    The main challenges to the commercial viability of polymer electrolyte membrane fuel cells are (i) the high cost associated with using large amounts of Pt in fuel cell cathodes to compensate for the sluggish kinetics of the oxygen reduction reaction, (ii) catalyst degradation, and (iii) carbon-support corrosion. To address these obstacles, our group has focused on robust, carbon-free transition metal nitride materials with low Pt content that exhibit tunable physical and catalytic properties. Here, we report on the high performance of a novel catalyst with low Pt content, prepared by placing several layers of Pt atoms on nanoparticles of titanium nickel binary nitride. For the ORR, the catalyst exhibited a more than 400% and 200% increase in mass activity and specific activity, respectively, compared with the commercial Pt/C catalyst. It also showed excellent stability/durability, experiencing only a slight performance loss after 10,000 potential cycles, while TEM results showed its structure had remained intact. The catalyst's outstanding performance may have resulted from the ultrahigh dispersion of Pt (several atomic layers coated on the nitride nanoparticles), and the excellent stability/durability may have been due to the good stability of nitride and synergetic effects between ultrathin Pt layer and the robust TiNiN support. PMID:26796872

  5. Transition metal nitride coated with atomic layers of Pt as a low-cost, highly stable electrocatalyst for the oxygen reduction reaction

    DOE PAGESBeta

    Tian, Xinlong; Adzic, Radoslav R.; Luo, Junming; Nan, Haoxiong; Zou, Haobin; Chen, Rong; Shu, Ting; Li, Xiuhua; Li, Yingwei; Song, Huiyi; et al

    2016-01-21

    Here, the main challenges to the commercial viability of polymer electrolyte membrane fuel cells are (i) the high cost associated with using large amounts of Pt in fuel cell cathodes to compensate for the sluggish kinetics of the oxygen reduction reaction, (ii) catalyst degradation, and (iii) carbon-support corrosion. To address these obstacles, our group has focused on robust, carbon-free transition metal nitride materials with low Pt content that exhibit tunable physical and catalytic properties. Here, we report on the high performance of a novel catalyst with low Pt content, prepared by placing several layers of Pt atoms on nanoparticles ofmore » titanium nickel binary nitride. For the ORR, the catalyst exhibited a more than 400% and 200% increase in mass activity and specific activity, respectively, compared with the commercial Pt/C catalyst. It also showed excellent stability/durability, experiencing only a slight performance loss after 10,000 potential cycles, while TEM results showed its structure had remained intact. The catalyst’s outstanding performance may have resulted from the ultrahigh dispersion of Pt (several atomic layers coated on the nitride nanoparticles), and the excellent stability/durability may have been due to the good stability of nitride and synergetic effects between ultrathin Pt layer and the robust TiNiN support.« less

  6. A Strategy to Promote the Electrocatalytic Activity of Spinels for Oxygen Reduction by Structure Reversal.

    PubMed

    Wu, Guangping; Wang, Jun; Ding, Wei; Nie, Yao; Li, Li; Qi, Xueqiang; Chen, Siguo; Wei, Zidong

    2016-01-22

    The electrocatalytic performance of a spinel for the oxygen reduction reaction (ORR) can be significantly promoted by reversing its crystalline structure from the normal to the inverse. As the spinel structure reversed, the activation and cleavage of O-O bonds are accelerated owing to a dissimilarity effect of the distinct metal atoms co-occupying octahedral sites. The Co(II)Fe(III)Co(III)O4 spinel with the Fe and Co co-occupying inverse structure exhibits an excellent ORR activity, which even exceeds that of the state-of-the-art commercial Pt/C by 42 mV in alkaline medium. PMID:26663768

  7. Theory and experiments for voltammetric and SECM investigations and application to ORR electrocatalysis at nanoelectrode ensembles of ultramicroelectrode dimensions.

    PubMed

    Fernández, José L; Wijesinghe, Manjula; Zoski, Cynthia G

    2015-01-20

    Theoretical and experimental approaches to characterizing nanoelectrode (NE) ensembles of ultramicroelectrode dimensions (UME-NEEs) as a function of fraction of active area and random NE distribution are described. UME-NEEs were fabricated by addressing microregions of a gold-filled polycarbonate membrane through the UMEs of an underlying microfabricated addressable array. Results of Comsol Multiphysics 3D simulations based on randomly spaced NEs of 15 nm radius on a UME disk geometry of radii up to 5 μm are shown for steady-state voltammetry (SSV) and scanning electrochemical microscopy (SECM) experiments. Analytical equations were developed to describe the diffusion-limited steady-state current and steady-state voltammogram at an UME-NEE. These equations are shown to be in good agreement with the simulations and enabled evaluation of experimental SSVs. Comparison of experimental and simulated SECM approach curves, images, and tip voltammograms enabled the fraction of active area and distribution of NEs to be visualized and determined for individual UME-NEEs. Gold UME-NEEs are shown to be unique platforms for electrodeposition in forming nanoparticle electrodes (UME-NPEs). Electrocatalysis results for the oxygen reduction reaction (ORR) on Pt UME-NPEs in 0.1 M H2SO4 are also shown. PMID:25495486

  8. Engineering self-assembled N-doped graphene-carbon nanotube composites towards efficient oxygen reduction electrocatalysts.

    PubMed

    Zhang, Yun; Jiang, Wen-Jie; Zhang, Xing; Guo, Lin; Hu, Jin-Song; Wei, Zidong; Wan, Li-Jun

    2014-07-21

    The importance of the oxygen reduction reaction (ORR) in fuel cells and high energy density metal-air batteries has attracted intense research interests in looking for low-cost ORR catalysts as substitutes for expensive and scarce Pt-based catalysts. N-doped graphene and carbon nanotubes prepared in a low-cost and scalable way have demonstrated their potential although the performance still needs to be improved. In view of the requirements for a high-performance ORR electrocatalyst, this work focused on developing the nanocomposites of N-doped reduced graphene oxide (N-rGO) and N-doped carbon nanotubes (N-CNT) as low-cost efficient ORR catalysts by integrating the advantages of abundant highly-active sites from N-rGO and a three-dimensional conductive network for efficient mass and electron transport from N-CNT. By optimizing the preparation method and dedicatedly tuning the composition, the much enhanced ORR activity and superior durability and tolerance to methanol were achieved for the self-assembled N-doped composite (N-rGO-CNT) at a mass ratio of 1 : 5 rGO/CNT. Further improvement of the ORR electrocatalytic activity of the composite was also demonstrated by introducing iron into the composite. PMID:24722811

  9. Metal-Organic Coordination Networks: Prussian Blue and Its Synergy with Pt Nanoparticles to Enhance Oxygen Reduction Kinetics.

    PubMed

    Du, Lei; Du, Chunyu; Chen, Guangyu; Kong, Fanpeng; Yin, Geping; Wang, Yong

    2016-06-22

    Oxygen reduction reaction (ORR) is the cornerstone in the electrochemical energy conversion devices such as fuel cells and metal-air batteries. It remains a great challenge to develop the ORR electrocatalysts with fast kinetics and high durability. Herein, we report the synthesis of a novel metal-organic coordination networks material, prussian blue crystalline nanograins mosaicked within amorphous membrane (PB CNG-M-AM). Such unique PB CNG-M-AM is designed to enhance the electrocatalysis of Pt toward the ORR by the electrostatic self-assembly. Thus, obtained Pt-PB/C catalysts form numerous Pt-PB-gas three-phase boundaries and present rather high intrinsic activity, four-electron selectivity and superior stability. Moreover, a completely new synergetic mechanism between PB and Pt is discovered, which delicately alters the ORR route and significantly enhances the ORR kinetics. This work provides not only a new strategy and mechanism for developing highly efficient ORR electrocatalysts, but also an alternative way to utilize metal-organic coordination networks materials. PMID:27253719

  10. Copper N-Heterocyclic Carbene: A Catalyst for Aerobic Oxidation or Reduction Reactions.

    PubMed

    Zhan, Le-Wu; Han, Lei; Xing, Ping; Jiang, Biao

    2015-12-18

    Copper N-heterocyclic carbene complexes can be readily used as catalysts for both aerobic oxidation of alcohols to aldehydes and reduction of imines to amines. Our methodology is universal for aromatic substrates and shows versatile tolerance to potential cascade reactions. A one-pot tandem synthetic strategy could afford useful imines and secondary amines via an oxidation-reduction strategy. PMID:26633757

  11. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NO x Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis.

    PubMed

    Gerken, James B; Stahl, Shannon S

    2015-08-26

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NO x ) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NO x species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NO x species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NO x species, together with kinetically efficient reduction of oxidized NO x species by TEMPO and other organic nitroxyls. PMID:27162977

  12. Superior oxygen reduction electrocatalysis enabled by integrating hierarchical pores, Fe3C nanoparticles and bamboo-like carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Yang, Wenxiu; Yue, Xiaoyu; Liu, Xiangjian; Chen, Lulu; Jia, Jianbo; Guo, Shaojun

    2015-12-01

    Hierarchical porous carbon nanostructures doped with nitrogen or other active elements have been demonstrated to be of importance in enhancing the oxygen reduction reaction (ORR) activity. However, their intrinsic limited active sites usually make them exhibit lower ORR activity than commercial Pt/C. In order to solve well this challenging issue, herein we develop a simple method for encapsulating more electrochemically active Fe3C nanoparticles (NPs) into the channels of bamboo-like carbon nanotubes (bCNTs) with interesting 3D hierarchical micro-, meso- and macropores by impregnating the bCNTs with a Fe(NO3)3 solution, followed by the calcination of the composite under a N2 atmosphere. The resulting bCNT/Fe3C hybrid electrocatalysts with much more active sites exhibit excellent ORR activity in acidic media with the half-wave potential of 0.710 V comparable to the commercial Pt/C catalyst (0.782 V). Furthermore, they show very high ORR activity in 0.10 M KOH with the half-wave potential of 0.879 V, 67 mV more positive than that of the Pt/C catalyst. Most importantly, the as-prepared new catalysts are very stable for ORR in both acidic and alkaline solutions with almost no ORR polarization curve shift after 3000 cycles, much better than that of the Pt/C catalyst. To the best of our knowledge, our new bCNT/Fe3C catalyst is the best non-noble-metal catalyst ever reported for ORR under both acidic and alkaline conditions. The present work highlights the important roles of introducing more stable Fe3C NPs and hierarchical micro-, meso- and macropores as much more active sites in maximizing the ORR electrocatalysis performance.Hierarchical porous carbon nanostructures doped with nitrogen or other active elements have been demonstrated to be of importance in enhancing the oxygen reduction reaction (ORR) activity. However, their intrinsic limited active sites usually make them exhibit lower ORR activity than commercial Pt/C. In order to solve well this challenging issue

  13. Electrocatalytic reduction of acetone in a proton-exchange-membrane reactor: a model reaction for the electrocatalytic reduction of biomass.

