Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yu-Heng; Pegis, Michael L.; Mayer, James M.

A series of mononuclear pseudo-macrocyclic cobalt complexes have been investigated as catalysts for O2 reduction. Each of these complexes, with CoIII/II reduction potentials that span nearly 400 mV, mediate highly selective two- electron reduction of O2 to H2O2 (93–99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first- order dependence on [Co] and [AcOH], but no dependence on [O2] or [Fc*]. A linear correlation is observed between log(TOF) vs. E1/2(CoIII/II) for the different cobalt complexes (TOF = turnover frequency). The thermodynamic potential for+ O2 reduction to H2O2more » was estimated by measuring the H /H2 open-circuit potential under the reaction conditions. This value provides the basis for direct assessment of the thermodynamic efficiency of the different catalysts and shows that H2O2 is formed with overpotentials as low as 90 mV. These results are compared with a recently reported series of Fe-porphyrin complexes, which catalyze four-electron reduction of O2 to H2O. The data show that the TOFs of the Co complexes exhibit a shallower dependence on E1/2(MIII/II) than the Fe complexes. This behavior, which underlies the low overpotential, is rationalized on the basis of the catalytic rate law.« less

Silicon Photoelectrode Thermodynamics and Hydrogen Evolution Kinetics Measured by Intensity-Modulated High-Frequency Resistivity Impedance Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Nicholas C.; Carroll, Gerard M.; Pekarek, Ryan T.

Here, we present an impedance technique based on light intensity-modulated high-frequency resistivity (IMHFR) that provides a new way to elucidate both the thermodynamics and kinetics in complex semiconductor photoelectrodes. We apply IMHFR to probe electrode interfacial energetics on oxide-modified semiconductor surfaces frequently used to improve the stability and efficiency of photoelectrochemical water splitting systems. Combined with current density-voltage measurements, the technique quantifies the overpotential for proton reduction relative to its thermodynamic potential in Si photocathodes coated with three oxides (SiO x, TiO 2, and Al 2O 3) and a Pt catalyst. In pH 7 electrolyte, the flatband potentials of TiOmore » 2- and Al 2O 3-coated Si electrodes are negative relative to samples with native SiO x, indicating that SiO x is a better protective layer against oxidative electrochemical corrosion than ALD-deposited crystalline TiO 2 or Al 2O 3. Adding a Pt catalyst to SiO x/Si minimizes proton reduction overpotential losses but at the expense of a reduction in available energy characterized by a more negative flatband potential relative to catalyst-free SiO x/Si.« less

Silicon Photoelectrode Thermodynamics and Hydrogen Evolution Kinetics Measured by Intensity-Modulated High-Frequency Resistivity Impedance Spectroscopy

DOE PAGES

Anderson, Nicholas C.; Carroll, Gerard M.; Pekarek, Ryan T.; ...

2017-10-05

Here, we present an impedance technique based on light intensity-modulated high-frequency resistivity (IMHFR) that provides a new way to elucidate both the thermodynamics and kinetics in complex semiconductor photoelectrodes. We apply IMHFR to probe electrode interfacial energetics on oxide-modified semiconductor surfaces frequently used to improve the stability and efficiency of photoelectrochemical water splitting systems. Combined with current density-voltage measurements, the technique quantifies the overpotential for proton reduction relative to its thermodynamic potential in Si photocathodes coated with three oxides (SiO x, TiO 2, and Al 2O 3) and a Pt catalyst. In pH 7 electrolyte, the flatband potentials of TiOmore » 2- and Al 2O 3-coated Si electrodes are negative relative to samples with native SiO x, indicating that SiO x is a better protective layer against oxidative electrochemical corrosion than ALD-deposited crystalline TiO 2 or Al 2O 3. Adding a Pt catalyst to SiO x/Si minimizes proton reduction overpotential losses but at the expense of a reduction in available energy characterized by a more negative flatband potential relative to catalyst-free SiO x/Si.« less

Effect of betaine in the successful synthesis of CoFe2O4 containing octahedron nanoparticles for electrocatalytic water oxidation

NASA Astrophysics Data System (ADS)

Valdez, R.; Olivas, A.; Grotjahn, D. B.; Barrios, E.; Arjona, N.; Antaño, R.; Oropeza-Guzman, M. T.

2017-12-01

The development of robust catalysts that oxidize water is necessary for their application in artificial photosynthesis cells. Here we report the synthesis and characterization of octahedral CoFe2O4 nanoparticles obtained through a novel aqueous method that employs betaine, (CH3)3+NCH2COO-, as the stabilizer agent. The synthetic conditions are modified changing the betaine content and the metal precursor ratios. These conditions modify the shape of CoFe2O4 finding both, octahedral and semi-spherical nanoparticles. Linear voltammetry measurements show the octahedral CoFe2O4 lead to an overpotential of ∼390 mV at the onset potential for water oxidation at alkaline conditions. Among the as-synthesized cobalt-ferrite nanomaterials, the CoFe(1:2)-C in the form of tiny nanoparticles performed a superior electrocatalytic water oxidation in alkaline conditions, showing an overpotential of ∼335 mV, which is lower than other similar catalysts in literature.

Homogenous electrocatalytic oxygen reduction rates correlate with reaction overpotential in acidic organic solutions

DOE PAGES

Pegis, Michael L.; McKeown, Bradley A.; Kumar, Neeraj; ...

2016-10-28

Improvement of electrocatalysts for the oxygen reduction reaction (ORR) is critical for the advancement of fuel cell technologies. Herein, we report a series of eleven soluble iron porphyrin ORR electrocatalysts that possess turnover frequencies (TOFs) from 3 s -1 to an unprecedented 2.2 x 10 6 s -1. These TOFs correlate with the ORR overpotential, which can be changed by modulating the ancillary ligand, by varying the reaction conditions or by changing the catalyst’s protonation state. This is the first such correlation for homogeneous ORR electrocatalysis, and it demonstrates that the remarkably fast TOFs are a consequence of the highmore » overpotential. Computational studies indicate that the correlation is analogous to the volcano plot analysis developed for heterogeneous ORR materials. This unique parallel between homo- and heterogeneous ORR electrocatalysts allows a fundamental understanding of intrinsic barriers associated with the ORR, which can aid the design of new catalytic systems that operate at low overpotential. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Additional data is given in the Electronic Supporting Information.« less

Voltage Oscillations in a Polymer Electrolyte Membrane Fuel Cell with Pd‐Pt/C and Pd/C Anodes

PubMed Central

Nogueira, Jéssica Alves

2017-01-01

Abstract Polymer electrolyte membrane fuel cells (PEMFC) fed with H2 contaminated with CO may exhibit oscillatory behavior when operated galvanostatically. The self‐organization of the anodic overpotential is interesting because it can be accompanied by an increase in the average performance. Herein we report experimental studies of voltage oscillations that emerge in a PEMFC equipped with a Pd/C or PdPt/C anode and fed with H2 contaminated with CO (100 ppm). We used on‐line mass spectrometry to investigate how the mass fragments associated with CO2 and CO (m/z 44 and 28, respectively) varied with the voltage oscillations. Overall, we observed that oscillations in the anodic overpotential are in phase with that of the CO and CO2 signals. This fact is consistent with an autonomous adsorption–oxidation cyclic process. For both anodes, it has been observed that, in general, an increase in current density implies an increase in oscillatory frequency. By using CO stripping, we also discuss how the onset of CO oxidation is related to the maximum overpotential reached during a cycle, whereas the minimum overpotential can be associated with the catalytic activity of the electrode for H2 oxidation. PMID:29046857

Degradation of (La(0.8)Sr(0.2))(0.98)MnO(3-δ)-Zr(0.84)Y(0.16)O(2-γ) composite electrodes during reversing current operation.

PubMed

Hughes, Gareth A; Railsback, Justin G; Yakal-Kremski, Kyle J; Butts, Danielle M; Barnett, Scott A

2015-01-01

Reversing-current operation of solid oxide cell (La(0.8)Sr(0.2))(0.98)MnO(3-δ)-Zr(0.84)Y(0.16)O(2-γ) (LSM-YSZ) oxygen electrodes is described. Degradation was characterized by impedance spectroscopy in symmetric cells tested at 800 °C in air with a symmetric current cycle with a period of 12 hours. No change in cell resistance could be detected, in 1000 h tests with a sensitivity of ∼1% per kh, at a current density of 0.5 A cm(-2) corresponding to an overpotential of 0.18 V. At a current density to 0.6 A cm(-2) (0.33 V overpotential) measurable resistance degradation at a rate of 3% per kh was observed, while higher current/overpotential values led to faster degradation. Degradation was observed mainly in the ohmic resistance for current densities of 0.6, 0.8 and 0.9 A cm(-2), with little change in the polarization resistance. Polarization degradation, mainly observed at higher current density, was present as an increase in an impedance response at ∼30 kHz, apparently associated with the resistance of YSZ grain boundaries within the electrode. Microstructural and chemical analysis showed significant changes in electrode structure after the current cycling, including an increase in LSM particle size and a reduction in the amount of YSZ and LSM at the electrode/electrolyte interface - the latter presumably a precursor to delamination.

Enabling rechargeable non-aqueous Mg-O2 battery operations with dual redox mediators.

PubMed

Dong, Qi; Yao, Xiahui; Luo, Jingru; Zhang, Xizi; Hwang, Hajin; Wang, Dunwei

2016-12-11

Dual redox mediators (RMs) were introduced for Mg-O 2 batteries. 1,4-Benzoquinone (BQ) facilitates the discharge with an overpotential reduction of 0.3 V. 5,10,15,20-Tetraphenyl-21H,23H-porphine cobalt(ii) (Co(ii)TPP) facilitates the recharge with an overpotential decrease of up to 0.3 V. Importantly, the two redox mediators are compatible in the same DMSO-based electrolyte.

Nonlinear coupled equations for electrochemical cells as developed by the general equation for nonequilibrium reversible-irreversible coupling.

PubMed

Bedeaux, Dick; Kjelstrup, Signe; Öttinger, Hans Christian

2014-09-28

We show how the Butler-Volmer and Nernst equations, as well as Peltier effects, are contained in the general equation for nonequilibrium reversible and irreversible coupling, GENERIC, with a unique definition of the overpotential. Linear flux-force relations are used to describe the transport in the homogeneous parts of the electrochemical system. For the electrode interface, we choose nonlinear flux-force relationships. We give the general thermodynamic basis for an example cell with oxygen electrodes and electrolyte from the solid oxide fuel cell. In the example cell, there are two activated chemical steps coupled also to thermal driving forces at the surface. The equilibrium exchange current density obtains contributions from both rate-limiting steps. The measured overpotential is identified at constant temperature and stationary states, in terms of the difference in electrochemical potential of products and reactants. Away from these conditions, new terms appear. The accompanying energy flux out of the surface, as well as the heat generation at the surface are formulated, adding to the general thermodynamic basis.

Nonlinear coupled equations for electrochemical cells as developed by the general equation for nonequilibrium reversible-irreversible coupling

NASA Astrophysics Data System (ADS)

Bedeaux, Dick; Kjelstrup, Signe; Öttinger, Hans Christian

2014-09-01

We show how the Butler-Volmer and Nernst equations, as well as Peltier effects, are contained in the general equation for nonequilibrium reversible and irreversible coupling, GENERIC, with a unique definition of the overpotential. Linear flux-force relations are used to describe the transport in the homogeneous parts of the electrochemical system. For the electrode interface, we choose nonlinear flux-force relationships. We give the general thermodynamic basis for an example cell with oxygen electrodes and electrolyte from the solid oxide fuel cell. In the example cell, there are two activated chemical steps coupled also to thermal driving forces at the surface. The equilibrium exchange current density obtains contributions from both rate-limiting steps. The measured overpotential is identified at constant temperature and stationary states, in terms of the difference in electrochemical potential of products and reactants. Away from these conditions, new terms appear. The accompanying energy flux out of the surface, as well as the heat generation at the surface are formulated, adding to the general thermodynamic basis.

A Molecular Ni-complex Containing Tetrahedral Nickel Selenide Core as Highly Efficient Electrocatalyst for Water Oxidation.

PubMed

Masud, Jahangir; Ioannou, Polydoros-Chrysovalantis; Levesanos, Nikolaos; Kyritsis, Panayotis; Nath, Manashi

2016-11-23

We report the highly efficient catalytic activity of a transition metal selenide-based coordination complex, [Ni{(SeP i Pr 2 ) 2 N} 2 ], (1) for oxygen evolution and hydrogen evolution reactions (OER and HER, respectively) in alkaline solution. Very low overpotentials of 200 mV and 310 mV were required to achieve 10 mA cm -2 for OER and HER, respectively. The overpotential for OER is one of the lowest that has been reported up to now, making this one of the best OER electrocatalysts. In addition, this molecular complex exhibits an exceptionally high mass activity (111.02 A g -1 ) and a much higher TOF value (0.26 s -1 ) at a overpotential of 300 mV. This bifunctional electrocatalyst enables water electrolysis in alkaline solutions at a cell voltage of 1.54 V. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the mobility of carbon-supported platinum nanoparticles towards unveiling cathode degradation in water electrolysis

NASA Astrophysics Data System (ADS)

Paciok, Paul; Schalenbach, Maximilian; Carmo, Marcelo; Stolten, Detlef

2017-10-01

This study investigates the influence of the hydrogen evolution reaction (HER) overpotential on the mobility of carbon-supported platinum particles. The migration of the platinum over the carbon support was analyzed by means of identical location transmission electron microscopy (IL-TEM). While at potentials of 0.1 and 0 V vs. reversible hydrogen electrode (RHE), no changes to the Pt/C material were observed. With a decrease of the overpotential to -0.1 V vs. RHE, an increase in the quantity of migrating platinum particles took place. At -0.2 V vs. RHE, a further rise in the particle migration was observed. The effect of the overpotential on the migration was explained by a higher hydrogen generation rate, the formation of a hydrogen monolayer on the platinum and the resulting changes of the platinum support distance. The mechanisms revealed in this study could describe a relevant source of degradation of PEM water electrolyzers.

Improving halide-containing magnesium-ion electrolyte performance via sterically hindered alkoxide ligands

NASA Astrophysics Data System (ADS)

Nist-Lund, Carl A.; Herb, Jake T.; Arnold, Craig B.

2017-09-01

While homoleptic magnesium dialkoxides (MgR2, R = alkoxide) have shown promise as precursors for magnesium-ion electrolytes, the effect of ligand steric bulk on the performance of electrolytes based on these compounds is not fully understood. Increasing steric hindrance, studied via R groups with additional phenyl moieties, produces electrolytes with sequentially lower deposition overpotentials (less than -90 mV), higher purity Mg deposits (ca. 100% Mg), and lower overall cell impedances. The two largest alkoxide ligands show consistent cycling behavior and low stripping and plating overpotentials over 200 constant-current plating/stripping cycles. A deep-red visual change and the presence of large solubilized magnesium particulates above 450 nm in size is observed in an electrolyte containing magnesium bis(triphenylmethoxide) and aluminum chloride in contact with an abraded magnesium anode. Further morphological and impedance characterization show that this electrolyte system rapidly activates the magnesium metal anode surface to produce low overpotentials and, as such, is a candidate for further investigation.