    PubMed

    Green, Sara K; Tompsett, Geoffrey A; Kim, Hyung Ju; Bae Kim, Won; Huber, George W

    2012-12-01

    Acetone was electrocatalytically reduced to isopropanol in a proton-exchange-membrane (PEM) reactor on an unsupported platinum cathode. Protons needed for the reduction were produced on the unsupported Pt-Ru anode from either hydrogen gas or electrolysis of water. The current efficiency (the ratio of current contributing to the desired chemical reaction to the overall current) and reaction rate for acetone conversion increased with increasing temperature or applied voltage for the electrocatalytic acetone/water system. The reaction rate and current efficiency went through a maximum with respect to acetone concentration. The reaction rate for acetone conversion increased with increasing temperature for the electrocatalytic acetone/hydrogen system. Increasing the applied voltage for the electrocatalytic acetone/hydrogen system decreased the current efficiency due to production of hydrogen gas. Results from this study demonstrate the commercial feasibility of using PEM reactors to electrocatalytically reduce biomass-derived oxygenates into renewable fuels and chemicals. PMID:22961747

  14. 33. 20HORSE POWER VERTICAL BOILER WAS MANUFACTURED BY ORR & ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    33. 20-HORSE POWER VERTICAL BOILER WAS MANUFACTURED BY ORR & SEMBOWER, FROM READING, PA. IT WAS INSTALLED IN 1929 TO REPLACE THE ORIGINAL BOILER. THE BOILER PROVIDED STEAM TO THE STEAM ENGINE. TO LUBRICATING THE DIE OF THE BRICK AUGER, AND TO THE STEAM PIPES OF THE DRYING ROOM ON THE FLOOR ABOVE. - Moravian Pottery & Tile Works, Southwest side of State Route 313 (Swamp Road), Northwest of East Court Street, Doylestown, Bucks County, PA

  15. The role of the central Fe atom in the N4-macrocyclic structure for the enhancement of oxygen reduction reaction in a heteroatom nitrogen-carbon nanosphere.

    PubMed

    Kim, Dae-wook; Li, Oi Lun; Saito, Nagahiro

    2014-07-28

    In the present work, we demonstrated the significance of a central transition metal, Fe, in a N4-macrocycle for the enhancement of ORR activity and other electrochemical properties. The catalysts were synthesized by a solution plasma process. Fe-phthalocyanine/benzene and phthalocyanine/benzene were chosen as the precursors of Fe-phthalocyanine based mesoporous carbon (FP-MCS) and phthalocyanine based mesoporous carbon (P-MCS) catalysts, respectively. The existence of Fe-N4 and N4 macrocyclic structures was confirmed by X-ray photoelectron spectroscopy. From the chemical bonding structure, FP-MCS demonstrated that the Me-N peaks increased as the amount of iron-phthalocyanine introduced in the experiment increased. The dominant active site was shifted from pyridinic nitrogen to Me-N when iron-phthalocyanine was present. The analysis of Tof-SIMS indicated that the relative intensity of FeN4Cy(+) ions was approximately 50% of the total amount of ionized species of ∑FeNxCy(+). Both XPS and Tof-SIMS results confirmed that the Fe-N4 site was the most favourable structure in the matrix. From CV measurements, the cathodic peak current corresponding to ORR activity slightly shifted from -0.19 V to -0.17 V when the active site changed from N4 to Fe-N4 macrocyclic structure. The current density increased more than 30% in the presence of iron. Based on the calculation of Koutecky-Levich plots, the electron transfer numbers for ORR reaction in P- and FP-MCSs were 3.25 and 3.98, respectively. These results clearly demonstrated that the presence of a Fe central ion in the N4-macrocyclic structure significantly enhanced the ORR and charge transfer number in ORR activities. PMID:24931058

  16. Superior oxygen reduction electrocatalysis enabled by integrating hierarchical pores, Fe3C nanoparticles and bamboo-like carbon nanotubes.

    PubMed

    Yang, Wenxiu; Yue, Xiaoyu; Liu, Xiangjian; Chen, Lulu; Jia, Jianbo; Guo, Shaojun

    2016-01-14

    Hierarchical porous carbon nanostructures doped with nitrogen or other active elements have been demonstrated to be of importance in enhancing the oxygen reduction reaction (ORR) activity. However, their intrinsic limited active sites usually make them exhibit lower ORR activity than commercial Pt/C. In order to solve well this challenging issue, herein we develop a simple method for encapsulating more electrochemically active Fe3C nanoparticles (NPs) into the channels of bamboo-like carbon nanotubes (bCNTs) with interesting 3D hierarchical micro-, meso- and macropores by impregnating the bCNTs with a Fe(NO3)3 solution, followed by the calcination of the composite under a N2 atmosphere. The resulting bCNT/Fe3C hybrid electrocatalysts with much more active sites exhibit excellent ORR activity in acidic media with the half-wave potential of 0.710 V comparable to the commercial Pt/C catalyst (0.782 V). Furthermore, they show very high ORR activity in 0.10 M KOH with the half-wave potential of 0.879 V, 67 mV more positive than that of the Pt/C catalyst. Most importantly, the as-prepared new catalysts are very stable for ORR in both acidic and alkaline solutions with almost no ORR polarization curve shift after 3000 cycles, much better than that of the Pt/C catalyst. To the best of our knowledge, our new bCNT/Fe3C catalyst is the best non-noble-metal catalyst ever reported for ORR under both acidic and alkaline conditions. The present work highlights the important roles of introducing more stable Fe3C NPs and hierarchical micro-, meso- and macropores as much more active sites in maximizing the ORR electrocatalysis performance. PMID:26658501

  17. Platinum-based oxygen reduction electrocatalysts.

    PubMed

    Wu, Jianbo; Yang, Hong

    2013-08-20

    An efficient oxygen reduction reaction (ORR) offers the potential for clean energy generation in low-temperature, proton-exchange membrane fuel cells running on hydrogen fuel and air. In the past several years, researchers have developed high-performance electrocatalysts for the ORR to address the obstacles of high cost of the Pt catalyst per kilowatt of output power and of declining catalyst activity over time. Current efforts are focused on new catalyst structures that add a secondary metal to change the d-band center and the surface atomic arrangement of the catalyst, altering the chemisorption of those oxygencontaining species that have the largest impact on the ORR kinetics and improving the catalyst activity and cost effectiveness. This Account reviews recent progress in the design of Pt-based ORR electrocatalysts, including improved understanding of the reaction mechanisms and the development of synthetic methods for producing catalysts with high activity and stability. Researchers have made several types of highly active catalysts, including an extended single crystal surface of Pt and its alloy, bimetallic nanoparticles, and self-supported, low-dimensional nanostructures. We focus on the design and synthetic strategies for ORR catalysts including controlling the shape (or facet) and size of Pt and its bimetallic alloys, and controlling the surface composition and structure of core-shell, monolayer, and hollow porous structures. The strong dependence of ORR performance on facet and size suggests that synthesizing nanocrystals with large, highly reactive {111} facets could be as important, if not more important, to increasing their activity as simply making smaller nanoparticles. A newly developed carbon-monoxide (CO)-assisted reduction method produces Pt bimetallic nanoparticles with controlled facets. This CO-based approach works well to control shapes because of the selective CO binding on different, low-indexed metal surfaces. Post-treatment under

  18. Regioselectivity and Enantioselectivity in Nickel-Catalysed Reductive Coupling Reactions of Alkynes

    PubMed Central

    Moslin, Ryan M.; Miller-Moslin, Karen; Jamison, Timothy F.

    2011-01-01

    Nickel-catalysed reductive coupling reactions of alkynes have emerged as powerful synthetic tools for the selective preparation of functionalized alkenes. One of the greatest challenges associated with these transformations is control of regioselectivity. Recent work from our laboratory has provided an improved understanding of several of the factors governing regioselectivity in these reactions, and related studies have revealed that the reaction mechanism can differ substantially depending on the ligand employed. A discussion of stereoselective transformations and novel applications of nickel catalysis in coupling reactions of alkynes is also included. PMID:17971951

  19. High-performance oxygen reduction catalyst derived from porous, nitrogen-doped carbon nanosheets.

    PubMed

    Wang, Hao; Chen, Kai; Cao, Yingjie; Zhu, Juntong; Jiang, Yining; Feng, Lai; Dai, Xiao; Zou, Guifu

    2016-10-01

    A facile, self-foaming strategy is reported to synthesize porous, nitrogen-doped carbon nanosheets (N-CNSs) as a metal-free electrocatalyst for oxygen reduction reaction (ORR). Benefiting from the synergistic functions of N-induced active sites, a highly specific surface area and continuous structure, the optimal N-CNS catalyst exhibits Pt-like ORR activity (positive onset potential of ∼0 V versus Ag/AgCl and limiting current density of 5 mA cm(-2)) through a four-electron transfer process in alkaline media with excellent cycle stability and methanol tolerance. This work not only provides a promising metal-free ORR catalyst but also opens up a new path for designing carbon-based materials towards broad applications. PMID:27575594

  20. Structural effects of a carbon matrix in non-precious metal O2-reduction electrocatalysts.

    PubMed

    He, Wenhui; Wang, Ying; Jiang, Chunhuan; Lu, Lehui

    2016-05-01

    Developing non-precious metal electrocatalysts (NPMCs) for the oxygen reduction reaction (ORR) is of paramount importance for commercial implementation of several clean energy techniques (e.g. proton exchange membrane fuel cells). However, limited understanding of the ORR catalytic mechanism of NPMCs greatly hinders the progress in the precise fabrication of NPMCs at the molecular or atomic level. Recently, an increasing number of studies have demonstrated the crucial role of a carbon matrix in exposing, stabilizing, and activating the catalytic sites, thus providing a platform to identify the nature of NPMCs. Herein, the unique structural effects of a carbon matrix in NPMCs are first reviewed to inspire the development of more advanced NPMCs for the ORR. PMID:26955940

  1. Metal molybdate nanorods as non-precious electrocatalysts for the oxygen reduction

    NASA Astrophysics Data System (ADS)

    Wu, Tian; Zhang, Lieyu

    2015-12-01

    Development of non-precious electrocatalysts with applicable electrocatalytic activity towards the oxygen reduction reaction (ORR) is important to fulfill broad-based and large-scale applications of metal/air batteries and fuel cells. Herein, nickel and cobalt molybdates with uniform nanorod morphology are synthesized using a facile one-pot hydrothermal method. The ORR activity of the prepared metal molybdate nanorods in alkaline media are investigated by using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperomety in rotating disk electrode (RDE) techniques. The present study suggests that the prepared metal molybdate nanorods exhibit applicable electrocatalytic activities towards the ORR in alkaline media, promising the applications as non-precious cathode in fuel cells and metal-air batteries.

  2. Tungsten nitride nanocrystals on nitrogen-doped carbon black as efficient electrocatalysts for oxygen reduction reactions.

    PubMed

    Dong, Youzhen; Li, Jinghong

    2015-01-11

    The direct synthesis of tungsten nitride (WN) nanoparticles on nitrogen-doped carbon black (N-carbon black) was achieved through facile nucleation and growth of WN nanoparticles on simultaneously generated N-carbon black under ammonia annealing. As a noble-metal-free catalyst, the WN/N-carbon black hybrid exhibited excellent performance in ORR, coupled with superior methanol tolerance and long-term stability in comparison to commercial Pt/C catalysts, through an efficient four-electron-dominant ORR process. PMID:25413157

  3. Role of Cu-Ion Doping in Cu-α-MnO2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction

    SciTech Connect

    Davis, Danae J.; Lambert, Timothy N.; Vigil, Julian A.; Rodriguez, Mark A.; Brumbach, Michael T.; Coker, Eric N.; Limmer, Steven J.

    2014-07-09

    The role of Cu-ion doping in α-MnO2 electrocatalysts for the oxygen reduction reaction in alkaline electrolyte was investigated. Copper doped α-MnO2 nanowires (Cu-α-MnO2) were prepared with varying amounts of Cu2+ using a solvothermal method. The electrocatalytic dataindicates that Cu-α-MnO2 nanowires have higher terminal current densities, enhanced kinetic rate constants, and improved charge transfer resistances that trend with Cu-content, exceeding values attained by α-MnO2 alone. The observed improvement in catalytic behavior correlates with an increase in Mn3+ content for the Cu-α-MnO2 nanowires. The Mn3+/Mn4+ couple is themediator for the rate-limiting redox driven O2-/OH- exchange. It is proposed that O2 adsorbs viaan axial site (the eg orbital on the Mn3+ d4 ion) at the surface, or at edge defects, of the nanowireand that the increase in covalent nature of the nanowire with Cu-ion doping leads to stabilization of O2 adsorbates and faster rates of reduction. This work is applicable to other manganese oxide electrocatalysts and shows for the first time there is a correlation for manganese oxides between electrocatalytic activity for the ORR in alkaline electrolyte and an increase in Mn3+ character of the oxide.

  4. A comparative study of ORR at the Pt electrode in ammonium ion-contaminated H2SO4 and HClO4 solutions

    NASA Astrophysics Data System (ADS)

    Rahman, Mohammad R.; Awad, Mohamed I.; Kitamura, Fusao; Okajima, Takeyoshi; Ohsaka, Takeo

    2012-12-01

    Poisoning of the poly-Pt electrode by low concentration ammonium ion was investigated in H2SO4 and HClO4 solutions and a significant poisoning was observed in H2SO4 solution. An extraordinary recovery of the poisoned electrode was achieved in HClO4 solution by cycling the electrode potential between the onset potentials of the hydrogen and oxygen evolution. The extent of recovery was marked using the oxygen reduction reaction (ORR) as a probing reaction. Ammonium ion poisoning of the electrodes in H2SO4 caused a significant contribution of the two-electron reduction of O2 to hydrogen peroxide, as indicated by the rotating ring-disk voltammetry. The Tafel slopes at the low and high current densities were also affected by the presence of ammonium ion in H2SO4 solution and an increase in the Tafel slope was recognized with increasing the concentration of ammonium ion. However, the Tafel slopes at the low and high current densities were hardly affected by the ammonium ion in HClO4 solution.

  5. Evidence for Localization of Reaction Upon Reduction of Carbon Tetrachloride by Granular Iron

    SciTech Connect

    Gaspar, Daniel J.; Lea, Alan S.; Engelhard, Mark H.; Baer, Donald R.; Miehr, R.; Tratnyek, Paul G.

    2002-10-01

    The distribution of reaction sites on iron particles exposed to water containing carbon tetrachloride has been examined by measuring the locations of reaction products. The uniformity or localization of reaction sites has implications for understanding and modeling the reduction of environmental contaminants by iron in ground water systems. Granular iron surfaces similar to those being used for environmental remediation applications were studied using surfaces analysis techniques to develop an understanding of the physical and chemical structure of the surface and oxide films. Scanning Auger microscopy and imaging time-of-flight secondary ion mass spectrometry revealed that granular iron exposed to carbon tetrachloride-saturated water exhibits chloride-enriched regions occurred at pits rather than on the passive oxide film on the metal. Understanding the nature of the local solute reduction sites will play an important role in modeling the kinetics of reaction at passive iron oxide films in environmental systems.

  6. Systematic Analysis of Electrochemical CO₂ Reduction with Various Reaction Parameters using Combinatorial Reactors.

    PubMed

    Hashiba, Hiroshi; Yotsuhashi, Satoshi; Deguchi, Masahiro; Yamada, Yuka

    2016-04-11

    Applying combinatorial technology to electrochemical CO2 reduction offers a broad range of possibilities for optimizing the reaction conditions. In this work, the CO2 pressure, stirring speed, and reaction temperature were varied to investigate the effect on the rate of CO2 supply to copper electrode and the associated effects on reaction products, including CH4. Experiments were performed in a 0.5 M KCl solution using a combinatorial screening reactor system consisting of eight identical, automatically controlled reactors. Increasing the CO2 pressure and stirring speed, or decreasing the temperature, steadily suppressed H2 production and increased the production of other reaction products including CH4 across a broad range of current densities. Our analysis shows that the CO2 pressure, stirring speed, and reaction temperature independently contributed to the limiting rate of CO2 supply to the electrode (Jlim). At a constant temperature, the limiting current density of CH4 increased proportionally with Jlim, illustrating that the production rate of CH4 was proportional to CO2 supply. Varying the CO2 pressure and stirring speed hardly affected the maximum Faradaic efficiency of CH4 production. However, changes to the reaction temperature showed a significant contribution to CH4 selectivity. This study highlights the importance of quantitative analysis of CO2 supply in clarifying the role of various reaction parameters and understanding more comprehensively the selectivity and reaction rate of electrochemical CO2 reduction. PMID:27003626

  7. Aqueous Complexation Reactions Governing the Rate and Extent of Biogeochemical U(VI) Reduction

    SciTech Connect

    Scott C. Brooks; Wenming Dong; Sue Carroll; James K. Fredrickson; Kenneth M. Kemner; Shelly D. Kelly

    2006-06-01

    The proposed research will elucidate the principal biogeochemical reactions that govern the concentration, chemical speciation, and reactivity of the redox-sensitive contaminant uranium. The results will provide an improved understanding and predictive capability of the mechanisms that govern the biogeochemical reduction of uranium in subsurface environments. In addition, the work plan is designed to: (1) Generate fundamental scientific understanding on the relationship between U(VI) chemical speciation and its susceptibility to biogeochemical reduction reactions. (2) Elucidate the controls on the rate and extent of contaminant reactivity. (3) Provide new insights into the aqueous and solid speciation of U(VI)/U(IV) under representative groundwater conditions.