Dissolution and ionization of sodium superoxide in sodium–oxygen batteries

PubMed Central

Kim, Jinsoo; Park, Hyeokjun; Lee, Byungju; Seong, Won Mo; Lim, Hee-Dae; Bae, Youngjoon; Kim, Haegyeom; Kim, Won Keun; Ryu, Kyoung Han; Kang, Kisuk

2016-01-01

With the demand for high-energy-storage devices, the rechargeable metal–oxygen battery has attracted attention recently. Sodium–oxygen batteries have been regarded as the most promising candidates because of their lower-charge overpotential compared with that of lithium–oxygen system. However, conflicting observations with different discharge products have inhibited the understanding of precise reactions in the battery. Here we demonstrate that the competition between the electrochemical and chemical reactions in sodium–oxygen batteries leads to the dissolution and ionization of sodium superoxide, liberating superoxide anion and triggering the formation of sodium peroxide dihydrate (Na2O2·2H2O). On the formation of Na2O2·2H2O, the charge overpotential of sodium–oxygen cells significantly increases. This verification addresses the origin of conflicting discharge products and overpotentials observed in sodium–oxygen systems. Our proposed model provides guidelines to help direct the reactions in sodium–oxygen batteries to achieve high efficiency and rechargeability. PMID:26892931

Dissolution and ionization of sodium superoxide in sodium-oxygen batteries.

PubMed

Kim, Jinsoo; Park, Hyeokjun; Lee, Byungju; Seong, Won Mo; Lim, Hee-Dae; Bae, Youngjoon; Kim, Haegyeom; Kim, Won Keun; Ryu, Kyoung Han; Kang, Kisuk

2016-02-19

With the demand for high-energy-storage devices, the rechargeable metal-oxygen battery has attracted attention recently. Sodium-oxygen batteries have been regarded as the most promising candidates because of their lower-charge overpotential compared with that of lithium-oxygen system. However, conflicting observations with different discharge products have inhibited the understanding of precise reactions in the battery. Here we demonstrate that the competition between the electrochemical and chemical reactions in sodium-oxygen batteries leads to the dissolution and ionization of sodium superoxide, liberating superoxide anion and triggering the formation of sodium peroxide dihydrate (Na2O2·2H2O). On the formation of Na2O2·2H2O, the charge overpotential of sodium-oxygen cells significantly increases. This verification addresses the origin of conflicting discharge products and overpotentials observed in sodium-oxygen systems. Our proposed model provides guidelines to help direct the reactions in sodium-oxygen batteries to achieve high efficiency and rechargeability.

Integrating a redox-coupled dye-sensitized photoelectrode into a lithium-oxygen battery for photoassisted charging.

PubMed

Yu, Mingzhe; Ren, Xiaodi; Ma, Lu; Wu, Yiying

2014-10-03

With a high theoretical specific energy, the non-aqueous rechargeable lithium-oxygen battery is a promising next-generation energy storage technique. However, the large charging overpotential remains a challenge due to the difficulty in electrochemically oxidizing the insulating lithium peroxide. Recently, a redox shuttle has been introduced into the electrolyte to chemically oxidize lithium peroxide. Here, we report the use of a triiodide/iodide redox shuttle to couple a built-in dye-sensitized titanium dioxide photoelectrode with the oxygen electrode for the photoassisted charging of a lithium-oxygen battery. On charging under illumination, triiodide ions are generated on the photoelectrode, and subsequently oxidize lithium peroxide. Due to the contribution of the photovoltage, the charging overpotential is greatly reduced. The use of a redox shuttle to couple a photoelectrode and an oxygen electrode offers a unique strategy to address the overpotential issue of non-aqueous lithium-oxygen batteries and also a distinct approach for integrating solar cells and batteries.

Multi-component Fe–Ni hydroxide nanocatalyst for oxygen evolution and methanol oxidation reactions under alkaline conditions

DOE PAGES

Candelaria, Stephanie L.; Bedford, Nicholas M.; Woehl, Taylor J.; ...

2016-11-29

Here, iron-incorporated nickel-based materials show promise as catalysts for the oxygen evolution reac-tion (OER) half-reaction of water electrolysis. Nickel has also exhibited high catalytic activity for methanol oxidation, particularly when in the form of a bimetallic catalyst. In this work, bimetallic iron-nickel nanoparticles were synthesized using a multi-step procedure in water under ambient conditions. When compared to monometallic iron and nickel nanoparticles, Fe-Ni nanoparticles show enhanced catalytic activity for both OER and methanol oxidation under alkaline conditions. At 1 mA/cm 2, the overpotential for monometallic iron and nickel nanoparticles was 421 mV and 476 mV, respectively, while the bimetallic Fe-Nimore » nanoparticles had a greatly reduced overpotential of 256 mV. At 10 mA/cm 2, bimetallic Fe-Ni nanoparticles had an overpotential of 311 mV. Spec-troscopy characterization suggests that the primary phase of nickel in Fe-Ni nanoparticles is the more disordered alpha phase of nickel hydroxide.« less

Electrocrystallization and scanning probe microscopy of ceramic thin films and superlattices

NASA Astrophysics Data System (ADS)

Hung, Chen-Jen

This dissertation presents an investigation of the electrocrystallization and scanning probe microscopy of ceramic thin films and superlattices. All of the films were deposited from aqueous solution at room temperature with no subsequent heat treatment needed to effect crystallization. Thallium(III) oxide defect chemistry superlattices were electrodeposited by pulsing the applied overpotential during deposition. The defect chemistry of the oxide is dependent on the applied overpotential. High overpotentials favor oxygen vacancies, while low overpotentials favor cation interstitials. Nanometer-scale holes were formed in thin thallium(III) oxide films using the scanning tunneling microscope in humid ambient conditions. Both cathodic and anodic etching reactions were performed on this metal oxide surface. The hole formation was attributed to localized electrochemical etching reactions beneath the STM tip. The scanning tunneling microscope (STM) was also used to both induce local surface modifications and image cleaved Pb-Tl-O superlattices. A trench of 100 nm in width, 32 nm in depth, and over 1 μm in length was formed after sweeping a bias voltage of ±2.5 V for 1 minute using a fixed STM tip. It has been suggested that STM results obtained under ambient conditions must be evaluated with great care because of the possibility of localized electrochemcial reactions. A novel synthesis method for the production of Cu(II) oxide from an alkaline solution containing Cu(II) tartrate was developed. Rietveld refinement of the cupric oxide films reveals pure Cu(II) oxide with no Cu(I) oxide present in the film.

Electrochemical water splitting using nano-zeolite Y supported tungsten oxide electrocatalysts

NASA Astrophysics Data System (ADS)

Anis, Shaheen Fatima; Hashaikeh, Raed

2018-02-01

Zeolites are often used as supports for metals and metal oxides because of their well-defined microporous structure and high surface area. In this study, nano-zeolite Y (50-150 nm range) and micro-zeolite Y (500-800 nm range) were loaded with WO3, by impregnating the zeolite support with ammonium metatungstate and thermally decomposing the salt thereafter. Two different loadings of WO3 were studied, 3 wt.% and 5 wt.% with respect to the overall catalyst. The prepared catalysts were characterized for their morphology, structure, and surface areas through scanning electron microscope (SEM), XRD, and BET. They were further compared for their electrocatalytic activity for hydrogen evolution reaction (HER) in 0.5 M H2SO4. On comparing the bare micro-zeolite particles with the nano-form, the nano-zeolite Y showed higher currents with comparable overpotentials and lower Tafel slope of 62.36 mV/dec. WO3 loading brought about a change in the electrocatalytic properties of the catalyst. The overpotentials and Tafel slopes were observed to decrease with zeolite-3 wt.% WO3. The smallest overpotential of 60 mV and Tafel slope of 31.9 mV/dec was registered for nano-zeolite with 3 wt.% WO3, while the micro-zeolite gave an overpotential of 370 mV and a Tafel slope of 98.1 mV/dec. It was concluded that even with the same metal oxide loading, nano-zeolite showed superior performance, which is attributed to its size and hence easier escape of hydrogen bubbles from the catalyst.

Effect of Chloride Anions on the Synthesis and Enhanced Catalytic Activity of Silver Nanocoral Electrodes for CO 2 Electroreduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsieh, Yu-Chi; Senanayake, Sanjaya D.; Zhang, Yu

2015-09-04

Metallic silver (Ag) is known as an efficient electrocatalyst for the conversion of carbon dioxide (CO 2) to carbon monoxide (CO) in aqueous or nonaqueous electrolytes. However, polycrystalline silver electrocatalysts require significant overpotentials in order to achieve high selectivity toward CO 2 reduction, as compared to the side reaction of hydrogen evolution. Here we report a high-surface-area Ag nanocoral catalyst, fabricated by an oxidation–reduction method in the presence of chloride anions in an aqueous medium, for the electro-reduction of CO 2 to CO with a current efficiency of 95% at the low overpotential of 0.37 V and the current densitymore » of 2 mA cm –2. A lower limit of TOF of 0.4 s –1 and TON > 8.8 × 10 4 (over 72 h) was estimated for the Ag nanocoral catalyst at an overpotential of 0.49 V. The Ag nanocoral catalyst demonstrated a 32-fold enhancement in surface-area-normalized activity, at an overpotential of 0.49 V, as compared to Ag foil. We found that, in addition to the effect on nanomorphology, the adsorbed chloride anions play a critical role in the observed enhanced activity and selectivity of the Ag nanocoral electrocatalyst toward CO 2 reduction. Synchrotron X-ray photoelectron spectroscopy (XPS) studies along with a series of control experiments suggest that the chloride anions, remaining adsorbed on the catalyst surface under electrocatalytic conditions, can effectively inhibit the side reaction of hydrogen evolution and enhance the catalytic performance for CO 2 reduction.« less

Electrodeposition of platinum on highly oriented pyrolytic graphite. Part I: electrochemical characterization.

PubMed

Lu, Guojin; Zangari, Giovanni

2005-04-28

The electrochemical deposition of Pt on highly oriented pyrolytic graphite (HOPG) from H2PtCl6 solutions was investigated by cyclic voltammetry and chronoamperometry. The effects of deposition overpotential, H2PtCl6 concentration, supporting electrolyte, and anion additions on the deposition process were evaluated. Addition of chloride inhibits Pt deposition due to adsorption on the substrate and blocking of reduction sites, while SO4(2-) and ClO4- slightly promote Pt reduction. By comparing potentiostatic current-time transients with the Scharifker-Hills model, a transition from progressive to instantaneous nucleation was observed when increasing the deposition overpotential. Following addition of chloride anions the fit of experimental transients with the instantaneous nucleation mode improves, while the addition of SO4(2-) induces only small changes. Chloride anions strongly inhibit the reduction process, which is shifted in the cathodic direction. The above results indicate that the most appropriate conditions for growing Pt nanoparticles on HOPG with narrow size distribution are to use an H2PtCl6 solution with HCl as supporting electrolyte and to apply a high cathodic overpotential.

Nitrogen-doped graphene interpenetrated 3D Ni-nanocages: efficient and stable water-to-dioxygen electrocatalysts

NASA Astrophysics Data System (ADS)

Dhavale, Vishal M.; Gaikwad, Sachin S.; George, Leena; Devi, R. Nandini; Kurungot, Sreekumar

2014-10-01

Herein, we report the synthesis of a nitrogen-doped graphene (NGr) interpenetrated 3D Ni-nanocage (Ni-NGr) electrocatalyst by a simple water-in-oil (w/o) emulsion technique for oxidation of water to dioxygen. Correlation of adsorption of NGr and subsequent interpenetration through the specific surface plane of nickel particles as well as the concomitant interaction of N and C with Ni in the nano-regime has been investigated. Apart from the benefits of the synergistic interactions between Ni, N, and C, the overall integrity of the structure and its intra-molecular connectivity within the framework help in achieving better oxygen evolution characteristics at a significantly reduced overpotential. The engineered Ni-NGr nanocage displays a substantially low overpotential of ~290 mV at a practical current density of 20 mA cm-2 in 0.1 M KOH. In comparison, NGr and Ni-particles as separate entities give overpotentials of ~570 and ~370 mV under similar conditions. Moreover, the long term stability of Ni-NGr was investigated by anodic potential cycling for 500 cycles and an 8.5% increment in the overpotential at 20 mA cm-2 was observed. Additionally, a chronoamperometric test was performed for 15 h at 20 mA cm-2, which highlights the better sustainability of Ni-NGr under the actual operating conditions. Finally, the quantitative estimation of evolved oxygen was monitored by gas chromatography and was found to be 70 mmol h-1 g-1 of oxygen, which is constant in the second cycle as well.Herein, we report the synthesis of a nitrogen-doped graphene (NGr) interpenetrated 3D Ni-nanocage (Ni-NGr) electrocatalyst by a simple water-in-oil (w/o) emulsion technique for oxidation of water to dioxygen. Correlation of adsorption of NGr and subsequent interpenetration through the specific surface plane of nickel particles as well as the concomitant interaction of N and C with Ni in the nano-regime has been investigated. Apart from the benefits of the synergistic interactions between Ni, N, and C, the overall integrity of the structure and its intra-molecular connectivity within the framework help in achieving better oxygen evolution characteristics at a significantly reduced overpotential. The engineered Ni-NGr nanocage displays a substantially low overpotential of ~290 mV at a practical current density of 20 mA cm-2 in 0.1 M KOH. In comparison, NGr and Ni-particles as separate entities give overpotentials of ~570 and ~370 mV under similar conditions. Moreover, the long term stability of Ni-NGr was investigated by anodic potential cycling for 500 cycles and an 8.5% increment in the overpotential at 20 mA cm-2 was observed. Additionally, a chronoamperometric test was performed for 15 h at 20 mA cm-2, which highlights the better sustainability of Ni-NGr under the actual operating conditions. Finally, the quantitative estimation of evolved oxygen was monitored by gas chromatography and was found to be 70 mmol h-1 g-1 of oxygen, which is constant in the second cycle as well. Electronic supplementary information (ESI) available: An experimental procedure for the synthesis of GO, Gr, Ni-particles, and Ni-Gr. TEM images of Gr, NGr, and Ni-Gr. XPS of C 1s and O 1s of Ni-NGr. C 1s, O 1s and N 1s spectra of NGr. A comparative cyclic voltammogram of NGr and Ni-NGr. A Tafel plot, RRDE, HR-TEM image of Ni-NGr and the corresponding line profile showing the lattice spacing values, anodic scan of NGr. Comparative anodic scan of Ni-particles, Ni-Gr and Ni-NGr. CV of the Pt-electrode and capacitive CV. SEM elemental mapping and the mechanism of OER. See DOI: 10.1039/c4nr03578j

Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts

DOE PAGES

Matheu, Roc; Ertem, Mehmed Z.; Gimbert-Surinach, Carolina; ...

2017-08-15

In this paper, we describe the synthesis, structural characterization, and redox properties of two new Ru complexes containing the dianionic potentially pentadentate [2,2':6',2"-terpyridine]-6,6"-dicarboxylate (tda 2–) ligand that coordinates Ru at the equatorial plane and with additional pyridine or dmso acting as monondentate ligand in the axial positions: [Ru II(tda-κ-N 3O)(py)(dmso)], 1 II and [Ru III(tda-κ-N 3O 2)(py)(H 2O) ax] +, 2 III(H 2O) +. Complex 1 II has been characterized by single-crystal XRD in the solid state and in solution by NMR spectroscopy. The redox properties of 1 II and 2 III(H 2O) + have been thoroughly investigated by meansmore » of cyclic voltammetry and differential pulse voltammetry. Complex 2 II(H 2O) displays poor catalytic activity with regard to the oxidation of water to dioxygen, and its properties have been analyzed on the basis of foot of the wave analysis and catalytic Tafel plots. The activity of 2 II(H 2O) has been compared with related water oxidation catalysts (WOCs) previously described in the literature. Despite its moderate activity, 2 II(H 2O) constitutes the cornerstone that has triggered the rationalization of the different factors that govern overpotentials as well as efficiencies in molecular WOCs. The present work uncovers the interplay between different parameters, namely, coordination number, number of anionic groups bonded to the first-coordination sphere of the metal center, water oxidation catalysis overpotential, p K a and hydrogen bonding, and the performance of a given WOC. It thus establishes the basic principles for the design of efficient WOCs operating at low overpotentials.« less

Electrode Reactions in Slowly Relaxing Media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matyushov, Dmitry V.; Newton, Marshall D.