  8. Size-Dependent Enhancement of Electrocatalytic Oxygen-Reduction and Hydrogen-Evolution Performance of MoS2 Particles.

    PubMed

    Wang, Tanyuan; Gao, Dongliang; Zhuo, Junqiao; Zhu, Zhiwei; Papakonstantinou, Pagona; Li, Yan; Li, Meixian

    2013-09-01

    MoS2 particles with different size distributions were prepared by simple ultrasonication of bulk MoS2 followed by gradient centrifugation. Relative to the inert microscale MoS2, nanoscale MoS2 showed significantly improved catalytic activity toward the oxygen-reduction reaction (ORR) and hydrogen-evolution reaction (HER). The decrease in particle size was accompanied by an increase in catalytic activity. Particles with a size of around 2 nm exhibited the best dual ORR and HER performance with a four-electron ORR process and an HER onset potential of -0.16 V versus the standard hydrogen electrode (SHE). This is the first investigation on the size-dependent effect of the ORR activity of MoS2, and a four-electron transfer route was found. The exposed abundant Mo edges of the MoS2 nanoparticles were proven to be responsible for the high ORR catalytic activity, whereas the origin of the improved HER activity of the nanoparticles was attributed to the plentiful exposed S edges. This newly discovered process provides a simple protocol to produce inexpensive highly active MoS2 catalysts that could easily be scaled up. Hence, it opens up possibilities for wide applications of MoS2 nanoparticles in the fields of energy conversion and storage. PMID:23873743

  9. Bifunctional Perovskite Oxide Catalysts for Oxygen Reduction and Evolution in Alkaline Media.

    PubMed

    Gupta, Shiva; Kellogg, William; Xu, Hui; Liu, Xien; Cho, Jaephil; Wu, Gang

    2016-01-01

    Oxygen electrocatalysis, namely of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), governs the performance of numerous electrochemical energy systems such as reversible fuel cells, metal-air batteries, and water electrolyzers. However, the sluggish kinetics of these two reactions and their dependency on expensive noble metal catalysts (e.g, Pt or Ir) prohibit the sustainable commercialization of these highly innovative and in-demand technologies. Bifunctional perovskite oxides have emerged as a new class of highly efficient non-precious metal catalysts (NPMC) for oxygen electrocatalysis in alkaline media. In this review, we discuss the state-of-the-art understanding of bifunctional properties of perovskites with regards to their OER/ORR activity in alkaline media and review the associated reaction mechanisms on the oxides surface and the related activity descriptors developed in the recent literature. We also summarize the present strategies to modify their electronic structure and to further improve their performance for the ORR/OER through highlighting the new concepts relating to the role of surface redox chemistry and oxygen deficiency of perovskite oxides for the ORR/OER activity. In addition, we provide a brief account of recently developed advanced perovskite-nanocarbon hybrid bifunctional catalysts with much improved performances. PMID:26247625

  10. Nanocrystalline Fe-Fe2O3 particle-deposited N-doped graphene as an activity-modulated Pt-free electrocatalyst for oxygen reduction reaction.

    PubMed

    Dhavale, Vishal M; Singh, Santosh K; Nadeema, Ayasha; Gaikwad, Sachin S; Kurungot, Sreekumar

    2015-12-21

    The size-controlled growth of nanocrystalline Fe-Fe2O3 particles (2-3 nm) and their concomitant dispersion on N-doped graphene (Fe-Fe2O3/NGr) could be attained when the mutually assisted redox reaction between NGr and Fe(3+) ions could be controlled within the aqueous droplets of a water-in-oil emulsion. The synergistic interaction existing between Fe-Fe2O3 and NGr helped the system to narrow down the overpotential for the oxygen reduction reaction (ORR) by bringing a significant positive shift to the reduction onset potential, which is just 15 mV higher than its Pt-counterpart. In addition, the half-wave potential (E1/2) of Fe-Fe2O3/NGr is found to be improved by a considerable amount of 135 mV in comparison to the system formed by dispersing Fe-Fe2O3 nanoparticles on reduced graphene oxide (Fe-Fe2O3/RGO), which indicates the presence of a higher number of active sites in Fe-Fe2O3/NGr. Despite this, the ORR kinetics of Fe-Fe2O3/NGr are found to be shifted significantly to the preferred 4-electron-transfer pathway compared to NGr and Fe-Fe2O3/RGO. Consequently, the H2O2% was found to be reduced by 78.3% for Fe-Fe2O3/NGr (13.0%) in comparison to Fe-Fe2O3/RGO (51.2%) and NGr (41.0%) at -0.30 V (vs. Hg/HgO). This difference in the yield of H2O2 formed between the systems along with the improvements observed in terms of the oxygen reduction onset and E1/2 in the case of Fe-Fe2O3/NGr reveals the activity modulation achieved for the latter is due to the coexistence of factors such as the presence of the mixed valancies of iron nanoparticles, small size and homogeneous distribution of Fe-Fe2O3 nanoparticles and the electronic modifications induced by the doped nitrogen in NGr. A controlled interplay of these factors looks like worked favorably in the case of Fe-Fe2O3/NGr. As a realistic system level validation, Fe-Fe2O3/NGr was employed as the cathode electrode of a single cell in a solid alkaline electrolyte membrane fuel cell (AEMFC). The system could display an open

  11. Quenchers and inhibitors of chemiluminescence in the reduction reactions of Mn3+

    NASA Astrophysics Data System (ADS)

    Tsaplev, Yu. B.; Vasil'ev, R. F.; Trofimov, A. V.

    2015-06-01

    The effect of NaF and CH3CN on the chemiluminescent reactions of Mn(III) reduction in solutions of sulfuric acid is studied. It is established that NaF is an inhibitor of these reactions, and the quenching of chemiluminescence under the effect of NaF is nominal. Acetonitrile does not affect the kinetics of reactions under similar conditions and acts as a specific quencher of the chemiexcited emitter. The Stern-Volmer quenching constant is 52 ± 11 M-1.

  12. Enhanced oxygen reduction performance by novel pyridine substituent groups of iron (II) phthalocyanine with graphene composite

    NASA Astrophysics Data System (ADS)

    Cui, Lili; Lv, Guojun; He, Xingquan

    2015-05-01

    In this paper, a novel iron (II) tetrapyridyloxyphthalocyanine decorated graphene (FeTPPc/Gr) is synthesized through a simple solvothermal method. The catalytic performance of the fabricated FeTPPc/Gr for the oxygen reduction reaction (ORR) is accessed by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and i-t chronoamperometry methods. The FeTPPc/Gr composite catalyst for the ORR displays an enhanced electrocatalytic activity compared with other FePc/Gr catalysts. More importantly, the proposed FeTPPc/Gr catalyst towards the ORR outperforms the commercial Pt/C catalyst in terms of higher diffusion-limiting current, more positive onset potential and half-wave potential, better stability and tolerance to methanol crossover. The improved ORR performance is attributed to the activity of peripheral pyridine substituents in the FePc, which facilitate O2 absorption and increase the additional active sites. Based on our experimental results, designing novel metal-N4 macrocycles and incorporating them into graphene or graphene derivatives, with both optimal activity and durability for the ORR, may hold great promise for application in alkaline direct methanol fuel cells (DMFCs).

  13. Advanced oxygen reduction electrocatalyst based on nitrogen-doped graphene derived from edible sugar and urea.

    PubMed

    Pan, Fuping; Jin, Jutao; Fu, Xiaogang; Liu, Qiao; Zhang, Junyan

    2013-11-13

    Designing and fabricating advanced oxygen reduction reaction (ORR) electrocatalysts is critical importance for the sake of promoting widespread application of fuel cells. In this work, we report that nitrogen-doped graphene (NG), synthesized via one-step pyrolysis of naturally available sugar in the presence of urea, can serve as metal-free ORR catalyst with excellent electrocatalytic activity, outstanding methanol crossover resistance as well as long-term operation stability in alkaline medium. The resultant NG1000 (annealed at 1000 °C) exhibits a high kinetic current density of 21.33 mA/cm(2) at -0.25 V (vs Ag/AgCl) in O2-saturated 0.1 M KOH electrolyte, compared with 16.01 mA/cm(2) at -0.25 V for commercial 20 wt % Pt/C catalyst. Notably, the NG1000 possesses comparable ORR half-wave potential to Pt/C. The effects of pyrolysis temperature on the physical prosperity and ORR performance of NG are also investigated. The obtained results demonstrate that high activation temperature (1000 °C) results in low nitrogen doping level, high graphitization degree, enhanced electrical conductivity, and high surface area and pore volume, which make a synergetic contribution to enhancing the ORR performance for NG. PMID:24099362

  14. Nanocrystalline Fe-Fe2O3 particle-deposited N-doped graphene as an activity-modulated Pt-free electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Dhavale, Vishal M.; Singh, Santosh K.; Nadeema, Ayasha; Gaikwad, Sachin S.; Kurungot, Sreekumar

    2015-11-01

    The size-controlled growth of nanocrystalline Fe-Fe2O3 particles (2-3 nm) and their concomitant dispersion on N-doped graphene (Fe-Fe2O3/NGr) could be attained when the mutually assisted redox reaction between NGr and Fe3+ ions could be controlled within the aqueous droplets of a water-in-oil emulsion. The synergistic interaction existing between Fe-Fe2O3 and NGr helped the system to narrow down the overpotential for the oxygen reduction reaction (ORR) by bringing a significant positive shift to the reduction onset potential, which is just 15 mV higher than its Pt-counterpart. In addition, the half-wave potential (E1/2) of Fe-Fe2O3/NGr is found to be improved by a considerable amount of 135 mV in comparison to the system formed by dispersing Fe-Fe2O3 nanoparticles on reduced graphene oxide (Fe-Fe2O3/RGO), which indicates the presence of a higher number of active sites in Fe-Fe2O3/NGr. Despite this, the ORR kinetics of Fe-Fe2O3/NGr are found to be shifted significantly to the preferred 4-electron-transfer pathway compared to NGr and Fe-Fe2O3/RGO. Consequently, the H2O2% was found to be reduced by 78.3% for Fe-Fe2O3/NGr (13.0%) in comparison to Fe-Fe2O3/RGO (51.2%) and NGr (41.0%) at -0.30 V (vs. Hg/HgO). This difference in the yield of H2O2 formed between the systems along with the improvements observed in terms of the oxygen reduction onset and E1/2 in the case of Fe-Fe2O3/NGr reveals the activity modulation achieved for the latter is due to the coexistence of factors such as the presence of the mixed valancies of iron nanoparticles, small size and homogeneous distribution of Fe-Fe2O3 nanoparticles and the electronic modifications induced by the doped nitrogen in NGr. A controlled interplay of these factors looks like worked favorably in the case of Fe-Fe2O3/NGr. As a realistic system level validation, Fe-Fe2O3/NGr was employed as the cathode electrode of a single cell in a solid alkaline electrolyte membrane fuel cell (AEMFC). The system could display an open

  15. Complete magnesiothermic reduction reaction of vertically aligned mesoporous silica channels to form pure silicon nanoparticles

    PubMed Central

    Kim, Kyoung Hwan; Lee, Dong Jin; Cho, Kyeong Min; Kim, Seon Joon; Park, Jung-Ki; Jung, Hee-Tae

    2015-01-01

    Owing to its simplicity and low temperature conditions, magnesiothermic reduction of silica is one of the most powerful methods for producing silicon nanostructures. However, incomplete reduction takes place in this process leaving unconverted silica under the silicon layer. This phenomenon limits the use of this method for the rational design of silicon structures. In this effort, a technique that enables complete magnesiothermic reduction of silica to form silicon has been developed. The procedure involves magnesium promoted reduction of vertically oriented mesoporous silica channels on reduced graphene oxides (rGO) sheets. The mesopores play a significant role in effectively enabling magnesium gas to interact with silica through a large number of reaction sites. Utilizing this approach, highly uniform, ca. 10 nm sized silicon nanoparticles are generated without contamination by unreacted silica. The new method for complete magnesiothermic reduction of mesoporous silica approach provides a foundation for the rational design of silicon structures. PMID:25757800

  16. Complete magnesiothermic reduction reaction of vertically aligned mesoporous silica channels to form pure silicon nanoparticles

    NASA Astrophysics Data System (ADS)

    Kim, Kyoung Hwan; Lee, Dong Jin; Cho, Kyeong Min; Kim, Seon Joon; Park, Jung-Ki; Jung, Hee-Tae

    2015-03-01

    Owing to its simplicity and low temperature conditions, magnesiothermic reduction of silica is one of the most powerful methods for producing silicon nanostructures. However, incomplete reduction takes place in this process leaving unconverted silica under the silicon layer. This phenomenon limits the use of this method for the rational design of silicon structures. In this effort, a technique that enables complete magnesiothermic reduction of silica to form silicon has been developed. The procedure involves magnesium promoted reduction of vertically oriented mesoporous silica channels on reduced graphene oxides (rGO) sheets. The mesopores play a significant role in effectively enabling magnesium gas to interact with silica through a large number of reaction sites. Utilizing this approach, highly uniform, ca. 10 nm sized silicon nanoparticles are generated without contamination by unreacted silica. The new method for complete magnesiothermic reduction of mesoporous silica approach provides a foundation for the rational design of silicon structures.

  17. Lattice theory of reaction efficiency in compartmentalized systems. II. Reduction of dimensionality

    NASA Astrophysics Data System (ADS)

    Lee, Pil H.; Kozak, John J.

    1984-01-01

    The timing and efficiency of a diffusion-controlled kinetic process in a compartmentalized system can be enhanced by reducing the dimensionality of the reaction space of the system. This idea, introduced by Adam and Delbrück and referred to as ``reduction of dimensionality,'' is explored quantitatively in this paper using a lattice theory of reaction efficiency developed in our earlier work. In particular, we study the interplay between system geometry and reaction efficiency using an approach in which group theoretic arguments are used within the framework of the theory of finite Markov processes to determine the average number of steps required for a diffusing coreactant A to undergo an irreversible reaction with a stationary target molecule B. We study in detail three classes of problems in this paper. First, we study as a function of the position of the reaction center how the efficiency of the underlying, irreversible, reaction-diffusion process A+B → C changes with increase in system size for symmetrical geometries. We show how reducing the dimensionality of the flow of the diffusing co-reactant leads to a crossover in reaction efficiency with increase in the size of the system, and document this effect as a function of N (the total number of sites characterizing the reaction space of the system), d (the dimensionality of the system), and ν (the valency or connectivity between adjacent sites in the reaction space). Secondly, we study how the calculated value of , and hence the efficiency of the process, changes when the compartmentalized system is characterized by tubular or platelet geometries, and show how the process of reduction of dimensionality is dependent on the further geometrical characteristics of eccentricity ɛ and the surface-to-volume ratio S/V. Finally, we study the consequences of reduction of dimensionality for (two) consecutive (say, enzymatic) reactions taking place in a compartmentalized system and demonstrate the advantages of

  18. REDUCTION OF NITROSOBENZENES AND N-HYDROXYLANILINES BY FE (II) SPECIES: ELUCIDATION OF REACTION MECHANISM

    EPA Science Inventory

    There has been a substantial effort toward understanding the reduction of nitroaromatics in Fe(II)-treated ferric oxide systems, little has been done to gain insight into the factors controlling the transformation of their reaction intermediates, nitrosobenzenes and N-hydroxylani...

  19. Further studies on vinamidinium salt amine exchange reactions, borohydride reductions and subsequent transformations

    PubMed Central

    Gupton, John T.; Telang, Nakul; Jia, Xin; Giglio, Benjamin C.; Eaton, James E.; Barelli, Peter J.; Hovaizi, Mona; Hall, Kayleigh E.; Welden, R. Scott; Keough, Matthew J.; Worrall, Eric F.; Finzel, Kara L.; Kluball, Emily J.; Kanters, Rene P.F.; Smith, Timothy M.; Smith, Stanton Q.; Nunes, Shane R.; Wright, Mathew T.; Birnstihl, Jennifer M.

    2010-01-01

    Studies directed at the amine exchange reaction of vinamidinium salts followed by sodium borohydride reduction to secondary and tertiary allylic amines are described. The tertiary allylic amines were alkylated and subjected to base mediated rearrangement to yield a variety of highly functionalized tertiary homoallylic amines. PMID:21113324

  20. Reaction Mechanism of Siderite Lump in Coal-Based Direct Reduction

    NASA Astrophysics Data System (ADS)

    Zhu, Deqing; Luo, Yanhong; Pan, Jian; Zhou, Xianlin

    2016-02-01

    Siderite is one of the significant iron ore resources in China and yet is difficult to upgrade by traditional beneficiation processes. A process of coal-based direct reduction-magnetic separation was successfully developed for the beneficiation of siderite. However, few studies have thoroughly investigated the mechanism of the direct reduction of siderite. In order to reveal the reaction mechanism of coal-based direct reduction of siderite lump, thermodynamics of direct reduction was investigated with coal as the reductant. The thermodynamics results indicate that coal-based direct reduction process of siderite lump at 1,050°C follows the steps as FeCO3→ Fe3O4→ FeO → Fe, which is verified by chemical titration analysis, X-ray diffraction and scanning electron microscope. The microstructure of siderite sample varies with different reduction stages and some 45% porosity induced by thermal decomposition of siderite is conductive to subsequent reduction. The conversion of FeO to Fe is the main reduction rate-controlling step. The reduced product with the metallic iron size over 30 μm can be effectively beneficiated by wet magnetic separation after grinding. The obvious layered structure of reduced product is due to different heat transfer resistance, CO and CO2 concentration.

  1. Reaction of 1,1,1-trichloroethane with zero-valent metals and bimetallic reductants

    SciTech Connect

    Fennelly, J.P.; Roberts, A.L.

    1998-07-01

    Information concerning the pathways and products of reaction of 1,1,1-trichloroethane (1,1,1-TCA) with zero-valent metals may be critical to the success of in situ treatment techniques. Many researchers assume that alkyl polyhalides undergo reduction via stepwise hydrogenolysis (replacement of halogen by hydrogen). Accordingly, 1,1,1-TCA should react to 1,1-dichloroethane (1,1-DCA), to chloroethane, and finally to ethane. Experiments conducted in laboratory-scale batch reactors indicate, however, that with zinc, iron, and two bimetallic reductants (nickel-plated iron and copper-plated iron) this simplistic stepwise scheme cannot explain observed results. 1,1,1-TCA was found to react rapidly with zinc to form ethane and 1,1-DCA. Independent experiments confirmed that 1,1-DCA reacts too slowly to represent an intermediate in the formation of ethane. In reactions with iron, nickel/iron, and copper/iron, cis-2-butene, ethylene, and 2-butyne were also observed as minor products. Product ratios were dependent on the identity of the metal or bimetallic reductant, with zinc resulting in the lowest yield of chlorinated product. For reactions with iron and bimetallic reductants, a scheme involving successive one-electron reduction steps to form radicals and carbenoids can be invoked to explain the absence of observable intermediates, as well as the formation of products originating from radical or possibly from carbenoid coupling.

  2. Reaction engineering for materials processing in space: Reduction of ilmenite by hydrogen and carbon monoxide

    NASA Technical Reports Server (NTRS)

    Zhao, Y.; Shadman, F.

    1991-01-01

    Oxygen is a consumable material which needs to be produced continuously in most space missions. Its use for propulsion as well as life support makes oxygen one of the largest volume chemicals to be produced in space. Production of oxygen from lunar materials is of particular interest and is very attractive possibility. The kinetics and mechanism of reduction of ilmenite by carbon monoxide and hydrogen at 800 to 1100 C were investigated. The temporal profiles of conversion for carbon monoxide have a sigmoidal shape and indicate the presence of three different stages (induction, acceleration, and deceleration) during the reduction reaction. The apparent activation energy decreases from 18 kcal/mole at 10 percent conversion to 10 kcal/mole at 50 percent conversion. The reaction is first order with respect to carbon monoxide under the experimental conditions studied. Both SEM and EDX analysis show that the diffusion of Fe product away from the reaction front and through the TiO2 phase, followed by the nucleation and growth of a separate Fe phase are important steps affecting the process kinetics. The results from hydrogen reduction show that the mechanism of ilmenite reduction by hydrogen is similar to that by carbon monoxide. However, the titanium dioxide can be further reduced by hydrogen at 800 to 1000 C. The detailed comparison and theoretical modeling of both reduction processes is presented.

  3. Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

    SciTech Connect

    Zheng, Dong; Zhang, Xuran; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-04-21

    Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O2/O2•- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O2 reduction reaction is from mass diffusion. Li2O2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O22- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings reveal an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.

  4. Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

    DOE PAGESBeta

    Zheng, Dong; Zhang, Xuran; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-04-21

    Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O2/O2•- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O2 reduction reaction is from mass diffusion. Li2O2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O22- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings reveal an opportunity for recharging Li-air batteries efficiently andmore » a new strategy of developing the catalyst for oxygen evolution reaction.« less

  5. Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium-oxygen batteries

    NASA Astrophysics Data System (ADS)

    Zheng, Dong; Zhang, Xuran; Qu, Deyu; Yang, Xiao-Qing; Lee, Hung-Sui; Qu, Deyang

    2015-08-01

    Oxygen reduction and oxygen evolution reactions were studied on graphite electrodes with different crystal orientations. The kinetics for the redox couple O2 /O2 rad - are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O2 reduction reaction is from mass diffusion. Li2O2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B -O2 2 - ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings reveal an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.