Here, standard models of reaction kinetics in condensed materials rely on the Boltzmann-Gibbs distribution for the population of reactants at the top of the free energy barrier separating them from the products. While energy dissipation and quantum effects at the barrier top can potentially affect the transmission coefficient entering the rate preexponential factor, much stronger dynamical effects on the reaction barrier are caused by the breakdown of ergodicity for populating the reaction barrier (violation of the Boltzmann-Gibbs statistics). When the spectrum of medium modes coupled to the reaction coordinate includes fluctuations slower than the reaction rate, such nuclear motions dynamicallymore » freeze on the reaction time-scale and do not contribute to the activation barrier. In this paper, we consider the consequences of this scenario for electrode reactions in slowly relaxing media. Changing electrode overpotential speeds electrode electron transfer up, potentially cutting through the spectrum of nuclear modes coupled to the reaction coordinate. The reorganization energy of electrochemical electron transfer becomes a function of the electrode overpotential, switching between the thermodynamic value at low rates to the nonergodic limit at higher rates. The sharpness of this transition depends of the relaxation spectrum of the medium. The reorganization energy experiences a sudden drop with increasing overpotential for a medium with a Debye relaxation, but becomes a much shallower function of the overpotential for media with stretched exponential dynamics. The latter scenario characterizes electron transfer in ionic liquids. The analysis of electrode reactions in room-temperature ionic liquids shows that the magnitude of the free energy of nuclear solvation is significantly below its thermodynamic limit. Finally, this result applies to reaction times faster than microseconds and is currently limited by the available dielectric relaxation data.« less

Electrode Reactions in Slowly Relaxing Media

DOE PAGES

Matyushov, Dmitry V.; Newton, Marshall D.

2017-11-17

Here, standard models of reaction kinetics in condensed materials rely on the Boltzmann-Gibbs distribution for the population of reactants at the top of the free energy barrier separating them from the products. While energy dissipation and quantum effects at the barrier top can potentially affect the transmission coefficient entering the rate preexponential factor, much stronger dynamical effects on the reaction barrier are caused by the breakdown of ergodicity for populating the reaction barrier (violation of the Boltzmann-Gibbs statistics). When the spectrum of medium modes coupled to the reaction coordinate includes fluctuations slower than the reaction rate, such nuclear motions dynamicallymore » freeze on the reaction time-scale and do not contribute to the activation barrier. In this paper, we consider the consequences of this scenario for electrode reactions in slowly relaxing media. Changing electrode overpotential speeds electrode electron transfer up, potentially cutting through the spectrum of nuclear modes coupled to the reaction coordinate. The reorganization energy of electrochemical electron transfer becomes a function of the electrode overpotential, switching between the thermodynamic value at low rates to the nonergodic limit at higher rates. The sharpness of this transition depends of the relaxation spectrum of the medium. The reorganization energy experiences a sudden drop with increasing overpotential for a medium with a Debye relaxation, but becomes a much shallower function of the overpotential for media with stretched exponential dynamics. The latter scenario characterizes electron transfer in ionic liquids. The analysis of electrode reactions in room-temperature ionic liquids shows that the magnitude of the free energy of nuclear solvation is significantly below its thermodynamic limit. Finally, this result applies to reaction times faster than microseconds and is currently limited by the available dielectric relaxation data.« less

In situ evolution of highly dispersed amorphous CoO x clusters for oxygen evolution reaction

DOE PAGES

Chen, Dawei; Dong, Chung-Li; Zou, Yuqin; ...

2017-07-24

Electrocatalytic water splitting is a key technique to produce hydrogen fuels, which can be considered as an efficient strategy to store renewable energy. Oxygen evolution reaction (OER) that occurs at the anode side requires a four-electron transfer under highly oxidizing conditions. OER has a large overpotential and therefore determines the overall efficiency. Certain electrocatalysts can efficiently help to improve the reaction kinetics. Owing to the high cost of precious metals such as Pt, Ru, and Ir, non-precious metal oxide catalysts have been vigorously investigated under alkaline conditions. Herein, we synthesized novel highly dispersed amorphous CoO x for the first timemore » in the form of a cluster favorable to enhance the OER activity using a facile method via the air dielectric barrier discharge (DBD) plasma. Compared with the pristine biopolymer–cobalt complex, the amorphous CoO x cluster exhibits a much higher current density and a lower overpotential for OER, e.g., the overpotential of 290 mV at 10 mA cm -2 and the overpotential of only 350 mV at 300 mA cm -1. The excellent electrocatalytic OER activity was attributed to the unsaturated catalytic sites on the amorphous CoO x cluster. In addition, we studied the reaction mechanism, and it was observed that pure O 2 DBD plasma could lead to the evolution of crystalline CoO x; however, the presence of N 2 and O 2 in DBD plasma could ensure the facile evolution of amorphous CoO x clusters. This study provides a new strategy, therefore, to design amorphous materials for electrocatalysis and beyond.« less

In situ evolution of highly dispersed amorphous CoO x clusters for oxygen evolution reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Dawei; Dong, Chung-Li; Zou, Yuqin

Electrocatalytic water splitting is a key technique to produce hydrogen fuels, which can be considered as an efficient strategy to store renewable energy. Oxygen evolution reaction (OER) that occurs at the anode side requires a four-electron transfer under highly oxidizing conditions. OER has a large overpotential and therefore determines the overall efficiency. Certain electrocatalysts can efficiently help to improve the reaction kinetics. Owing to the high cost of precious metals such as Pt, Ru, and Ir, non-precious metal oxide catalysts have been vigorously investigated under alkaline conditions. Herein, we synthesized novel highly dispersed amorphous CoO x for the first timemore » in the form of a cluster favorable to enhance the OER activity using a facile method via the air dielectric barrier discharge (DBD) plasma. Compared with the pristine biopolymer–cobalt complex, the amorphous CoO x cluster exhibits a much higher current density and a lower overpotential for OER, e.g., the overpotential of 290 mV at 10 mA cm -2 and the overpotential of only 350 mV at 300 mA cm -1. The excellent electrocatalytic OER activity was attributed to the unsaturated catalytic sites on the amorphous CoO x cluster. In addition, we studied the reaction mechanism, and it was observed that pure O 2 DBD plasma could lead to the evolution of crystalline CoO x; however, the presence of N 2 and O 2 in DBD plasma could ensure the facile evolution of amorphous CoO x clusters. This study provides a new strategy, therefore, to design amorphous materials for electrocatalysis and beyond.« less

Engineered cost-effective growth of Co-based nanoflakes as a sustainable water oxidation electrocatalyst

NASA Astrophysics Data System (ADS)

Pourreza, M.; Naseri, N.

2017-11-01

Developing low-cost, scalable and reproducible synthesis methods for water oxidation reaction (WOR) catalysts is highly desirable and also challenging in energy, environmental and industrial applications. In this context, electrochemical deposition is known as an easy and cost-effective technique in nanomaterial growth. Herein, cobalt-based nanoflakes were grown on a flexible and commercially available steel mesh substrate by electrodeposition approach with a crystalline structure as a mixture of oxide, hydroxide and oxyhydroxide phases. For the first time, the correlation between electrodeposition parameters, time and current density, and morphological characteristics of the grown nanoflakes (density and aspect ratio based on SEM results) has been derived. According to a comprehensive study of the flakes’ electrocatalytic performance in WOR, the optimized sample fabricated with a moderate electrodeposition current density (7 mA cm-2) and duration time (2000 s) revealed the highest density (7.6  ×  108 cm-2) and aspect ratio (7.1) as well as the lowest values for overpotential (OP  =  324 mV) and charge transfer resistance (14 Ω). This designed array of Co-based nanoflakes also showed the lowest value of overpotential for bare cobalt-based WOR electrocatalysts reported yet. High and low values for deposition current density and/or deposition time had a negative effect on the sample surface, leaving some areas without any flakes or with incomplete and inefficient formation of nanoflakes with low densities and aspect ratios. A similar effect was observed for annealed samples in the range of 200-400 °C. Based on recorded overpotentials and extracted surface morphological parameters, a linear and logarithmic behavior in overpotential-flake density dependency was proposed for current density and time controlled systems, respectively.

Electrodeposited Co-doped NiSe2 nanoparticles film: a good electrocatalyst for efficient water splitting

NASA Astrophysics Data System (ADS)

Liu, Tingting; Asiri, Abdullah M.; Sun, Xuping

2016-02-01

In this communication, we report that a Co-doped NiSe2 nanoparticles film electrodeposited on a conductive Ti plate (Co0.13Ni0.87Se2/Ti) behaves as a robust electrocatalyst for both HER and OER in strongly basic media, with good activity over a NiSe2/Ti counterpart. This Co0.13Ni0.87Se2/Ti catalytic electrode delivers 10 mA cm-2 at an overpotential of 64 mV for HER and 100 mA cm-2 at an overpotential of 320 mV for OER in 1.0 M KOH. A voltage of only 1.62 V is required to drive 10 mA cm-2 for the two-electrode alkaline water electrolyzer using Co0.13Ni0.87Se2/Ti as an anode and cathode.In this communication, we report that a Co-doped NiSe2 nanoparticles film electrodeposited on a conductive Ti plate (Co0.13Ni0.87Se2/Ti) behaves as a robust electrocatalyst for both HER and OER in strongly basic media, with good activity over a NiSe2/Ti counterpart. This Co0.13Ni0.87Se2/Ti catalytic electrode delivers 10 mA cm-2 at an overpotential of 64 mV for HER and 100 mA cm-2 at an overpotential of 320 mV for OER in 1.0 M KOH. A voltage of only 1.62 V is required to drive 10 mA cm-2 for the two-electrode alkaline water electrolyzer using Co0.13Ni0.87Se2/Ti as an anode and cathode. Electronic supplementary information (ESI) available: Experimental section and supplementary figures. See DOI: 10.1039/c5nr07170d

Measuring Li + inventory losses in LiCoO 2/graphite cells using Raman microscopy

DOE PAGES

Snyder, Chelsea Marie; Apblett, Christopher A.; Grillet, Anne; ...

2016-03-25

Here, the contribution from loss of Li + inventory to capacity fade is described for slow rates (C/10) and long-term cycling (up to 80 cycles). It was found through electrochemical testing and ex-situ Raman analysis that at these slow rates, the entirety of capacity loss up to 80 cycles can be explained by loss of Li + inventory in the cell. The Raman spectrum of LiCoO 2 is sensitive to the state of lithiation and can therefore be leveraged to quantify the state of lithiation for individual particles. With these Raman derived estimates, the lithiation state of the cathode inmore » the discharged state is compared to electrochemical data as a function of cycle number. High correlation is found between Raman quantifications of cycleable lithium and the capacity fade. Additionally, the linear relationship between discharge capacity and cell overpotential suggests that the loss of capacity stems from an impedance rise of the electrodes, which based on Li inventory losses, is caused by SEI formation and repair.« less

Intercalation of Cobalt into the Interlayer of Birnessite Improves Oxygen Evolution Catalysis

DOE PAGES

Thenuwara, Akila C.; Shumlas, Samantha L.; Attanayake, Nuwan H.; ...

2016-10-10

Here we show that the activity of cobalt for the oxygen evolution reaction (OER) can be enhanced by confining it in the interlayer region of birnessite (layered manganese oxide). The cobalt intercalation was verified by employing state-of-the-art characterization techniques such as XRD, Raman and electron microscopy. It is demonstrated that the Co 2+/birnessite electrocatalyst can reach 10 mA cm -2 at an overpotential of 360 mV with near unity Faradaic efficiency. This overpotential is lower than that which can be achieved by using a pure cobalt hydroxide electrocatalyst for the OER. Furthermore, the Co 2+/birnessite catalyst shows no degradation aftermore » 1000 electrochemical cycles.« less

The analysis of energy efficiency in water electrolysis under high temperature and high pressure

NASA Astrophysics Data System (ADS)

Hourng, L. W.; Tsai, T. T.; Lin, M. Y.

2017-11-01

This paper aims to analyze the energy efficiency of water electrolysis under high pressure and high temperature conditions. The effects of temperature and pressure on four different kinds of reaction mechanisms, namely, reversible voltage, activation polarization, ohmic polarization, and concentration polarization, are investigated in details. Results show that the ohmic and concentration over-potentials are increased as temperature is increased, however, the reversible and activation over-potentials are decreased as temperature is increased. Therefore, the net efficiency is enhanced as temperature is increased. The efficiency of water electrolysis at 350°C/100 bars is increased about 17%, compared with that at 80°C/1bar.

Arginine-Containing Ligands Enhance H-2 Oxidation Catalyst Performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Arnab; Roberts, John A.; Shaw, Wendy J.

2014-06-16

In H2 fuel cells, performance depends on factors controlling turnover frequency and energy efficiency in the electrocatalytic oxidation of H2. Nature uses the hydrogenase enzymes to oxidize H2 at high turnover frequencies (up to 20,000 s-1) and low overpotentials (<100 mV), while the fastest synthetic catalyst reported to date only oxidizes H2 at 50 s-1 under 1 atm H2. Here we report a water-soluble complex incorporating the amino acid arginine, [NiII(PCy2NArg2)2]6+, that operates at 210 s-1 (180 mV overpotential) under 1 atm H2 and 144,000 s-1 (460 mV overpotential) under 133 atm H2. The complex functions from pH 0-14 withmore » rates increasing at lower pH values. The arginine groups impart water solubility and play a critical role in enhancing turnover frequency, most consistent with an intramolecular Arg-Arg interaction that controls the structure of the catalyst active site. This work was funded by the Office of Science Early Career Research Program through the US DOE, BES (AD, WJS), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US DOE, BES (JASR). PNNL is operated by Battelle for the US DOE.« less

Tailoring the Edge Structure of Molybdenum Disulfide toward Electrocatalytic Reduction of Carbon Dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abbasi, Pedram; Asadi, Mohammad; Liu, Cong

2017-01-24

Electrocatalytic conversion of carbon dioxide (CO2) into energy-rich fuels is considered to be the most efficient approach to achieve a carbon neutral cycle. Transition-metal dichalcogenides (TMDCs) have recently shown a very promising catalytic performance for CO2 reduction reaction in an ionic liquid electrolyte. Here, we report that the catalytic performance of molybdenum disulfide (MoS2), a member of TMDCs, can be significantly improved by using an appropriate dopant. Our electrochemical results indicate that 5% niobium (Nb)-doped vertically aligned MoS2 in ionic liquid exhibits 1 order of magnitude higher CO formation turnover frequency (TOF) than pristine MoS2 at an overpotential range ofmore » 50-150 mV. The TOF of this catalyst is also 2 orders of magnitude higher than that of Ag nanoparticles over the entire range of studied overpotentials (100-650 mV). Moreover, the in situ differential electrochemical mass spectrometry experiment shows the onset overpotential of 31 mV for this catalyst, which is the lowest onset potential for CO2 reduction reaction reported so far. Our density functional theory calculations reveal that low concentrations of Nb near the Mo edge atoms can enhance the TOF of CO formation by modifying the binding energies of intermediates to MoS2 edge atoms.« less

Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel.