  6. Carbon Nitrogen Nanotubes as Efficient Bifunctional Electrocatalysts for Oxygen Reduction and Evolution Reactions.

    PubMed

    Yadav, Ram Manohar; Wu, Jingjie; Kochandra, Raji; Ma, Lulu; Tiwary, Chandra Sekhar; Ge, Liehui; Ye, Gonglan; Vajtai, Robert; Lou, Jun; Ajayan, Pulickel M

    2015-06-10

    Oxygen reduction and evolution reactions are essential for broad range of renewable energy technologies such as fuel cells, metal-air batteries and hydrogen production through water splitting, therefore, tremendous effort has been taken to develop excellent catalysts for these reactions. However, the development of cost-effective and efficient bifunctional catalysts for both reactions still remained a grand challenge. Herein, we report the electrocatalytic investigations of bamboo-shaped carbon nitrogen nanotubes (CNNTs) having different diameter distribution synthesized by liquid chemical vapor deposition technique using different nitrogen containing precursors. These CNNTs are found to be efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions. The electrocatalytic activity strongly depends on the nanotube diameter as well as nitrogen functionality type. The higher diameter CNNTs are more favorable for these reactions. The increase in nanotube diameter itself enhances the catalytic activity by lowering the oxygen adsorption energy, better conductivity, and further facilitates the reaction by increasing the percentage of catalytically active nitrogen moieties in CNNTs. PMID:25970133

  7. A hybrid-assembly approach towards nitrogen-doped graphene aerogel supported cobalt nanoparticles as high performance oxygen reduction electrocatalysts.

    PubMed

    Liu, Ruili; Jin, Yeqing; Xu, Peimin; Xing, Xia; Yang, Yuxing; Wu, Dongqing

    2016-02-15

    As a novel electrocatalyst for oxygen reduction reaction (ORR), nitrogen-doped graphene aerogel supported cobalt nanoparticles (Co-NGA) is archived by a hybrid-assembly of graphene oxide (GO), o-phthalonitrile and cobalt acetate and the following thermal treatment. The hybrid-assembly process successfully combines the ionic assembly of GO sheets and Co ions with the coordination between o-phthalonitrile and Co ions, which can be converted to nitrogen doped carbon and Co nanoparticles in the pyrolysis process under nitrogen flow. Remarkable features of Co-NGA including the macroporous graphene scaffolds, high surface area, and N/Co-doping effect can lead to a high catalytic efficiency for ORR. As the results, the composites pyrolyzed at 600°C (Co-NGA600) shows excellent electrocatalytic activities and kinetics for ORR in basic media, which are comparable with those of Pt/C catalyst, together with superior durability. PMID:26609926

  8. Pig bones derived N-doped carbon with multi-level pores as electrocatalyst for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Wang, Rongfang; Wang, Kai; Wang, Zihan; Song, Huihui; Wang, Hui; Ji, Shan

    2015-11-01

    In this work, a N-doped highly porous carbon material with multi-level pores and high activity for oxygen reduction reaction (ORR) is successfully prepared by carbonizing pig bones instead of separated carbon/nitrogen-containing and template precursors. The N-doped porous carbon material has high specific surface area of ca. 562.6 m2 g-1. Due to its high surface area and N-doped active sites, the ORR activity of obtained carbon in alkaline media is higher than that of commercial Pt/C catalyst (10 wt.%). In addition, it shows a higher methanol tolerance than Pt/C catalyst and long term-operating stability, rendering it as promising ORR catalyst material for fuel cells.

  9. Cathodic current enhancement via manganese and oxygen related reactions in marine biofilms

    NASA Astrophysics Data System (ADS)

    Strom, Matthew James

    Corrosion is a threat that has economic, and environmental impacts worldwide. Many types of corrosive attack are the subject of ongoing research. One of these areas of research is microbiologically influenced corrosion, which is the enhancement and/or initiation of corrosion events caused by microorganisms. It is well known that colonies of microorganisms can enhance cathodic currents through biofilm formation. The aim of the present work was to elucidate the role of manganese in enhancing cathodic currents in the presence of biofilms. Repeated polarizations conducted in Delaware Bay waters, on biofilm coated Cr identified potentially sustainable reduction reactions. The reduction of MnO2 and the enhancement of the oxygen reduction reaction (ORR) were proven to be factors that influence cathodic current enhancement. The removal of ambient oxygen during polarizations resulted in a shutdown of cathodic current enhancement. These field data led to an exploration of the synergistic relationship between MnO2 and the ORR. Laboratory studies of the catalysis of peroxide disproportionation by MnO2 were monitored using a hanging mercury drop electrode. Experiments were run at an ambient sweater pH of 8 and pH 9, which simulated the near-surface conditions typical of cathodes immersed in seawater. Rapid reoxidation at the more basic pH was shown to allow manganese to behave as a persistent catalyst under the typical electrochemical surface conditions of a cathode. As a result a mechanism for ORR enhancement by manganese was proposed as a unique mechanism for cathodic current enhancement in biofilms. A separate field study of Delaware biofilms on stainless steel coupled to a sacrificial Al anode was carried out to identify the ORR enhancement mechanism and sustainable redox reactions at the cathode. Chemical treatments of glutaraldehyde and formaldoxime were applied to cathodes with biofilms to distinguish between enzymatic and MnO2 related ORR enhancement. The results ruled

  10. Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique: II. Influence of Ink Formulation, Catalyst Layer Uniformity and Thickness

    SciTech Connect

    Shinozaki, Kazuma; Zack, Jason W.; Pylypenko, Svitlana; Pivovar, Bryan S.; Kocha, Shyam S.

    2015-09-17

    Platinum electrocatalysts supported on high surface area and Vulcan carbon blacks (Pt/HSC, Pt/V) were characterized in rotating disk electrode (RDE) setups for electrochemical area (ECA) and oxygen reduction reaction (ORR) area specific activity (SA) and mass specific activity (MA) at 0.9 V. Films fabricated using several ink formulations and film-drying techniques were characterized for a statistically significant number of independent samples. The highest quality Pt/HSC films exhibited MA 870 ± 91 mA/mgPt and SA 864 ± 56 μA/cm2 Pt while Pt/V had MA 706 ± 42 mA/mgPt and SA 1120 ± 70 μA/cm2 Pt when measured in 0.1 M HClO4, 20 mV/s, 100 kPa O2 and 23±2°C. An enhancement factor of 2.8 in themeasured SA was observable on eliminating Nafion ionomer and employing extremely thin, uniform films (~4.5 μg/cm2 Pt) of Pt/HSC. The ECA for Pt/HSC (99 ± 7 m2/gPt) and Pt/V (65 ± 5 m2/gPt) were statistically invariant and insensitive to film uniformity/thickness/fabrication technique; accordingly, enhancements in MA are wholly attributable to increases in SA. Impedance measurements coupled with scanning electron microscopy were used to de-convolute the losses within the catalyst layer and ascribed to the catalyst layer resistance, oxygen diffusion, and sulfonate anion adsorption/blocking. The ramifications of these results for proton exchange membrane fuel cells have also been examined.

  11. Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique: II. Influence of Ink Formulation, Catalyst Layer Uniformity and Thickness

    DOE PAGESBeta

    Shinozaki, Kazuma; Zack, Jason W.; Pylypenko, Svitlana; Pivovar, Bryan S.; Kocha, Shyam S.

    2015-09-17

    Platinum electrocatalysts supported on high surface area and Vulcan carbon blacks (Pt/HSC, Pt/V) were characterized in rotating disk electrode (RDE) setups for electrochemical area (ECA) and oxygen reduction reaction (ORR) area specific activity (SA) and mass specific activity (MA) at 0.9 V. Films fabricated using several ink formulations and film-drying techniques were characterized for a statistically significant number of independent samples. The highest quality Pt/HSC films exhibited MA 870 ± 91 mA/mgPt and SA 864 ± 56 μA/cm2 Pt while Pt/V had MA 706 ± 42 mA/mgPt and SA 1120 ± 70 μA/cm2 Pt when measured in 0.1 M HClO4,more » 20 mV/s, 100 kPa O2 and 23±2°C. An enhancement factor of 2.8 in themeasured SA was observable on eliminating Nafion ionomer and employing extremely thin, uniform films (~4.5 μg/cm2 Pt) of Pt/HSC. The ECA for Pt/HSC (99 ± 7 m2/gPt) and Pt/V (65 ± 5 m2/gPt) were statistically invariant and insensitive to film uniformity/thickness/fabrication technique; accordingly, enhancements in MA are wholly attributable to increases in SA. Impedance measurements coupled with scanning electron microscopy were used to de-convolute the losses within the catalyst layer and ascribed to the catalyst layer resistance, oxygen diffusion, and sulfonate anion adsorption/blocking. The ramifications of these results for proton exchange membrane fuel cells have also been examined.« less

  12. TiO2-modified CNx nanowires as a Pt electrocatalyst support with high activity and durability for the oxygen reduction reaction.