PubMed

Gao, Shan; Lin, Yue; Jiao, Xingchen; Sun, Yongfu; Luo, Qiquan; Zhang, Wenhua; Li, Dianqi; Yang, Jinlong; Xie, Yi

2016-01-07

Electroreduction of CO2 into useful fuels, especially if driven by renewable energy, represents a potentially 'clean' strategy for replacing fossil feedstocks and dealing with increasing CO2 emissions and their adverse effects on climate. The critical bottleneck lies in activating CO2 into the CO2(•-) radical anion or other intermediates that can be converted further, as the activation usually requires impractically high overpotentials. Recently, electrocatalysts based on oxide-derived metal nanostructures have been shown to enable CO2 reduction at low overpotentials. However, it remains unclear how the electrocatalytic activity of these metals is influenced by their native oxides, mainly because microstructural features such as interfaces and defects influence CO2 reduction activity yet are difficult to control. To evaluate the role of the two different catalytic sites, here we fabricate two kinds of four-atom-thick layers: pure cobalt metal, and co-existing domains of cobalt metal and cobalt oxide. Cobalt mainly produces formate (HCOO(-)) during CO2 electroreduction; we find that surface cobalt atoms of the atomically thin layers have higher intrinsic activity and selectivity towards formate production, at lower overpotentials, than do surface cobalt atoms on bulk samples. Partial oxidation of the atomic layers further increases their intrinsic activity, allowing us to realize stable current densities of about 10 milliamperes per square centimetre over 40 hours, with approximately 90 per cent formate selectivity at an overpotential of only 0.24 volts, which outperforms previously reported metal or metal oxide electrodes evaluated under comparable conditions. The correct morphology and oxidation state can thus transform a material from one considered nearly non-catalytic for the CO2 electroreduction reaction into an active catalyst. These findings point to new opportunities for manipulating and improving the CO2 electroreduction properties of metal systems, especially once the influence of both the atomic-scale structure and the presence of oxide are mechanistically better understood.

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

DOE PAGES

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan; ...

2017-03-20

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Atomically monodisperse nickel nanoclusters as highly active electrocatalysts for water oxidation

NASA Astrophysics Data System (ADS)

Joya, Khurram S.; Sinatra, Lutfan; Abdulhalim, Lina G.; Joshi, Chakra P.; Hedhili, M. N.; Bakr, Osman M.; Hussain, Irshad

2016-05-01

Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 which initiate oxygen evolution at an amazingly low overpotential of ~1.51 V (vs. RHE; η ~ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm-2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec-1 is observed using Ni4(PET)8. These results are comparable to the state-of-the-art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm-2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation.Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 which initiate oxygen evolution at an amazingly low overpotential of ~1.51 V (vs. RHE; η ~ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm-2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec-1 is observed using Ni4(PET)8. These results are comparable to the state-of-the-art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm-2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation. Electronic supplementary information (ESI) available: CCDC 1419754 and 1419731. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6nr00709k

Study on electrochemically deposited Mg metal

NASA Astrophysics Data System (ADS)

Matsui, Masaki

An electrodeposition process of magnesium metal from Grignard reagent based electrolyte was studied by comparing with lithium. The electrodeposition of magnesium was performed at various current densities. The obtained magnesium deposits did not show dendritic morphologies while all the lithium deposits showed dendritic products. Two different crystal growth modes in the electrodeposition process of magnesium metal were confirmed by an observation using scanning electron micro scope (SEM) and a crystallographic analysis using X-ray diffraction (XRD). An electrochemical study of the deposition/dissolution process of the magnesium showed a remarkable dependency of the overpotential of magnesium deposition on the electrolyte concentration compared with lithium. This result suggests that the dependency of the overpotential on the electrolyte concentration prevent the locally concentrated current resulting to form very uniform deposits.

Oxygen ion conducting materials

DOEpatents

Vaughey, John; Krumpelt, Michael; Wang, Xiaoping; Carter, J. David

2003-01-01

An oxygen ion conducting ceramic oxide that has applications in industry including fuel cells, oxygen pumps, oxygen sensors, and separation membranes. The material is based on the idea that substituting a dopant into the host perovskite lattice of (La,Sr)MnO.sub.3 that prefers a coordination number lower than 6 will induce oxygen ion vacancies to form in the lattice. Because the oxygen ion conductivity of (La,Sr)MnO.sub.3 is low over a very large temperature range, the material exhibits a high overpotential when used. The inclusion of oxygen vacancies into the lattice by doping the material has been found to maintain the desirable properties of (La,Sr)MnO.sub.3, while significantly decreasing the experimentally observed overpotential.

Oxygen ion conducting materials

DOEpatents

Carter, J. David; Wang, Xiaoping; Vaughey, John; Krumpelt, Michael

2004-11-23

An oxygen ion conducting ceramic oxide that has applications in industry including fuel cells, oxygen pumps, oxygen sensors, and separation membranes. The material is based on the idea that substituting a dopant into the host perovskite lattice of (La,Sr)MnO.sub.3 that prefers a coordination number lower than 6 will induce oxygen ion vacancies to form in the lattice. Because the oxygen ion conductivity of (La,Sr)MnO.sub.3 is low over a very large temperature range, the material exhibits a high overpotential when used. The inclusion of oxygen vacancies into the lattice by doping the material has been found to maintain the desirable properties of (La,Sr)MnO.sub.3, while significantly decreasing the experimentally observed overpotential.

Oxygen ion conducting materials

DOEpatents

Vaughey, John; Krumpelt, Michael; Wang, Xiaoping; Carter, J. David

2005-07-12

An oxygen ion conducting ceramic oxide that has applications in industry including fuel cells, oxygen pumps, oxygen sensors, and separation membranes. The material is based on the idea that substituting a dopant into the host perovskite lattice of (La,Sr)MnO.sub.3 that prefers a coordination number lower than 6 will induce oxygen ion vacancies to form in the lattice. Because the oxygen ion conductivity of (La,Sr)MnO.sub.3 is low over a very large temperature range, the material exhibits a high overpotential when used. The inclusion of oxygen vacancies into the lattice by doping the material has been found to maintain the desirable properties of (La,Sr)MnO.sub.3, while significantly decreasing the experimentally observed overpotential.

Frequency response of electrochemical cells

NASA Technical Reports Server (NTRS)

Thomas, Daniel L.

1989-01-01

Impedance concepts can be applied to the analysis of battery electrodes, yielding information about the structure of the electrode and the processes occurring in the electrode. Structural parameters such as the specific area (surface area per gram of electrode) can be estimated. Electrode variables such as surface overpotential, ohmic losses, and diffusion limitations may be studied. Nickel and cadmium electrodes were studied by measuring the ac impedance as a function of frequency, and the specific areas that were determined were well within the range of specific areas determined from BET measurements. Impedance spectra were measured for the nickel and cadmium electrodes, and for a 20 A-hr NiCd battery as functions of the state of charge. More work is needed to determine the feasibility of using frequency response as a nondestructive testing technique for batteries.

Stability of carbon electrodes for aqueous lithium-air secondary batteries

NASA Astrophysics Data System (ADS)

Ohkuma, Hirokazu; Uechi, Ichiro; Matsui, Masaki; Takeda, Yasuo; Yamamoto, Osamu; Imanishi, Nobuyuki

2014-01-01

The air electrode performance of various carbon materials, such as Ketjen black (KB), acetylene black (AB and AB-S), Vulcan XC-72R (VX), and vapor grown carbon fiber (VGCF) with and without La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) catalyst were examined in an aqueous solution of saturated LiOH with 10 M LiCl in the current density range 0.2-2.0 mA cm-2. The best performance for oxygen reduction and evolution reactions was observed for the KB electrode, which has the highest surface area among the carbon materials examined. A steady over-potential of 0.2 V was obtained for the oxygen reduction reaction using the KB electrode without the catalyst, while the over-potential was 0.15 V for KB with the LSCF catalyst at 2.0 mA cm-2. The over-potentials for the oxygen evolution reaction were slightly higher than those for the oxygen reduction reaction, and gradually increased with the polarization period. Analysis of the gas in the cell after polarization above 0.4 V revealed the evolution of a small amount of CO during the oxygen evolution reaction by the decomposition of carbon in the electrode. The amount of CO evolved was significantly decreased by the addition of LSCF to the carbon electrode.

3D structured Mo-doped Ni3S2 nanosheets as efficient dual-electrocatalyst for overall water splitting

NASA Astrophysics Data System (ADS)

Wu, Chengrong; Liu, Bitao; Wang, Jun; Su, Yongyao; Yan, Hengqing; Ng, Chuntan; Li, Cheng; Wei, Jumeng

2018-05-01

Searching for a cost-effective, high efficient and stable bifunctional electrocatalyst for overall water-splitting is critical to renewable energy systems. In this study, three-dimensional (3D) curved nanosheets of Mo-doped Ni3S2 grown on nickel foam were successfully synthesized via a one-step hydrothermal process. The hydrogen-evolution reaction (HER) and the oxygen-evolution reaction (OER) in alkaline environment of this 3D catalyst are investigated in detail. The results show that it possesses lower overpotential, high current densities and small Tafel slopes both in OER and HER. For HER, the catalysts show excellent electrochemical performance, demonstrating a low over-potential of 212 mV at 10 mA cm-2 with a large decrease of 127 mV compared to the undoped Ni3S2. And it also shows a lower overpotential of 260 mV at 10 mA cm-2 which decreases 30 mV for OER. In addition, it is only need 1.67 V for the overall water splitting at 10 mA cm-2 which is 70 mV. It found that the Mo element would change the morphology of Ni3S2 and induce much more active sites for HER and OER. The as-prepared Mo-doped Ni3S2 bi-functional electrocatalyst could act as the promising electrode materials for water splitting.

Porous Co3O4 nanorods anchored on graphene nanosheets as an effective electrocatalysts for aprotic Li-O2 batteries

NASA Astrophysics Data System (ADS)

Yuan, Mengwei; Yang, Yan; Nan, Caiyun; Sun, Genban; Li, Huifeng; Ma, Shulan

2018-06-01

The large over-potential during the battery operation is a great obstacle for the application of Li-O2 batteries. The porous structure and electrical conductivity of the electrocatalysts are significant for the electrocatalytic performance of Li-O2 batteries. In this work, a porous Co3O4/GN nanocomposite (Co3O4 nanorods anchored on graphene nanosheets) is prepared via a facile hydrothermal method assisted with heat treatment. The unique structure of Co3O4/GN endows efficient electrocatalystic activity for Li-O2 batteries. In comparison to the Co3O4, the Co3O4/GN demonstrates a better cycle performance showing more than 40 cycles with a 1500 mAh g-1 capacity limit strategy at a current density of 300 mA g-1, and a reduced over-potential of 110 mV at high current density (1200 mA g-1). The Co3O4/GN also displays a high initial specific capacity (7600 mAh g-1) and a good reversibility in full cycle with a coulombic efficiency of 99.8% in the first cycle. The impressed cyclability, specific capacity, rate performance, and low over-potentials indicate that the as-prepared Co3O4/GN nanocomposite is a promising catalyst candidate for reversible Li-O2 batteries.

Characteristics of the high-rate discharge capability of a nickel/metal hydride battery electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geng, M.; Han, J.; Feng, F.

1999-10-01

The high rate discharge capability of the negative electrode in a Ni/MH battery is mainly determined by the charge transfer process at the interface between the metal hydride (MH) alloy powder and the electrolyte, and the mass transfer process in the bulk MH alloy powder. In this study, the anodic polarization curves of a MH electrode were measured and analyzed. An alloy of nominal composition Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{sub 0.35}Al{sub 0.35} was used as the negative electrode material. With increasing number of charge/discharge cycles, the MH alloy powders microcrack into particles several micrometers in diameter. The decrease in themore » MH alloy particle size results in an increase in both the activation surface area and the exchange current density of the MH alloy electrode. The electrode overpotentials of the MH electrode decreases with increasing number of cycles at a large value of anodic polarization current. The decrease in electrode overpotential leads to an increase in the high rate discharge capability of the MH electrode. By using the limiting current, the hydrogen diffusion coefficient in the MH alloy was estimated to be 1.2 x 10{sup {minus}11}cm{sup 2}s{sup {minus}1} assuming an average particle radius of 5 {micro}m.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pezeshki, Alan M.; Sacci, Robert L.; Delnick, Frank M.

Here, an improved method for quantitative measurement of the charge transfer, finite diffusion, and ohmic overpotentials in redox flow batteries using electrochemical impedance spectroscopy is presented. The use of a pulse dampener in the hydraulic circuit enables the collection of impedance spectra at low frequencies with a peristaltic pump, allowing the measurement of finite diffusion resistances at operationally relevant flow rates. This method is used to resolve the rate-limiting processes for the V 2+/V 3+ redox couple on carbon felt and carbon paper electrodes in the vanadium redox flow battery. Carbon felt was limited by both charge transfer and ohmicmore » resistance, while carbon paper was limited by charge transfer, finite diffusion, and ohmic resistances. The influences of vanadium concentration and flow field design also are quantified.« less

Investigations by Protein Film Electrochemistry of Alternative Reactions of Nickel-Containing Carbon Monoxide Dehydrogenase.

PubMed

Wang, Vincent C-C; Islam, Shams T A; Can, Mehmet; Ragsdale, Stephen W; Armstrong, Fraser A

2015-10-29

Protein film electrochemistry has been used to investigate reactions of highly active nickel-containing carbon monoxide dehydrogenases (CODHs). When attached to a pyrolytic graphite electrode, these enzymes behave as reversible electrocatalysts, displaying CO2 reduction or CO oxidation at minimal overpotential. The O2 sensitivity of CODH is suppressed by adding cyanide, a reversible inhibitor of CO oxidation, or by raising the electrode potential. Reduction of N2O, isoelectronic with CO2, is catalyzed by CODH, but the reaction is sluggish, despite a large overpotential, and results in inactivation. Production of H2 and formate under highly reducing conditions is consistent with calculations predicting that a nickel-hydrido species might be formed, but the very low rates suggest that such a species is not on the main catalytic pathway.

Self-Supported Copper Oxide Electrocatalyst for Water Oxidation at Low Overpotential and Confirmation of Its Robustness by Cu K-edge X-ray Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiang; Cui, Shengsheng; Sun, Zijun

Developing efficient water oxidation catalysts made of earth-abundant elements is a demanding challenge that should be met to fulfill the promise of water splitting for clean energy. Herein we report an annealing approach to synthesize binder-free, self-supported heterogeneous copper oxide (CuO) on conductive electrodes for oxygen evolution reaction (OER), producing electrodes with excellent electrocatalytic properties such as high efficiency, low overpotential, and good stability. The catalysts were grown in situ on fluorine-doped tin oxide (FTO) by electrodeposition from a simple Cu(II) salt solution, followed by annealing at a high temperature. Under optimal conditions, the CuO-based OER catalyst shows an onsetmore » potential of <0.58 V (vs Ag/AgCl) in 1.0 M KOH at pH 13.6. From the Tafel plot, the required overpotentials for current densities of 0.1 and 1.0 mA/cm2 are only 360 and 430 mV, respectively. The structure and the presence of a CuO motif in the catalyst have been identified by high-energy X-ray diffraction (HE-XRD), Cu K-edge X-ray absorption (XAS) spectra including X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS). To the best of our knowledge, this represents the best catalytic activity for CuO-based OER catalysts to date.« less

Synthesis of nickel germanide (Ge12Ni19) nanoparticles for durable hydrogen evolution reaction in acid solutions.

PubMed

Chen, Jee-Yee; Jheng, Shao-Lou; Tuan, Hsing-Yu

2018-06-14

Desigining advanced materials as electrochemical catalysts for the hydrogen evolution reaction (HER) has caught great attention owing to the growing demand for clean and renewable energy. Nickel (Ni)-based compounds and alloys are promising non-noble-metal electrocatalysts due to their low cost and high activity. However, in most cases, Ni-based compounds and alloys have low durability in acid electrolyte, which limits their application in the electrolytic processes. In this study, monoclinic Ge12Ni19 nanoparticles were synthesized and exhibited high electrocatalytic activity and stability for the HER in acidic solution. Ge12Ni19 nanoparticles achieve an overpotential of 190 mV at cathodic current density of 10 mA cm-2 and a Tafel slope of 88.5 mV per decade in 0.50 M H2SO4 electrolyte. Moreover, the performance is maintained after a 10 000-cycle CV sweep (-0.3 to +0.1 V vs. RHE) or under a static overpotential of -0.7 V vs. RHE for 24 hours. The reported electrocatalytic performance of the Ge12Ni19 nanoparticles sufficiently proves the excellent endurance at lower required active overpotentials in acidic solution, enabling the broad applications of the Ni-based electrocatalysts. Finally, a large-area (5 cm2) electrocatalyst for HER was demonstrated for the first time. The great efficiency of the energy conversion performance sufficiently represented the potential of Ge12Ni19 nanoparticles as electrocatalysts in commercial fuel cells.

Copper nanoparticle ensembles for selective electroreduction of CO 2 to C 2-C 3 products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Dohyung; Kley, Christopher S.; Li, Yifan

Direct conversion of carbon dioxide to multicarbon products remains as a grand challenge in electrochemical CO 2 reduction. Various forms of oxidized copper have been demonstrated as electrocatalysts that still require large overpotentials. Here in this paper, we show that an ensemble of Cu nanoparticles (NPs) enables selective formation of C 2–C 3 products at low overpotentials. Densely packed Cu NP ensembles underwent structural transformation during electrolysis into electrocatalytically active cube-like particles intermixed with smaller nanoparticles. Ethylene, ethanol, and n-propanol are the major C 2–C 3 products with onset potential at -0.53 V (vs. reversible hydrogen electrode, RHE) and Cmore » 2–C 3 faradaic efficiency (FE) reaching 50% at only -0.75 V. Thus, the catalyst exhibits selective generation of C 2–C 3 hydrocarbons and oxygenates at considerably lowered overpotentials in neutral pH aqueous media. In addition, this approach suggests new opportunities in realizing multicarbon product formation from CO 2, where the majority of efforts has been to use oxidized copper-based materials. Robust catalytic performance is demonstrated by 10 h of stable operation with C 2–C 3 current density 10 mA/cm 2 (at -0.75 V), rendering it attractive for solar-to-fuel applications. Lastly, Tafel analysis suggests reductive CO coupling as a rate determining step for C 2 products, while n-propanol (C 3) production seems to have a discrete pathway.« less

Copper nanoparticle ensembles for selective electroreduction of CO 2 to C 2-C 3 products

DOE PAGES

Kim, Dohyung; Kley, Christopher S.; Li, Yifan; ...

2017-09-18

Direct conversion of carbon dioxide to multicarbon products remains as a grand challenge in electrochemical CO 2 reduction. Various forms of oxidized copper have been demonstrated as electrocatalysts that still require large overpotentials. Here in this paper, we show that an ensemble of Cu nanoparticles (NPs) enables selective formation of C 2–C 3 products at low overpotentials. Densely packed Cu NP ensembles underwent structural transformation during electrolysis into electrocatalytically active cube-like particles intermixed with smaller nanoparticles. Ethylene, ethanol, and n-propanol are the major C 2–C 3 products with onset potential at -0.53 V (vs. reversible hydrogen electrode, RHE) and Cmore » 2–C 3 faradaic efficiency (FE) reaching 50% at only -0.75 V. Thus, the catalyst exhibits selective generation of C 2–C 3 hydrocarbons and oxygenates at considerably lowered overpotentials in neutral pH aqueous media. In addition, this approach suggests new opportunities in realizing multicarbon product formation from CO 2, where the majority of efforts has been to use oxidized copper-based materials. Robust catalytic performance is demonstrated by 10 h of stable operation with C 2–C 3 current density 10 mA/cm 2 (at -0.75 V), rendering it attractive for solar-to-fuel applications. Lastly, Tafel analysis suggests reductive CO coupling as a rate determining step for C 2 products, while n-propanol (C 3) production seems to have a discrete pathway.« less

First-principles study of oxygen evolution reaction on Co doped NiFe-layered double hydroxides

NASA Astrophysics Data System (ADS)

Yu, Jie; Perdew, John; Yan, Qimin

The conversion of solar energy to renewable fuels is a grand challenge. One of the crucial steps for this energy conversion process is the discovery of efficient catalysts with lower overpotential for the oxygen evolution reaction (OER). Layered double hydroxides (LDH) with earth abundant elements such as Ni and Fe have been found as promising OER catalysts and shown to be active for water oxidation. Doping is one of the feasible ways to even lower the overpotential of host materials and breaks the linear scaling law. In this talk we'll present our study on the reaction mechanism of OER on pure and Co-doped NiFe-LDH systems in alkaline solution. We study the absorption energetics of reaction intermediate states and calculate the thermodynamic reaction energy using density functional theory with the PBE +U and the newly developed SCAN functionals. It is shown that the NiFe-LDH system with Co dopants has lower overpotential and higher activity compared with the undoped system. The improvement in activity is related to the presence of Co states in the electronic structure. The work provides a clear clue for the further improvement of the OER activity of LDH systems by chemical doping. The work was supported as part of the Center for the Computational Design of Functional Layered Materials, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science.

Thermochemical and mechanistic studies of electrocatalytic hydrogen production by cobalt complexes containing pendant amines.

PubMed

Wiedner, Eric S; Appel, Aaron M; DuBois, Daniel L; Bullock, R Morris

2013-12-16

Two cobalt(tetraphosphine) complexes [Co(P(nC-PPh2)2N(Ph)2)(CH3CN)](BF4)2 with a tetradentate phosphine ligand (P(nC-PPh2)2N(Ph)2 = 1,5-diphenyl-3,7-bis((diphenylphosphino)alkyl)-1,5-diaza-3,7-diphosphacyclooctane; alkyl = (CH2)2, n = 2 (L2); (CH2)3, n = 3 (L3)) have been studied for electrocatalytic hydrogen production using 1:1 [(DMF)H](+):DMF. A turnover frequency (TOF) of 980 s(-1) with an overpotential at Ecat/2 of 1210 mV was measured for [Co(II)(L2)(CH3CN)](2+), and a TOF of 980 s(-1) with an overpotential at Ecat/2 of 930 mV was measured for [Co(II)(L3)(CH3CN)](2+). Addition of water increases the TOF of [Co(II)(L2)(CH3CN)](2+) to 18,000 s(-1). The catalytic wave for each of these complexes occurs at the reduction potential of the corresponding HCo(III) complex. Comprehensive thermochemical studies of [Co(II)(L2)(CH3CN)](2+) and [Co(II)(L3)(CH3CN)](2+) and species derived from them by addition/removal of protons/electrons were carried out using values measured experimentally and calculated using density functional theory (DFT). Notably, HCo(I)(L2) and HCo(I)(L3) were found to be remarkably strong hydride donors, with HCo(I)(L2) being a better hydride donor than BH4(-). Mechanistic studies of these catalysts reveal that H2 formation can occur by protonation of a HCo(II) intermediate, and that the pendant amines of these complexes facilitate proton delivery to the cobalt center. The rate-limiting step for catalysis is a net intramolecular isomerization of the protonated pendant amine from the nonproductive exoisomer to the productive endo isomer.

Oxygen Reduction at Very Low Overpotential on Nanoporous Ag Catalysts

DOE PAGES

Zhou, Yang; Lu, Qi; Zhuang, Zhongbin; ...

2015-05-07

Here we report a monolithic nanoporous Ag (np-Ag) material, synthesized using the dealloying method, as high-performance catalysts for ORR in alkaline media. As shown in Scheme 1, when there is insufficient potential input, the O 2 molecules are more likely to rebound off from a planar electrode surface (i.e. bulk polycrystalline metal, films made from nanoparticles or nanowires) before they could be reduced. In contrast, they are more likely to be trapped inside the monolithic nanoporous structure, contacting with catalytic surface for multiple time, which greatly enhances the chance for them to be fully reduced. As a result, the np-Agmore » catalyst is able to achieve an equivalent or better ORR performance than the state-of the-art Pt/C catalyst at low overpotentials, which is most desired in electrochemical energy applications for maximizing efficiency.« less

Amorphous Nickel-Cobalt-Borate Nanosheet Arrays for Efficient and Durable Water Oxidation Electrocatalysis under Near-Neutral Conditions.

PubMed

Chen, Lanlan; Ren, Xiang; Teng, Wanqing; Shi, Pengfei

2017-07-21

Electrolytic hydrogen generation needs earth-abundant oxygen evolution reaction electrocatalysts that perform efficiently at mild pH. Here, the development of amorphous nickel-cobalt-borate nanosheet arrays on macroporous nickel foam (NiCo-Bi/NF) as a 3D catalyst electrode for high-performance water oxidation in near-neutral media is reported. To drive a current density of 10 mA cm -2 , the resulting NiCo-Bi/NF demands an overpotential of only 430 mV in 0.1 m potassium borate (K-Bi, pH 9.2). Moreover, it also shows long-term electrochemical durability with maintenance of catalytic activity for 20 h, achieving a high turnover frequency of 0.21 s -1 at an overpotential of 550 mV. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE PAGES

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.; ...

2018-01-19

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Oxygen evolution reaction in nanoconfined carbon nanotubes

NASA Astrophysics Data System (ADS)

Li, Ying; Lu, Xuefeng; Li, Yunfang; Zhang, Xueqing

2018-05-01

Improving oxygen electrochemistry through nanoscopic confinement has recently been highlighted as a promising strategy. In-depth understanding the role of confinement is therefore required. In this study, we simulate the oxygen evolution reaction (OER) on iron oxide nanoclusters under confinement of (7,7) and (8,8) armchair carbon nanotubes (CNTs). The free energies of the four proton coupled electron transfer (PCET) steps and the OER overpotentials are calculated. The Fe4O6 nanocluster confined in (7,7) CNT is found to be the most active for OER among the systems considered in this work. This leads to an increase in catalytic efficiency of OER compared to the hematite (110) surface, which was reported recently as an active surface towards OER. The calculated results show that the OER overpotential depends strongly on the magnetic properties of the iron oxide nanocluster. These findings are helpful for experimental design of efficient catalyst for water splitting applications.

Highly efficient hydrogen evolution based on Ni3S4@MoS2 hybrids supported on N-doped reduced graphene oxide

NASA Astrophysics Data System (ADS)

Xu, Xiaobing; Zhong, Wei; Wu, Liqian; Sun, Yuan; Wang, Tingting; Wang, Yuanqi; Du, Youwei

2018-01-01

Hydrogen evolution reaction (HER) through water splitting at low overpotential is an appealing technology to produce renewable energy, wherein the design of stable electrocatalysts is very critical. To achieve optimal electrochemical performance, a highly efficient and stable noble-metal-free HER catalyst is synthesized by means of a facile hydrothermal co-synthesis. It consists of Ni3S4 nanosheets and MoS2 nanolayers supported on N-doped reduced graphene oxide (Ni3S4/MoS2@N-rGO). The optimized sample provides a large amount of active sites that benefit electron transfer in 3D conductive networks. Thanks to the strong synergistic effect in the catalyst network, we achieved a low overpotential of 94 mV, a small Tafel slope of 56 mV/dec and remarkable durability in an acidic medium.

Homogeneously dispersed, multimetal oxygen-evolving catalysts

DOE PAGES

Zhang, Bo; Zheng, Xueli; Voznyy, Oleksandr; ...

2016-03-24

Earth-abundant first-row (3d) transition-metal-based catalysts have been developed for the oxygen-evolution reaction (OER); however, they operate at overpotentials significantly above thermodynamic requirements. Density functional theory suggested that non-3d high-valency metals such as tungsten can modulate 3d metal oxides, providing near-optimal adsorption energies for OER intermediates. We developed a room-temperature synthesis to produce gelled oxy-hydroxide materials with an atomically homogeneous metal distribution. These gelled FeCoW oxy-hydroxide exhibits the lowest overpotential (191 mV) reported at 10 mA per square centimeter in alkaline electrolyte. Here, the catalyst shows no evidence of degradation following more than 500 hours of operation. X-ray absorption and computationalmore » studies reveal a synergistic interplay between W, Fe and Co in producing a favorable local coordination environment and electronic structure that enhance the energetics for OER.« less

Increasing round trip efficiency of hybrid Li-air battery with bifunctional catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, K; Li, YF; Xing, YC

2013-07-30

Previously it was shown that Pt as cathode catalyst ha's a large overpotential during charge in rechargeable hybrid Li-air battery with sulfuric acid catholyte. This article demonstrates that a bifunctional catalyst composed of Pt and IrO2 supported on carbon nanotubes can address this problem. The specially designed and synthesized bifunctional catalyst showed significant overpotential reduction and achieved a round trip energy efficiency of 81% after 10 cycles, higher than many achieved in aprotic Li-O-2 batteries. The hybrid Li-air battery was discharged and recharged for 20 cycles at 0.2 mA/cm(2), showing a fairly stable cell performance. A specific capacity of 306more » mAh/g and a specific energy of 1110 Wh/kg were obtained for the hybrid Li-air battery in terms of acid weight. (c) 2013 Elsevier Ltd. All rights reserved.« less

Exergy analysis of a solid oxide fuel cell micropowerplant

NASA Astrophysics Data System (ADS)

Hotz, Nico; Senn, Stephan M.; Poulikakos, Dimos

In this paper, an analytical model of a micro solid oxide fuel cell (SOFC) system fed by butane is introduced and analyzed in order to optimize its exergetic efficiency. The micro SOFC system is equipped with a partial oxidation (POX) reformer, a vaporizer, two pre-heaters, and a post-combustor. A one-dimensional (1D) polarization model of the SOFC is used to examine the effects of concentration overpotentials, activation overpotentials, and ohmic resistances on cell performance. This 1D polarization model is extended in this study to a two-dimensional (2D) fuel cell model considering convective mass and heat transport along the fuel cell channel and from the fuel cell to the environment. The influence of significant operational parameters on the exergetic efficiency of the micro SOFC system is discussed. The present study shows the importance of an exergy analysis of the fuel cell as part of an entire thermodynamic system (transportable micropowerplant) generating electric power.

Intrinsic borohydride fuel cell/battery hybrid power sources

NASA Astrophysics Data System (ADS)

Hong, Jian; Fang, Bin; Wang, Chunsheng; Currie, Kenneth

The electrochemical oxidation behaviors of NaBH 4 on Zn, Zn-MH, and MH (metal-hydride) electrodes were investigated, and an intrinsic direct borohydride fuel cell (DBFC)/battery hybrid power source using MH (or Zn-MH) as the anode and MnO 2 as the cathode was tested. Borohydride cannot be effectively oxidized on Zn electrodes at the Zn oxidation potential because of the poor electrocatalytic ability of Zn for borohydride oxidation and the high overpotential, even though borohydride has the same oxidation potential of Zn in an alkaline solution. The borohydride can be electrochemically oxidized on Ni and MH electrodes through a 4e reaction at a high overpotential. Simply adding borohydride into an alkaline electrolyte of a Zn/air or MH/air battery can greatly increase the capacity, while an intrinsic DBFC/MH(or Zn)-MnO 2 battery can deliver a higher peak power than regular DBFCs.