    PubMed

    Tang, J; Meng, H M

    2016-01-21

    A Pt/TiO2-modified carbon nitride nanofiber (Pt/TiO2-CNx) catalyst has been synthesized by a chemical method for the oxygen reduction reaction (ORR). The material characteristics confirmed by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) have indicated that the TiO2-CNx nanowires have a diameter of about 35-85 nm, the TiO2 nanoparticles are embedded in CNx nanowires and Pt nanoparticles are about 2.21 nm in size. The X-ray photoelectron spectra (XPS) show that Ti has a shift in the binding energy of Ti 2p, implying suboxide formation. Pt/0.2 g TiO2-CNx has about 3% loss in the (electrochemical surface area) ESA after 1000 cycles, however, the Pt/C catalyst has about 50.8% loss in the ESA. Pt/0.2 g TiO2-CNx has much better activity than Pt/C, which is proposed to be due to the high total surface area of Pt. The durability test shows that the Pt/0.2 g TiO2-CNx catalyst has no loss of activity after 5000 cycles. After 5000 cycles, the average size of Pt nanoparticles and the peaks of Pt 4f almost remain unchanged. The high durability of Pt/0.2 g TiO2-CNx is attributed to the corrosion-resistance of 0.2 g TiO2-CNx nanowires support and the good interaction between the 0.2 g TiO2-CNx support and the Pt nanoparticles. PMID:26660293

  13. Palladium(0)/NHC-Catalyzed Reductive Heck Reaction of Enones: A Detailed Mechanistic Study.

    PubMed

    Raoufmoghaddam, Saeed; Mannathan, Subramaniyan; Minnaard, Adriaan J; de Vries, Johannes G; Reek, Joost N H

    2015-12-14

    We have studied the mechanism of the palladium-catalyzed reductive Heck reaction of para-substituted enones with 4-iodoanisole by using N,N-diisopropylethylamine (DIPEA) as the reductant. Kinetic studies and in situ spectroscopic analysis have provided a detailed insight into the reaction. Progress kinetic analysis demonstrated that neither catalyst decomposition nor product inhibition occurred during the catalysis. The reaction is first order in the palladium and aryl iodide, and zero order in the activated alkene, N-heterocyclic carbene (NHC) ligand, and DIPEA. The experiments with deuterated solvent ([D7]DMF) and deuterated base ([D15]Et3N) supported the role of the amine as a reductant in the reaction. The palladium complex [Pd(0)(NHC)(1)] has been identified as the resting state. The kinetic experiments by stopped-flow UV/Vis also revealed that the presence of the second substrate, benzylideneacetone 1, slows down the oxidative addition of 4-iodoanisole through its competing coordination to the palladium center. The kinetic and mechanistic studies indicated that the oxidative addition of the aryl iodide is the rate-determining step. Various scenarios for the oxidative addition step have been analyzed by using DFT calculations (bp86/def2-TZVP) that supported the inhibiting effect of substrate 1 by formation of resting state [Pd(0)(NHC)(1)] species at the cost of further increase in the energy barrier of the oxidative addition step. PMID:26561034

  14. The bifurcation point of the oxygen reduction reaction on Au-Pd nanoalloys.

    PubMed

    Staszak-Jirkovský, Jakub; Ahlberg, Elisabet; Panas, Itai; Schiffrin, David J

    2016-07-01

    The oxygen reduction reaction is of major importance in energy conversion and storage. Controlling electrocatalytic activity and its selectivity remains a challenge of modern electrochemistry. Here, first principles calculations and analysis of experimental data unravel the mechanism of this reaction on Au-Pd nanoalloys in acid media. A mechanistic model is proposed from comparison of the electrocatalysis of oxygen and hydrogen peroxide reduction on different Au-Pd ensembles. A H2O production channel on contiguous Pd sites proceeding through intermediates different from H2O2 and OOH(σ) adsorbate is identified as the bifurcation point for the two reaction pathway alternatives to yield either H2O or H2O2. H2O2 is a leaving group, albeit reduction of H2O2 to H2O can occur by electrocatalytic HO-OH dissociation that is affected by the presence of adsorbed OOH(σ). Similarities and differences between electrochemical and direct synthesis from H2 + O2 reaction on Au-Pd nanoalloys are discussed. PMID:27089504

  15. The eigenvalue spectrum of the Orr-Sommerfeld problem

    NASA Technical Reports Server (NTRS)

    Antar, B. N.

    1976-01-01

    A numerical investigation of the temporal eigenvalue spectrum of the ORR-Sommerfeld equation is presented. Two flow profiles are studied, the plane Poiseuille flow profile and the Blasius boundary layer (parallel): flow profile. In both cases a portion of the complex c-plane bounded by 0 less than or equal to CR sub r 1 and -1 less than or equal to ci sub i 0 is searched and the eigenvalues within it are identified. The spectra for the plane Poiseuille flow at alpha = 1.0 and R = 100, 1000, 6000, and 10000 are determined and compared with existing results where possible. The spectrum for the Blasius boundary layer flow at alpha = 0.308 and R = 998 was found to be infinite and discrete. Other spectra for the Blasius boundary layer at various Reynolds numbers seem to confirm this result. The eigenmodes belonging to these spectra were located and discussed.

  16. Unusual High Oxygen Reduction Performance in All-Carbon Electrocatalysts

    PubMed Central

    Wei, Wei; Tao, Ying; Lv, Wei; Su, Fang-Yuan; Ke, Lei; Li, Jia; Wang, Da-Wei; Li, Baohua; Kang, Feiyu; Yang, Quan-Hong

    2014-01-01

    Carbon-based electrocatalysts are more durable and cost-effective than noble materials for the oxygen reduction reaction (ORR), which is an important process in energy conversion technologies. Heteroatoms are considered responsible for the excellent ORR performance in many carbon-based electrocatalysts. But whether an all-carbon electrocatalyst can effectively reduce oxygen is unknown. We subtly engineered the interfaces between planar graphene sheets and curved carbon nanotubes (G-CNT) and gained a remarkable activity/selectivity for ORR (larger current, and n = 3.86, ~93% hydroxide + ~7% peroxide). This performance is close to that of Pt; and the durability is much better than Pt. We further demonstrate the application of this G-CNT hybrid as an all-carbon cathode catalyst for lithium oxygen batteries.We speculate that the high ORR activity of this G-CNT hybrid stems from the localized charge separation at the interface of the graphene and carbon nanotube, which results from the tunneling electron transfer due to the Fermi level mismatch on the planar and curved sp2 surfaces. Our result represents a conceptual breakthrough and pioneers the new avenues towards practical all-carbon electrocatalysis. PMID:25189141

  17. One pot aqueous synthesis of nanoporous Au85Pt15 material with surface bound Pt islands: an efficient methanol tolerant ORR catalyst.

    PubMed

    Anandha Ganesh, P; Jeyakumar, D

    2014-11-01

    For the first time, we are reporting the synthesis of Au100-xPtx nanoporous materials in the size range of 7-10 nm through the galvanic replacement of Ag by Pt from Au100-xAg2x spherical nano-alloys (x = 20, 15, 10 and 5) in an aqueous medium. The galvanic replacement reaction follows the 'Volmer-Weber' growth mode, resulting in the formation of surface bound platinum islands on a nanoporous gold surface. The high angle annular dark field image and low angle X-ray diffraction studies confirm the presence of nanoporous Au100-xPtx NPs. The electrochemical studies using the Au85Pt15/C catalyst show excellent methanol tolerance behaviour and better performance towards oxygen reduction reaction (ORR) in terms of high mass activity, mass-specific activity and figure of merit (FOM) when compared to HiSPEC Pt/C commercial catalyst. Preliminary studies on a full cell using nanoporous Au85Pt15/C (loading 1.0 mg cm(-2)) as the cathode material and Pt-Ru/C (loading: 0.5 mg cm(-2)) as the anode material performed better (38 mW cm(-2)) than the HiSPEC Pt/C cathode material (16 mW cm(-2)). PMID:25241856

  18. Reduction of nitroaromatics sorbed to black carbon by direct reaction with sorbed sulfides.

    PubMed

    Xu, Wenqing; Pignatello, Joseph J; Mitch, William A

    2015-03-17

    Sorption to black carbons is an important sink for organic contaminants in sediments. Previous research has suggested that black carbons (graphite, activated carbon, and biochar) mediate the degradation of nitrated compounds by sulfides by at least two different pathways: reduction involving electron transfer from sulfides through conductive carbon regions to the target contaminant (nitroglycerin) and degradation by sulfur-based intermediates formed by sulfide oxidation (RDX). In this study, we evaluated the applicability of black carbon-mediated reactions to a wider variety of contaminant structures, including nitrated and halogenated aromatic compounds, halogenated heterocyclic aromatic compounds, and halogenated alkanes. Among these compounds, black carbon-mediated transformation by sulfides over a 3-day time scale was limited to nitroaromatic compounds. The reaction for a series of substituted nitroaromatics proceeded by reduction, as indicated by formation of 3-bromoaniline from 3-bromonitrobenzene, and inverse correlation of log kobs with energy of the lowest unoccupied molecular orbital (ELUMO). The log kobs was correlated with sorbed sulfide concentration, but no reduction of 3-bromonitrobenzene was observed in the presence of graphite and sulfite, thiosulfate, or polysulfides. Whereas nitroglycerin reduction occurred in an electrochemical cell containing sheet graphite electrodes in which the reagents were placed in separate compartments, nitroaromatic reduction only occurred when sulfides were present in the same compartment. The results suggest that black carbon-mediated reduction of sorbed nitroaromatics by sulfides involves electron transfer directly from sorbed sulfides rather than transfer of electrons through conductive carbon regions. The existence of three different reaction pathways suggests a complexity to the sulfide-carbon system compared to the iron-carbon system, where contaminants are reduced by electron transfer through conductive carbon

  19. Investigation of hydrogen peroxide reduction reaction on graphene and nitrogen doped graphene nanoflakes in neutral solution

    NASA Astrophysics Data System (ADS)

    Amirfakhri, Seyed Javad; Binny, Dustin; Meunier, Jean-Luc; Berk, Dimitrios

    2014-07-01

    H2O2 reduction reaction (HPRR) is studied on both graphene (GNF) and nitrogen doped graphene nanoflakes in 0.1 M Na2SO4 solution by rotating disk electrode. The XPS results indicate that N-doped graphene nanoflakes with high nitrogen content, 32 at%N (N-GNF32), are synthesised successfully by an inductively-coupled thermal plasma (ICP) reactor. Pyridinic, pyrrolic and graphitic N species contribute up to 67% of the total nitrogen. Kinetic parameters such as Tafel slope and stoichiometric number suggest that HPRR occurs by the same mechanism on both GNF and N-GNF32. Although nitrogen does not change the mechanism of HPRR, the results indicate that the reaction rate of H2O2 reduction is enhanced on N-GNF32. The exchange current density of H2O2 reduction based on the active surface area of N-GNF32 is (8.3 ± 0.3) × 10-9 A cm-2, which is 6 times higher than the value determined for GNF. The apparent number of electrons involved in the process suggests that H2O2 decomposition competes with H2O2 reduction on both catalysts. Evaluation of the apparent heterogeneous reaction rate constant and the Tafel slope indicate that simultaneous reduction of O2 and H2O2 is negligible on the N-GNF32. On the other hand, the reduction of O2 and H2O2 occurs simultaneously on the GNF surface.