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Homogeneously dispersed multimetal oxygen-evolving catalysts.

PubMed

Zhang, Bo; Zheng, Xueli; Voznyy, Oleksandr; Comin, Riccardo; Bajdich, Michal; García-Melchor, Max; Han, Lili; Xu, Jixian; Liu, Min; Zheng, Lirong; García de Arquer, F Pelayo; Dinh, Cao Thang; Fan, Fengjia; Yuan, Mingjian; Yassitepe, Emre; Chen, Ning; Regier, Tom; Liu, Pengfei; Li, Yuhang; De Luna, Phil; Janmohamed, Alyf; Xin, Huolin L; Yang, Huagui; Vojvodic, Aleksandra; Sargent, Edward H

2016-04-15

Earth-abundant first-row (3d) transition metal-based catalysts have been developed for the oxygen-evolution reaction (OER); however, they operate at overpotentials substantially above thermodynamic requirements. Density functional theory suggested that non-3d high-valency metals such as tungsten can modulate 3d metal oxides, providing near-optimal adsorption energies for OER intermediates. We developed a room-temperature synthesis to produce gelled oxyhydroxides materials with an atomically homogeneous metal distribution. These gelled FeCoW oxyhydroxides exhibit the lowest overpotential (191 millivolts) reported at 10 milliamperes per square centimeter in alkaline electrolyte. The catalyst shows no evidence of degradation after more than 500 hours of operation. X-ray absorption and computational studies reveal a synergistic interplay between tungsten, iron, and cobalt in producing a favorable local coordination environment and electronic structure that enhance the energetics for OER. Copyright © 2016, American Association for the Advancement of Science.

Abstract - Cooperative Research and Development Agreement between Penn State University and National Energy Technology Laboratory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hickner, Michael A.; Matranga, Christopher S.

This project will use bipolar membranes to produce efficient vapor-phase electrolysis cells for splitting CO 2 to CO and oxygen. CO is a valuable chemical feedstock that can be combined catalytically with hydrogen in the Fischer-Tropsch process to make liquid fuels. CO is arguably the best target for CO 2 reduction since, as a gaseous product, it is easily collected and is relatively immune to membrane crossover losses. The keys to success in this project are to design and synthesize hydrophilic, low resistance bipolar membranes and to create optimized electrode/catalyst/ electrolyte architectures based on these new membranes and advanced catalystsmore » in order to achieve high current density at low overpotentials for CO 2 conversion. High current density is key to achieving industrially-relevant throughput for the process and low overpotentials maintain high overall efficiency for the process.« less

The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations.

PubMed

Montoya, Joseph H; Tsai, Charlie; Vojvodic, Aleksandra; Nørskov, Jens K

2015-07-08

The electrochemical production of NH3 under ambient conditions represents an attractive prospect for sustainable agriculture, but electrocatalysts that selectively reduce N2 to NH3 remain elusive. In this work, we present insights from DFT calculations that describe limitations on the low-temperature electrocatalytic production of NH3 from N2 . In particular, we highlight the linear scaling relations of the adsorption energies of intermediates that can be used to model the overpotential requirements in this process. By using a two-variable description of the theoretical overpotential, we identify fundamental limitations on N2 reduction analogous to those present in processes such as oxygen evolution. Using these trends, we propose new strategies for catalyst design that may help guide the search for an electrocatalyst that can achieve selective N2 reduction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrodeposition of nano-sized bismuth on copper foil as electrocatalyst for reduction of CO2 to formate

NASA Astrophysics Data System (ADS)

Lv, Weixin; Zhou, Jing; Bei, Jingjing; Zhang, Rui; Wang, Lei; Xu, Qi; Wang, Wei

2017-01-01

Electrochemical reduction of carbon dioxide (CO2) to formate is energetically inefficient because high overpotential is required for reduction of CO2 to formate on most traditional catalysts. In this paper, a novel nano-sized Bi-based electrocatalyst deposited on a Cu foil has been synthesized, which can be used as a cathode for electrochemical reduction of CO2 to formate with a low overpotential (0.69 V) and a high selectivity (91.3%). The electrocatalyst can show excellent catalytic performance toward reduction of CO2 which can probably be attributed to the nano-sized structure and the surface oxide layer. The energy efficiency for reduction of CO2 to formate can reach to 50% when an IrxSnyRuzO2/Ti electrode is used as anode, it is one of the highest values found in the literatures and very practicable for sustainable fuel synthesis.

Polarization loss correction derived from hydrogen local-resistance measurement in low Pt-loaded polymer-electrolyte fuel cells

DOE PAGES

Freiberg, Anna T. S.; Tucker, Michael C.; Weber, Adam Z.

2017-04-12

The reduction of platinum-loading on the cathode side of polymer-electrolyte fuel cells leads to a poorly understood increase in mass-transport resistance (MTR) at high current densities. This local resistance was measured using a facile hydrogen-pump technique with dilute active gases for membrane-electrode assemblies with catalyst layers of varying platinum-loading (0.03-0.40 mgPt/cm²). Furthermore, polarization curves in H 2/air were measured and corrected for the overpotential caused by the increased MTR for low loadings on the air side due to the reduced concentration of reactant gas at the catalyst surface. The difference in performance after correction for all resistances including the MTRmore » is minor, suggesting its origin to be diffusive in nature, and proving the meaningfulness of the facile hydrogen-pump technique for the characterization of the cathode catalyst layer under defined operation conditions.« less

Tuning the Morphology of Li2O2 by Noble and 3d metals: A Planar Model Electrode Study for Li-O2 Battery.

PubMed

Yang, Yao; Liu, Wei; Wu, Nian; Wang, Xiaochen; Zhang, Tao; Chen, Linfeng; Zeng, Rui; Wang, Yingming; Lu, Juntao; Fu, Lei; Xiao, Li; Zhuang, Lin

2017-06-14

In this work, a planar model electrode method has been used to investigate the structure-activity relationship of multiple noble and 3d metal catalysts for the cathode reaction of Li-O 2 battery. The result shows that the battery performance (discharge/charge overpotential) strongly depends not only on the type of catalysts but also on the morphology of the discharge product (Li 2 O 2 ). Specifically, according to electrochemical characterization and scanning electron microscopy (SEM) observation, noble metals (Pd, Pt, Ru, Ir, and Au) show excellent battery performance (smaller discharge/charge overpotential), with wormlike Li 2 O 2 particles with size less than 200 nm on their surfaces. On the other hand, 3d metals (Fe, Co, Ni, and Mn) offered poor battery performance (larger discharge/charge overpotential), with much larger Li 2 O 2 particles (1 μm to a few microns) on their surfaces after discharging. Further research shows that a "volcano plot" is found by correlating the discharging/charging plateau voltage with the adsorption energy of LiO 2 on different metals. The metals with better battery performance and worm-like-shaped Li 2 O 2 are closer to the top of the "volcano", indicating adsorption energy of LiO 2 is one of the key characters for the catalyst to reach a good performance for the oxygen electrode of Li-O 2 battery, and it has a strong influence on the morphology of the discharge product on the electrode surface.

"Unexpected" behaviour of the internal resistance of a vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Rudolph, S.; Schröder, U.; Bayanov, I. M.; Hage-Packhäuser, S.

2016-02-01

This article presents the results of experimental and theoretical studies of energy losses owing to the internal resistance of vanadium redox flow batteries (VRFBs). A dependence of the internal cell resistance (ICR) on the electric current was measured and calculated. During the cyclic operation of a test battery, the internal resistance was halved by increasing the electric current from 3 A to 9 A. This is due to a strongly non-linear dependence of an over-potential of the electrochemical reactions on the current density. However, the energy efficiency does not increase due to a squared dependence of the energy losses on the increasing electric current. The energy efficiency of the test battery versus the electric current was measured and simulated. The deviation between the simulation results and experimental data is less than ±3.5%.

Electrodeposited-film electrodes derived from a precursor dinitrosyl iron complex for electrocatalytic water splitting.

PubMed

Li, Wei-Liang; Chiou, Tzung-Wen; Chen, Chien-Hong; Yu, Yi-Ju; Chu, Li-Kang; Liaw, Wen-Feng

2018-05-29

In artificial photosynthesis, water splitting plays an important role for the conversion and storage of renewable energy sources. Here, we report a study on the electrocatalytic properties of the electrodeposited-film electrodes derived from irreversible electro-reduction/-oxidation of a molecular dinitrosyl iron complex (DNIC) {Fe(NO)2}9 [(Me6tren)Fe(NO)2]+ (Me6tren = tris[2-(dimethylamino)ethyl]amine) for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline solution, individually. For HER, the overpotential and Tafel slope for the electrodeposited-film cathode are lower than those of the equiv.-weight Pt/C electrode. The electrodeposited-film anode for the OER is stable for 139 h. Integration of the electrodeposited-film cathode and anode into a single electrode-pair device for electrocatalytic water splitting exhibits an onset voltage of 1.77 V, achieving a geometrical current density of 10 mA cm-2.

Effect and interactions of commercial additives and chloride ion in copper electrowinning

NASA Astrophysics Data System (ADS)

Cui, Wenyuan

This thesis is to understand and compare the effects and interactions of modified polysaccharide (HydroStar), polyacrylamide (Cyquest N-900) and chloride ion on copper electrowinning. A study of the nucleation and growth was conducted in a synthetic electrolyte (40 g/L Cu, 160 g/L H2SO 4, 20 mg/L Cl-) with the addition of HydroStar or Cyquest N-900 using potential step measurements. The current responses generated were compared to theoretical models of nucleation and growth mechanisms. The nucleation and growth mechanism changed as function of potential and the presence of organic additives. The nucleation and growth mechanisms were confirmed using scanning electron microscopy (SEM). At low overpotentials, electrodeposition from the electrolyte without additives proceeded by progressive nucleation with three-dimensional (3-D) growth. The addition of HydroStar produced smaller nuclei and changed the mechanism to progressive nucleation and 2-D growth. Cyquest N-900 used there appeared to be progressive nucleation with 2-D growth and polarize the cathodes. In addition, instantaneous nucleation under diffusion control occurred at high overpotentials. Chloride ion and its interaction with HydroStar and Cyquest N-900 were further characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The trends observed from Nyquist plots and equivalent circuit models were consistent with the CV results. Chloride, on its own, depolarized copper electrodeposition, while chloride ion associated with Cyquest N-900 inhibited the reaction. It is proposed that Cl- acted as a bridging ligand between copper and Cyquest N-900. The addition of HydroStar depolarized copper deposition, but it did not interact with.

Bimetallic Cobalt-Based Phosphide Zeolitic Imidazolate Framework: CoP x Phase-Dependent Electrical Conductivity and Hydrogen Atom Adsorption Energy for Efficient Overall Water Splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Junhua; Zhu, Chengzhou; Xu, Bo Z.

Cobalt-based bimetallic phosphide encapsulated in carbonized zeolitic imadazolate frameworks has been successfully synthesized and showed excellent activities toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Density functional theory calculation and electrochemical measurements reveal that the electrical conductivity and electrochemical activity are closely associated with the Co2P/CoP mixed phase behaviors upon Cu metal doping. This relationship is found to be the decisive factor for enhanced electrocatalytic performance. Moreover, the precise control of Cu content in Co-host lattice effectively alters the Gibbs free energy for H* adsorption, which is favorable for facilitating reaction kinetics. Impressively, an optimized performance hasmore » been achieved with mild Cu doping in Cu0.3Co2.7P/nitrogen-doped carbon (NC) which exhibits an ultralow overpotential of 0.19 V at 10 mA cm–2 and satisfying stability for OER. Cu0.3Co2.7P/NC also shows excellent HER activity, affording a current density of 10 mA cm–2 at a low overpotential of 0.22 V. In addition, a homemade electrolyzer with Cu0.3Co2.7P/NC paired electrodes shows 60% larger current density than Pt/ RuO2 couple at 1.74 V, along with negligible catalytic deactivation after 50 h operation. The manipulation of electronic structure by controlled incorporation of second metal sheds light on understanding and synthesizing bimetallic transition metal phosphides for electrolysis-based energy conversion.« less

Dual Tuning of Ni-Co-A (A = P, Se, O) Nanosheets by Anion Substitution and Holey Engineering for Efficient Hydrogen Evolution.

PubMed

Fang, Zhiwei; Peng, Lele; Qian, Yumin; Zhang, Xiao; Xie, Yujun; Cha, Judy J; Yu, Guihua

2018-04-18

Seeking earth-abundant electrocatalysts with high efficiency and durability has become the frontier of energy conversion research. Mixed-transition-metal (MTM)-based electrocatalysts, owing to the desirable electrical conductivity, synergistic effect of bimetal atoms, and structural stability, have recently emerged as new-generation hydrogen evolution reaction (HER) electrocatalysts. However, the correlation between anion species and their intrinsic electrocatalytic properties in MTM-based electrocatalysts is still not well understood. Here we present a novel approach to tuning the anion-dependent electrocatalytic characteristics in MTM-based catalyst for HER, using holey Ni/Co-based phosphides/selenides/oxides (Ni-Co-A, A = P, Se, O) as the model materials. The electrochemical results, combined with the electrical conductivity measurement and DFT calculation, reveal that P substitution could modulate the electron configuration, lower the hydrogen adsorption energy, and facilitate the desorption of hydrogen on the active sites in Ni-Co-A holey nanostructures, resulting in superior HER catalytic activity. Accordingly we fabricate the NCP holey nanosheet electrocatalyst for HER with an ultralow onset overpotential of nearly zero, an overpotential of 58 mV, and long-term durability, along with an applied potential of 1.56 V to boost overall water splitting at 10 mA cm -2 , among the best electrocatalysts reported for non-noble-metal catalysts to date. This work not only presents a deeper understanding of the intrinsic HER electrocatalytic properties for MTM-based electrocatalyst with various anion species but also offers new insights to better design efficient and durable water-splitting electrocatalysts.

Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

NASA Astrophysics Data System (ADS)

Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

2015-04-01

The electro-catalytic behavior of Pt-CoOx/MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH4 as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoOx, Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of COads on Pt active sites by the participation of CoOx. Compared to Pt/MWCNTs, Pt-CoOx/MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoOx/MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups controls the total rate of MOR process.

Influence of Binders and Solvents on Stability of Ru/RuOx Nanoparticles on ITO Nanocrystals as Li-O2 Battery Cathodes.

PubMed

Vankova, Svetoslava; Francia, Carlotta; Amici, Julia; Zeng, Juqin; Bodoardo, Silvia; Penazzi, Nerino; Collins, Gillian; Geaney, Hugh; O'Dwyer, Colm

2017-02-08

Fundamental research on Li-O 2 batteries remains critical, and the nature of the reactions and stability are paramount for realising the promise of the Li-O 2 system. We report that indium tin oxide (ITO) nanocrystals with supported 1-2 nm oxygen evolution reaction (OER) catalyst Ru/RuO x nanoparticles (NPs) demonstrate efficient OER processes, reduce the recharge overpotential of the cell significantly and maintain catalytic activity to promote a consistent cycling discharge potential in Li-O 2 cells even when the ITO support nanocrystals deteriorate from the very first cycle. The Ru/RuO x nanoparticles lower the charge overpotential compared with those for ITO and carbon-only cathodes and have the greatest effect in DMSO electrolytes with a solution-processable F-free carboxymethyl cellulose (CMC) binder (<3.5 V) instead of polyvinylidene fluoride (PVDF). The Ru/RuO x /ITO nanocrystalline materials in DMSO provide efficient Li 2 O 2 decomposition from within the cathode during cycling. We demonstrate that the ITO is actually unstable from the first cycle and is modified by chemical etching, but the Ru/RuO x NPs remain effective OER catalysts for Li 2 O 2 during cycling. The CMC binders avoid PVDF-based side-reactions and improve the cyclability. The deterioration of the ITO nanocrystals is mitigated significantly in cathodes with a CMC binder, and the cells show good cycle life. In mixed DMSO-EMITFSI [EMITFSI=1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide] ionic liquid electrolytes, the Ru/RuO x /ITO materials in Li-O 2 cells cycle very well and maintain a consistently very low charge overpotential of 0.5-0.8 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Density Functional Theory Study of Oxygen Reduction Activity on Ultrathin Platinum Nanotubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2012-07-13

The structure, stability, and catalytic activity of a number of single- and double-wall platinum (n,m) nanotubes ranging in diameter from 0.3 to 2.0 nm were studied using plane-wave based density functional theory in the gas phase and water environment. The change in the catalytic activity toward the oxygen reduction reaction (ORR) with the size and chirality of the nanotube was studied by calculating equilibrium adsorption potentials for ORR intermediates and by constructing free energy diagrams in the ORR dissociative mechanism network. In addition, the stability of the platinum nanotubes is investigated in terms of electrochemical dissolution potentials and by determiningmore » the most stable state of the material as a function of pH and potential, as represented in Pourbaix diagrams. Our results show that the catalytic activity and the stability toward electrochemical dissolution depend greatly on the diameter and chirality of the nanotube. On the basis of the estimated overpotentials for ORR, we conclude that smaller, approximately 0.5 nm in diameter single-wall platinum nanotubes consistently show a huge, up to 400 mV larger overpotential than platinum, indicating very poor catalytic activity toward ORR. This is the result of substantial structural changes induced by the adsorption of any chemical species on these tubes. Single-wall n = m platinum nanotubes with a diameter larger than 1 nm have smaller ORR overpotentials than bulk platinum for up to 180 mV and thus show improved catalytic activity relative to bulk. We also predict that these nanotubes can endure the highest cell potentials but dissolution potentials are still for 110 mV lower than for the bulk, indicating a possible corrosion problem.« less

Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water.

PubMed

Bajdich, Michal; García-Mota, Mónica; Vojvodic, Aleksandra; Nørskov, Jens K; Bell, Alexis T

2013-09-11

The presence of layered cobalt oxides has been identified experimentally in Co-based anodes under oxygen-evolving conditions. In this work, we report the results of theoretical investigations of the relative stability of layered and spinel bulk phases of Co oxides, as well as the stability of selected surfaces as a function of applied potential and pH. We then study the oxygen evolution reaction (OER) on these surfaces and obtain activity trends at experimentally relevant electro-chemical conditions. Our calculated volume Pourbaix diagram shows that β-CoOOH is the active phase where the OER occurs in alkaline media. We calculate relative surface stabilities and adsorbate coverages of the most stable low-index surfaces of β-CoOOH: (0001), (0112), and (1014). We find that at low applied potentials, the (1014) surface is the most stable, while the (0112) surface is the more stable at higher potentials. Next, we compare the theoretical overpotentials for all three surfaces and find that the (1014) surface is the most active one as characterized by an overpotential of η = 0.48 V. The high activity of the (1014) surface can be attributed to the observation that the resting state of Co in the active site is Co(3+) during the OER, whereas Co is in the Co(4+) state in the less active surfaces. Lastly, we demonstrate that the overpotential of the (1014) surface can be lowered further by surface substitution of Co by Ni. This finding could explain the experimentally observed enhancement in the OER activity of Ni(y)Co(1-y)O(x) thin films with increasing Ni content. All energetics in this work were obtained from density functional theory using the Hubbard-U correction.

Highly Efficient Br-/NO3- Dual-Anion Electrolyte for Suppressing Charging Instabilities of Li-O2 Batteries.

PubMed

Xin, Xing; Ito, Kimihiko; Kubo, Yoshimi

2017-08-09

The main issues with Li-O 2 batteries are the high overpotential at the cathode and the dendrite formation at the anode during charging. Various types of redox mediators (RMs) have been proposed to reduce the charging voltage. However, the RMs tend to lose their activity during cycling owing to not only decomposition reactions but also undesirable discharge (shuttle effect) at the Li metal anode. Moreover, the dendrite growth of the Li metal anode is not resolved by merely adding RMs to the electrolytes. Here we report a simple yet highly effective method to reduce the charge overpotential while protecting the Li metal anode by incorporating LiBr and LiNO 3 in a tetraglyme solvent as the electrolyte for Li-O 2 cells. The Br - /Br 3 - couple acts as an RM to oxidize the discharge product Li 2 O 2 at the cathode, whereas the NO 3 - anion oxidizes the Li metal surface to prevent the shuttle reaction. In this work, we found that both anions work synergistically in the mixed Br - /NO 3 - electrolyte to dramatically suppress both parasitic reactions and dendrite formation by generating a solid Li 2 O thin film on the Li metal anode. As a result, the charge voltage was reduced to below 3.6 V over 40 cycles. The O 2 evolution during charging was more than 80% of the theoretical value, and CO 2 emission during charging was negligible. After cycling, the Li metal anode showed smooth surfaces with no indication of dendrite formation. These observations clearly demonstrate that the Br - /NO 3 - dual-anion electrolyte can solve the problems associated with both the overpotential at the cathode and the dendrite formation at the anode.

Electronic and Morphological Dual Modulation of Cobalt Carbonate Hydroxides by Mn Doping toward Highly Efficient and Stable Bifunctional Electrocatalysts for Overall Water Splitting.

PubMed

Tang, Tang; Jiang, Wen-Jie; Niu, Shuai; Liu, Ning; Luo, Hao; Chen, Yu-Yun; Jin, Shi-Feng; Gao, Feng; Wan, Li-Jun; Hu, Jin-Song

2017-06-21

Developing bifunctional efficient and durable non-noble electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is highly desirable and challenging for overall water splitting. Herein, Co-Mn carbonate hydroxide (CoMnCH) nanosheet arrays with controllable morphology and composition were developed on nickel foam (NF) as such a bifunctional electrocatalyst. It is discovered that Mn doping in CoCH can simultaneously modulate the nanosheet morphology to significantly increase the electrochemical active surface area for exposing more accessible active sites and tune the electronic structure of Co center to effectively boost its intrinsic activity. As a result, the optimized Co 1 Mn 1 CH/NF electrode exhibits unprecedented OER activity with an ultralow overpotential of 294 mV at 30 mA cm -2 , compared with all reported metal carbonate hydroxides. Benefited from 3D open nanosheet array topographic structure with tight contact between nanosheets and NF, it is able to deliver a high and stable current density of 1000 mA cm -2 at only an overpotential of 462 mV with no interference from high-flux oxygen evolution. Despite no reports about effective HER on metal carbonate hydroxides yet, the small overpotential of 180 mV at 10 mA cm -2 for HER can be also achieved on Co 1 Mn 1 CH/NF by the dual modulation of Mn doping. This offers a two-electrode electrolyzer using bifunctional Co 1 Mn 1 CH/NF as both anode and cathode to perform stable overall water splitting with a cell voltage of only 1.68 V at 10 mA cm -2 . These findings may open up opportunities to explore other multimetal carbonate hydroxides as practical bifunctional electrocatalysts for scale-up water electrolysis.

Targeted Synthesis of Unique Nickel Sulfide (NiS, NiS2) Microarchitectures and the Applications for the Enhanced Water Splitting System.

PubMed

Luo, Pan; Zhang, Huijuan; Liu, Li; Zhang, Yan; Deng, Ju; Xu, Chaohe; Hu, Ning; Wang, Yu

2017-01-25

Water splitting is one of the ideal technologies to meet the ever increasing demands of energy. Many materials have aroused great attention in this field. The family of nickel-based sulfides is one of the examples that possesses interesting properties in water-splitting fields. In this paper, a controllable and simple strategy to synthesize nickel sulfides was proposed. First, we fabricated NiS 2 hollow microspheres via a hydrothermal process. After a precise heat control in a specific atmosphere, NiS porous hollow microspheres were prepared. NiS 2 was applied in hydrogen evolution reaction (HER) and shows a marvelous performance both in acid medium (an overpotential of 174 mV to achieve a current density of 10 mA/cm 2 and the Tafel slope is only 63 mV/dec) and in alkaline medium (an overpotential of 148 mV to afford a current density of 10 mA/cm 2 and the Tafel slope is 79 mV/dec). NiS was used in oxygen evolution reaction (OER) showing a low overpotential of 320 mV to deliver a current density of 10 mA/cm 2 , which is meritorious. These results enlighten us to make an efficient water-splitting system, including NiS 2 as HER catalyst in a cathode and NiS as OER catalyst in an anode. The system shows high activity and good stabilization. Specifically, it displays a stable current density of 10 mA/cm 2 with the applying voltage of 1.58 V, which is a considerable electrolyzer for water splitting.

Alleviating the Common Confusion Caused by Polarity in Electrochemistry.

ERIC Educational Resources Information Center

Moran, P. J.; Gileadi, E.

1989-01-01

Discussed is some of the confusion encountered in electrochemistry due to misunderstandings of sign conventions and simple mathematical errors. Clarified are issues involving emf series, IUPAC sign conventions, calculation of cell potentials, reference electrodes, the polarity of electrodes in electrochemical devices, and overpotential. (CW)

Introducing Fe 2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Zhao; Zhou, Daojin; Wang, Maoyu

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe–LDHs) by partially substituting Ni 2+ with Fe 2+ to introduce Fe–O–Fe moieties. These Fe 2+–containing NiFe–LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm 2, which is among the best OER catalytic performance reported to date. In–situ X–ray absorption, Raman, and electrochemical analysis jointlymore » reveal that the Fe–O–Fe motifs could stabilize high–valent metal sites at low overpotentials, thereby enhancing the OER activity. Lastly, these results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.« less

One-step electrochemical deposition of Schiff base cobalt complex as effective water oxidation catalyst

NASA Astrophysics Data System (ADS)

Huang, Binbin; Wang, Yan; Zhan, Shuzhong; Ye, Jianshan

2017-02-01

Schiff base metal complexes have been applied in many fields, especially, a potential homogeneous catalyst for water splitting. However, the high overpotential, time consumed synthesis process and complicated working condition largely limit their application. In the present work, a one-step approach to fabricate Schiff base cobalt complex modified electrode is developed. Microrod clusters (MRC) and rough spherical particles (RSP) can be obtained on the ITO electrode through different electrochemical deposition condition. Both of the MRC and RSP present favorable activity for oxygen evolution reaction (OER) compared to the commercial Co3O4, taking an overpotential of 650 mV and 450 mV to drive appreciable catalytic current respectively. The highly active and stable RSP shows a Tafel plot of 84 mV dec-1 and negligible decrease of the current density for 12 h bulk electrolysis. The synthesis strategy of effective and stable catalyst in this work provide a simple method to fabricate heterogeneous OER catalyst with Schiff base metal complex.

Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mistry, Hemma; Choi, Yong-Wook; Bagger, Alexander

Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO 2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO 2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulkmore » of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. Finally, DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO 2 electroreduction.« less

Electrochemical behaviour of naked sub-nanometre sized copper clusters and effect of CO 2

DOE PAGES

Passalacqua, Rosalba; Parathoner, Siglinda; Centi, Gabriele; ...

2016-08-04

The study of the electrochemical behavior (in the presence of N 2 or CO 2) of size-controlled naked Cu 5 and Cu 20 nanoclusters, prepared using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques, evidences some relevant results regarding the redox behavior of these sub-nanometre sized copper particles and the effect of CO 2 on them. Cu 20 nanoclusters show anodic redox processes occurring at much lower potential with respect to Cu 5 nanoclusters, which behave relatively similar to much larger Cu particles. However, Cu 5 nanoclusters coordinate effectively CO 2 (hydrogen carbonate) in solution, differentmore » from Cu 20 nanoclusters and larger Cu particles. This effect, rather than the redox behavior, is apparently connected to the ability of Cu 5 nanoclusters to reduce CO 2 under cathodic conditions at low overpotential. In conclusion, although preliminary, these results provide rather exciting indications on the possibility of realizing low overpotential electrocatalytic conversion of CO 2.« less

Photoelectrochemical NADH Regeneration using Pt-Modified p -GaAs Semiconductor Electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stufano, Paolo; Paris, Aubrey R.; Bocarsly, Andrew

Cofactor regeneration in enzymatic reductions is crucial for the application of enzymes to both biological and energy-related catalysis. Specifically, regenerating NADH from NAD + is of great interest, and using electrochemistry to achieve this end is considered a promising option. Here in this paper, we report the first example of photoelectrochemical NADH regeneration at the illuminated (λ >600 nm), metal-modified p-type semiconductor electrode Pt/p-GaAs. Although bare p-GaAs electrodes produce only enzymatically inactive NAD 2, NADH was produced at the illuminated Pt-modified p-GaAs surface. At low overpotential (–0.75 V vs. Ag/AgCl), Pt/p-GaAs exhibited a seven-fold greater Faradaic efficiency for the formationmore » of NADH than Pt alone, with reduced competition from the hydrogen evolution reaction. Improved Faradaic efficiency and low overpotential suggest the possible utility of Pt/p-GaAs in energy-related NADH-dependent enzymatic processes.« less

Electrochemical behaviour of naked sub-nanometre sized copper clusters and effect of CO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Passalacqua, Rosalba; Parathoner, Siglinda; Centi, Gabriele

The study of the electrochemical behavior (in the presence of N 2 or CO 2) of size-controlled naked Cu 5 and Cu 20 nanoclusters, prepared using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques, evidences some relevant results regarding the redox behavior of these sub-nanometre sized copper particles and the effect of CO 2 on them. Cu 20 nanoclusters show anodic redox processes occurring at much lower potential with respect to Cu 5 nanoclusters, which behave relatively similar to much larger Cu particles. However, Cu 5 nanoclusters coordinate effectively CO 2 (hydrogen carbonate) in solution, differentmore » from Cu 20 nanoclusters and larger Cu particles. This effect, rather than the redox behavior, is apparently connected to the ability of Cu 5 nanoclusters to reduce CO 2 under cathodic conditions at low overpotential. In conclusion, although preliminary, these results provide rather exciting indications on the possibility of realizing low overpotential electrocatalytic conversion of CO 2.« less

Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution

DOE PAGES

Lu, Qi; Hutchings, Gregory S.; Yu, Weiting; ...

2015-03-16

One of the key components of carbon dioxide-free hydrogen production is a robust and efficient non-precious metal catalyst for the hydrogen evolution reaction. We report that a hierarchical nanoporous copper-titanium bimetallic electrocatalyst is able to produce hydrogen from water under a mild overpotential at more than twice the rate of state-of-the- art carbon-supported platinum catalyst. Although both copper and titanium are known to be poor hydrogen evolution catalysts, the combination of these two elements creates unique copper-copper-titanium hollow sites, which have a hydrogen-binding energy very similar to that of platinum, resulting in an exceptional hydrogen evolution activity. Moreover, the hierarchicalmore » porosity of the nanoporous-copper titanium catalyst also contributes to its high hydrogen evolution activity, because it provides a large-surface area for electrocatalytic hydrogen evolution, and improves the mass transport properties. Moreover, the catalyst is self-supported, eliminating the overpotential associated with the catalyst/support interface.« less

A low-overpotential potassium-oxygen battery based on potassium superoxide.