  20. Catalytic reduction of CN−, CO and CO2 by nitrogenase cofactors in lanthanide-driven reactions**

    PubMed Central

    Lee, Chi Chung

    2014-01-01

    Nitrogenase cofactors can be extracted into an organic solvent and added in an adenosine triphosphate (ATP)-free, organic solvent-based reaction medium to catalyze the reduction of cyanide (CN−), carbon monoxide (CO) and carbon dioxide (CO2) when samarium (II) iodide (SmI2) and 2,6-lutidinium triflate (Lut-H) are supplied as a reductant and a proton source, respectively. Driven by SmI2, the cofactors not only catalytically reduce CN− or CO to C1-C4 hydrocarbons, but also catalytically reduce CO2 to CO and C1-C3 hydrocarbons. The observation of C-C coupling from CO2 reveals a unique, Fischer-Tropsch-like reaction with an atypical carbonaceous substrate; whereas the achievement of catalytic turnover of CN−, CO and CO2 by isolated cofactors suggests the possibility to develop nitrogenase-based electrocatalysts for hydrocarbon production from these carbon-containing compounds. PMID:25420957

  1. Reaction mechanisms involved in reduction of halogenated hydrocarbons using sulfated iron

    SciTech Connect

    Hassan, S.M.; Cipollone, M.G.; Wolfe, N.L.

    1995-12-01

    Experiments were carried out to investigate the mechanisms and pathways involved in the reduction of halogenated hydrocarbons represented by trichloroethylene (TCE) and tetrachloroethylene (PCE) with sulfated iron aqueous media. Results suggested that iron sulfide acted as the dehalogenation center. Zero-valent iron acted as a generator for molecular hydrogen through its reaction with water. Results of experiments in which iron sulfide was replaced by other transition metal sulfides and experiments in which zero-valent iron was replaced by other sources of molecular hydrogen will be reported. The main reduction product of chloroethylene derivatives was ethyne which under the catalytic reaction of zero-valent iron was reduced further to ethene and finally to ethane. Intermediate products were identified using GC-MS. Mechanisms and pathways will be presented.

  2. Highly branched PtCu bimetallic alloy nanodendrites with superior electrocatalytic activities for oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Fu, Shaofang; Zhu, Chengzhou; Shi, Qiurong; Xia, Haibing; Du, Dan; Lin, Yuehe

    2016-02-01

    Morphology control is a promising strategy to improve the catalytic performance of Pt-based catalysts. In this work, we reported a facile synthesis of PtCu bimetallic alloy nanodendrites using Brij 58 as a template. The highly branched structures and porous features offer relatively large surface areas, which is beneficial to the enhancement of the catalytic activity for oxygen reduction reactions in fuel cells. In addition, the elimination of carbon supports showed an important effect on the stability of the catalysts. By tuning the ratio of Pt and Cu precursors, PtCu nanodendrites were almost four times more active on the basis of an equivalent Pt mass for oxygen reduction reactions than the commercial Pt/C catalyst.Morphology control is a promising strategy to improve the catalytic performance of Pt-based catalysts. In this work, we reported a facile synthesis of PtCu bimetallic alloy nanodendrites using Brij 58 as a template. The highly branched structures and porous features offer relatively large surface areas, which is beneficial to the enhancement of the catalytic activity for oxygen reduction reactions in fuel cells. In addition, the elimination of carbon supports showed an important effect on the stability of the catalysts. By tuning the ratio of Pt and Cu precursors, PtCu nanodendrites were almost four times more active on the basis of an equivalent Pt mass for oxygen reduction reactions than the commercial Pt/C catalyst. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07682j

  3. Metal-Catalyzed β-Functionalization of Michael Acceptors through Reductive Radical Addition Reactions.

    PubMed

    Streuff, Jan; Gansäuer, Andreas

    2015-11-23

    Transition-metal-catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β-unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today's developments. PMID:26471460

  4. Direct observation of ultrafast-electron-transfer reactions unravels high effectiveness of reductive DNA damage.

    PubMed

    Nguyen, Jenny; Ma, Yuhan; Luo, Ting; Bristow, Robert G; Jaffray, David A; Lu, Qing-Bin

    2011-07-19

    Both water and electron-transfer reactions play important roles in chemistry, physics, biology, and the environment. Oxidative DNA damage is a well-known mechanism, whereas the relative role of reductive DNA damage is unknown. The prehydrated electron (e(pre)-), a novel species of electrons in water, is a fascinating species due to its fundamental importance in chemistry, biology, and the environment. e(pre)- is an ideal agent to observe reductive DNA damage. Here, we report both the first in situ femtosecond time-resolved laser spectroscopy measurements of ultrafast-electron-transfer (UET) reactions of e(pre)- with various scavengers (KNO(3), isopropanol, and dimethyl sulfoxide) and the first gel electrophoresis measurements of DNA strand breaks induced by e(pre)- and OH(•) radicals co-produced by two-UV-photon photolysis of water. We strikingly found that the yield of reductive DNA strand breaks induced by each e(pre)- is twice the yield of oxidative DNA strand breaks induced by each OH(•) radical. Our results not only unravel the long-standing mystery about the relative role of radicals in inducing DNA damage under ionizing radiation, but also challenge the conventional notion that oxidative damage is the main pathway for DNA damage. The results also show the potential of femtomedicine as a new transdisciplinary frontier and the broad significance of UET reactions of e(pre)- in many processes in chemistry, physics, biology, and the environment. PMID:21730183

  5. Amorphous nickel boride membrane on a platinum–nickel alloy surface for enhanced oxygen reduction reaction

    PubMed Central

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-01-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum–nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum–nickel catalyst, and this composite catalyst composed of crystalline platinum–nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon. PMID:27503412

  6. Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-08-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

  7. Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

    PubMed Central

    Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

    2013-01-01

    Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

  8. Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

    PubMed

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-01-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon. PMID:27503412

  9. Archaeal (Per)Chlorate Reduction at High Temperature: An Interplay of Biotic and Abiotic Reactions

    NASA Astrophysics Data System (ADS)

    Liebensteiner, Martin G.; Pinkse, Martijn W. H.; Schaap, Peter J.; Stams, Alfons J. M.; Lomans, Bart P.

    2013-04-01

    Perchlorate and chlorate anions [(per)chlorate] exist in the environment from natural and anthropogenic sources, where they can serve as electron acceptors for bacteria. We performed growth experiments combined with genomic and proteomic analyses of the hyperthermophile Archaeoglobus fulgidus that show (per)chlorate reduction also extends into the archaeal domain of life. The (per)chlorate reduction pathway in A. fulgidus relies on molybdo-enzymes that have similarity with bacterial enzymes; however, chlorite is not enzymatically split into chloride and oxygen. Evidence suggests that it is eliminated by an interplay of abiotic and biotic redox reactions involving sulfur compounds. Biological (per)chlorate reduction by ancient archaea at high temperature may have prevented accumulation of perchlorate in early terrestrial environments and consequently given rise to oxidizing conditions on Earth before the rise of oxygenic photosynthesis.

  10. Experiments to Determine Neighborhood Reactions to Light Airplanes With and Without External Noise Reduction

    NASA Technical Reports Server (NTRS)

    Elwell, Fred S

    1953-01-01

    The work reported was part of a program of experimentation with external noise reduction on light airplanes. This particular study was in effect a byproduct survey conceived to utilize already available equipment and personnel to further the findings of the original research and to determine reactions in populated neighborhoods to light aircraft with and without noise-reduction equipment. The findings indicate that at the 10 sites within and about metropolitan Boston the degree of noise reduction previously found to be aerodynamically and structurally feasible did eliminate substantially all neighborhood objections to noise per se. The evidence clearly suggests that, when the noise nuisance is minimized to the extent found feasible, the number and severity of other objections also diminish -- evidently because the flight operations are noticed less when heard less.

  11. Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide.

    PubMed

    Kortlever, Ruud; Shen, Jing; Schouten, Klaas Jan P; Calle-Vallejo, Federico; Koper, Marc T M

    2015-10-15

    The electrochemical reduction of CO2 has gained significant interest recently as it has the potential to trigger a sustainable solar-fuel-based economy. In this Perspective, we highlight several heterogeneous and molecular electrocatalysts for the reduction of CO2 and discuss the reaction pathways through which they form various products. Among those, copper is a unique catalyst as it yields hydrocarbon products, mostly methane, ethylene, and ethanol, with acceptable efficiencies. As a result, substantial effort has been invested to determine the special catalytic properties of copper and to elucidate the mechanism through which hydrocarbons are formed. These mechanistic insights, together with mechanistic insights of CO2 reduction on other metals and molecular complexes, can provide crucial guidelines for the design of future catalyst materials able to efficiently and selectively reduce CO2 to useful products. PMID:26722779

  12. MnO2 nanotube-Pt/graphene mixture as an ORR catalyst for proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Divya, P.; Ramaprabhu, S.

    2013-02-01

    In the present study, MnO2 nanotubes are synthesized by hydrothermal method and Pt/graphene by co reduction of hexachloroplatinic acid and graphite oxide. The formation of MnO2 nanotubes and Pt/graphene are confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy. MnO2 nanotubes are mixed with Pt/graphene is applied as the ORR catalyst in proton exchange membrane fuel cell. The single cell measurement is carried out after fabricating the membrane electrode assembly and polarization curves are recorded at different temperatures and the results are discussed.

  13. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts.

    PubMed

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S; Kumta, Prashant N

    2016-01-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations. PMID:27380719

  14. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    DOE PAGESBeta

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-06

    We report that identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cel