PubMed

Ren, Xiaodi; Wu, Yiying

2013-02-27

Li-O(2) battery is regarded as one of the most promising energy storage systems for future applications. However, its energy efficiency is greatly undermined by the large overpotentials of the discharge (formation of Li(2)O(2)) and charge (oxidation of Li(2)O(2)) reactions. The parasitic reactions of electrolyte and carbon electrode induced by the high charging potential cause the decay of capacity and limit the battery life. Here, a K-O(2) battery is report that uses K(+) ions to capture O(2)(-) to form the thermodynamically stable KO(2) product. This allows for the battery to operate through the one-electron redox process of O(2)/O(2)(-). Our studies confirm the formation and removal of KO(2) in the battery cycle test. Furthermore, without the use of catalysts, the battery shows a low discharge/charge potential gap of less than 50 mV at a modest current density, which is the lowest one that has ever been reported in metal-oxygen batteries.

Molecular metal-Nx centres in porous carbon for electrocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Liang, Hai-Wei; Brüller, Sebastian; Dong, Renhao; Zhang, Jian; Feng, Xinliang; Müllen, Klaus

2015-08-01

Replacement of precious platinum with efficient and low-cost catalysts for electrocatalytic hydrogen evolution at low overpotentials holds tremendous promise for clean energy devices. Here we report a novel type of robust cobalt-nitrogen/carbon catalyst for the hydrogen evolution reaction (HER) that is prepared by the pyrolysis of cobalt-N4 macrocycles or cobalt/o-phenylenediamine composites and using silica colloids as a hard template. We identify the well-dispersed molecular CoNx sites on the carbon support as the active sites responsible for the HER. The CoNx/C catalyst exhibits extremely high turnover frequencies per cobalt site in acids, for example, 0.39 and 6.5 s-1 at an overpotential of 100 and 200 mV, respectively, which are higher than those reported for other scalable non-precious metal HER catalysts. Our results suggest the great promise of developing new families of non-precious metal HER catalysts based on the controlled conversion of homogeneous metal complexes into solid-state carbon catalysts via economically scalable protocols.

Introducing Fe2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity.

PubMed

Cai, Zhao; Zhou, Daojin; Wang, Maoyu; Bak, Seongmin; Wu, Yueshen; Wu, Zishan; Tian, Yang; Xiong, Xuya; Li, Yaping; Liu, Wen; Siahrostami, Samira; Kuang, Yun; Yang, Xiao-Qing; Duan, Haohong; Feng, Zhenxing; Wang, Hailiang; Sun, Xiaoming

2018-06-11

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel-iron layered double hydroxides (NiFe-LDHs) by partially substituting Ni2+ with Fe2+ to introduce Fe-O-Fe moieties. These Fe2+-containing NiFe-LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm2, which is among the best OER catalytic performance reported to date. In-situ X-ray absorption, Raman, and electrochemical analysis jointly reveal that the Fe-O-Fe motifs could stabilize high-valent metal sites at low overpotentials, thereby enhancing the OER activity. These results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Introducing Fe 2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

DOE PAGES

Cai, Zhao; Zhou, Daojin; Wang, Maoyu; ...

2018-06-11

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe–LDHs) by partially substituting Ni 2+ with Fe 2+ to introduce Fe–O–Fe moieties. These Fe 2+–containing NiFe–LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm 2, which is among the best OER catalytic performance reported to date. In–situ X–ray absorption, Raman, and electrochemical analysis jointlymore » reveal that the Fe–O–Fe motifs could stabilize high–valent metal sites at low overpotentials, thereby enhancing the OER activity. Lastly, these results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.« less

Nanostructuring one-dimensional and amorphous lithium peroxide for high round-trip efficiency in lithium-oxygen batteries.

PubMed

Dutta, Arghya; Wong, Raymond A; Park, Woonghyeon; Yamanaka, Keisuke; Ohta, Toshiaki; Jung, Yousung; Byon, Hye Ryung

2018-02-14

The major challenge facing lithium-oxygen batteries is the insulating and bulk lithium peroxide discharge product, which causes sluggish decomposition and increasing overpotential during recharge. Here, we demonstrate an improved round-trip efficiency of ~80% by means of a mesoporous carbon electrode, which directs the growth of one-dimensional and amorphous lithium peroxide. Morphologically, the one-dimensional nanostructures with small volume and high surface show improved charge transport and promote delithiation (lithium ion dissolution) during recharge and thus plays a critical role in the facile decomposition of lithium peroxide. Thermodynamically, density functional calculations reveal that disordered geometric arrangements of the surface atoms in the amorphous structure lead to weaker binding of the key reaction intermediate lithium superoxide, yielding smaller oxygen reduction and evolution overpotentials compared to the crystalline surface. This study suggests a strategy to enhance the decomposition rate of lithium peroxide by exploiting the size and shape of one-dimensional nanostructured lithium peroxide.

Chemical dynamics of the first proton-coupled electron transfer of water oxidation on TiO2 anatase.

PubMed

Chen, Jia; Li, Ye-Fei; Sit, Patrick; Selloni, Annabella

2013-12-18

Titanium dioxide (TiO2) is a prototype, water-splitting (photo)catalyst, but its performance is limited by the large overpotential for the oxygen evolution reaction (OER). We report here a first-principles density functional theory study of the chemical dynamics of the first proton-coupled electron transfer (PCET), which is considered responsible for the large OER overpotential on TiO2. We use a periodic model of the TiO2/water interface that includes a slab of anatase TiO2 and explicit water molecules, sample the solvent configurations by first principles molecular dynamics, and determine the energy profiles of the two electronic states involved in the electron transfer (ET) by hybrid functional calculations. Our results suggest that the first PCET is sequential, with the ET following the proton transfer. The ET occurs via an inner sphere process, which is facilitated by a state in which one electronic hole is shared by the two oxygen ions involved in the transfer.

Photoelectrochemical NADH Regeneration using Pt-Modified p -GaAs Semiconductor Electrodes

DOE PAGES

Stufano, Paolo; Paris, Aubrey R.; Bocarsly, Andrew

2017-02-22

Cofactor regeneration in enzymatic reductions is crucial for the application of enzymes to both biological and energy-related catalysis. Specifically, regenerating NADH from NAD + is of great interest, and using electrochemistry to achieve this end is considered a promising option. Here in this paper, we report the first example of photoelectrochemical NADH regeneration at the illuminated (λ >600 nm), metal-modified p-type semiconductor electrode Pt/p-GaAs. Although bare p-GaAs electrodes produce only enzymatically inactive NAD 2, NADH was produced at the illuminated Pt-modified p-GaAs surface. At low overpotential (–0.75 V vs. Ag/AgCl), Pt/p-GaAs exhibited a seven-fold greater Faradaic efficiency for the formationmore » of NADH than Pt alone, with reduced competition from the hydrogen evolution reaction. Improved Faradaic efficiency and low overpotential suggest the possible utility of Pt/p-GaAs in energy-related NADH-dependent enzymatic processes.« less

Enhanced Carbon Dioxide Electroreduction to Carbon Monoxide over Defect-Rich Plasma-Activated Silver Catalysts

DOE PAGES

Mistry, Hemma; Choi, Yong-Wook; Bagger, Alexander; ...

2017-07-14

Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO 2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO 2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulkmore » of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. Finally, DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO 2 electroreduction.« less

Characterization of mixed-conducting barium cerate-based perovskites for potential fuel cell applications

NASA Astrophysics Data System (ADS)

Mukundan, R.

Chemical modifications of barium cerium gadolinium oxide through the substitution of Bi, Tb, Pr, Nb and Ta were attempted in an effort to increase the p-type or n-type conductivity, and to develop new mixed-conducting electrodes that are chemically compatible with the Ba(Cesb{1-x}Gdsb{x})Osb{3-x/2} electrolyte. The structure, oxygen non-stoichiometry, electronic and ionic-conductivity of several compositions in the doped-barium cerate systems were studied by X-ray diffraction, TGA, DC and AC conductivity, and EMF measurements. The cathodic overpotential of the mixed (electronic/ionic) conducting compositions in this system, on a Ba(Cesb{0.8}Gdsb{0.2})Osb{2.9} electrolyte, were also studied using Current Interruption and AC impedance techniques. The substitution of Bi into Ba(Cesb{0.9}Gdsb{0.1})Osb{2.95} lead to a significant increase in the electronic conductivity, and a total conductivity of about 0.94 S/cm was obtained for Ba(Bisb{0.5}Cesb{0.4}Gdsb{0.1})Osb3 at 800sp°C in air. However, the concentration of oxygen-ion vacancies and hence the ionic conductivity decreased due to the oxidation of Bi to the 5sp{+} state. Compositions in the Ba(Bisb{0.5}Cesb{x}Gdsb{0.5-x})Osb3 system also exhibited significant oxygen non-stoichiometry depending upon the ordering of the B-site cations and the relative concentrations of Ce and Gd. However, the absence of any detectable EMF in the non-stoichiometric compositions implied that the oxygen vacancies are strongly associated with the Bisp{3+} cations. Although highly conductive, chemically stable compositions were prepared in the Ba(Bisb{x}Cesb{y}Gdsb{1-(x+y)})Osb{3-d} system, their ionic conductivities were low. The mixed-conduction properties of Ba(Cesb{1-x}Gdsb{x})Osb{3-d} were enhanced under cathode conditions (600-800sp°C in air) by the substitution of Ce by Tb and Pr. While the substitution of Tb resulted in a decrease in the total conductivity, Pr induced a significant increase in the total conductivity at high Pr levels (≥40 mole%) due to an enhancement of the electronic conductivity. The Ba(Prsb{0.8}Gdsb{0.2})Osb{2.9} sample was found to have the best mixed-conducting properties of all the perovskites evaluated, sigmasb{T}=0.75 S/cm in air at 800sp°C, tsb{H+}=0.15 in a wet argon//dry argon gradient, and tsb{0.2-}≈ 0.05 in a dry air//dry argon gradient. The cathodic overpotentials of the mixed-conducting Pr-doped barium cerates were low, and decreased with increasing ionic and electronic conductivity of the electrode. The lowest overpotential was obtained for the Ba(Prsb{0.8}Gdsb{0.2})Osb{2.9}, cathode, and at low current densities was comparable to that of an optimized porous Pt-electrode. While the substitution of Nb and Ta for Ce lead to an enhancement in the electronic conductivity under reducing conditions associated with the increased reduction of Cesp{4+} to Cesp{3+}, the ionic-conductivity of these perovskites was low. There was no evidence for any protonic conductivity in the 15 mole% Nb and Ta substituted barium cerates. Moreover the anodic overpotential and the anode resistance of these perovskites on a Ba(Cesb{0.8}Gdsb{0.2})Osb{2.9} electrolyte were both high.

Iron-doped nickel oxide nanocrystals as highly efficient electrocatalysts for alkaline water splitting.

PubMed

Fominykh, Ksenia; Chernev, Petko; Zaharieva, Ivelina; Sicklinger, Johannes; Stefanic, Goran; Döblinger, Markus; Müller, Alexander; Pokharel, Aneil; Böcklein, Sebastian; Scheu, Christina; Bein, Thomas; Fattakhova-Rohlfing, Dina

2015-05-26

Efficient electrochemical water splitting to hydrogen and oxygen is considered a promising technology to overcome our dependency on fossil fuels. Searching for novel catalytic materials for electrochemical oxygen generation is essential for improving the total efficiency of water splitting processes. We report the synthesis, structural characterization, and electrochemical performance in the oxygen evolution reaction of Fe-doped NiO nanocrystals. The facile solvothermal synthesis in tert-butanol leads to the formation of ultrasmall crystalline and highly dispersible FexNi1-xO nanoparticles with dopant concentrations of up to 20%. The increase in Fe content is accompanied by a decrease in particle size, resulting in nonagglomerated nanocrystals of 1.5-3.8 nm in size. The Fe content and composition of the nanoparticles are determined by X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy measurements, while Mössbauer and extended X-ray absorption fine structure analyses reveal a substitutional incorporation of Fe(III) into the NiO rock salt structure. The excellent dispersibility of the nanoparticles in ethanol allows for the preparation of homogeneous ca. 8 nm thin films with a smooth surface on various substrates. The turnover frequencies (TOF) of these films could be precisely calculated using a quartz crystal microbalance. Fe0.1Ni0.9O was found to have the highest electrocatalytic water oxidation activity in basic media with a TOF of 1.9 s(-1) at the overpotential of 300 mV. The current density of 10 mA cm(-2) is reached at an overpotential of 297 mV with a Tafel slope of 37 mV dec(-1). The extremely high catalytic activity, facile preparation, and low cost of the single crystalline FexNi1-xO nanoparticles make them very promising catalysts for the oxygen evolution reaction.

Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration

NASA Astrophysics Data System (ADS)

Liu, Min; Pang, Yuanjie; Zhang, Bo; de Luna, Phil; Voznyy, Oleksandr; Xu, Jixian; Zheng, Xueli; Dinh, Cao Thang; Fan, Fengjia; Cao, Changhong; de Arquer, F. Pelayo García; Safaei, Tina Saberi; Mepham, Adam; Klinkova, Anna; Kumacheva, Eugenia; Filleter, Tobin; Sinton, David; Kelley, Shana O.; Sargent, Edward H.

2016-09-01

Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the reaction suffers from slow kinetics owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption, but this comes at the cost of increased hydrogen (H2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at -0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at -0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.

Exploring Hydrogen Evolution and the Overpotential

ERIC Educational Resources Information Center

Lyon, Yana A.; Roberts, Adrienne A.; McMillin, David R.

2015-01-01

The laboratory experiment described provides insight into the energetics of hydrogen evolution at an electrode as well as the intrinsic barrier that typically impedes reaction. In the course of the exercise, students find that Sn(s) is thermodynamically capable of combining with protons to form hydrogen, but that the direct reaction occurs at a…

Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

ERIC Educational Resources Information Center

Duong, Hung Tuan

2009-01-01

The sluggish kinetics of oxygen reduction reaction (ORR) contributes significantly to the loss of cathode overpotential in fuel cells, thus requiring high loadings of platinum (Pt), which is an expensive metal with limited supply. However, Pt and Pt-based alloys are still the best available electrocatalysts for ORR thus far. The research presented…

Discovering Inexpensive, Effective Catalysts for Solar Energy Conversion: An Authentic Research Laboratory Experience

ERIC Educational Resources Information Center

Shaner, Sarah E.; Hooker, Paul D.; Nickel, Anne-Marie; Leichtfuss, Amanda R.; Adams, Carissa S.; de la Cerda, Dionisia; She, Yuqi; Gerken, James B.; Pokhrel, Ravi; Ambrose, Nicholas J.; Khaliqi, David; Stahl, Shannon S.; Schuttlefield Christus, Jennifer D.

2016-01-01

Electrochemical water oxidation is a major focus of solar energy conversion efforts. A new laboratory experiment has been developed that utilizes real-time, hands-on research to discover catalysts for solar energy conversion. The HARPOON, or Heterogeneous Anodes Rapidly Perused for Oxygen Overpotential Neutralization, experiment allows an array of…

Iron vs. cobalt clathrochelate electrocatalysts of HER: the first example on a cage iron complex.

PubMed

Dolganov, Alexander V; Belov, Alexander S; Novikov, Valentin V; Vologzhanina, Anna V; Mokhir, Andriy; Bubnov, Yurii N; Voloshin, Yan Z

2013-04-07

New macrobicyclic 2-thiopheneboron-capped iron and cobalt(II) tris-dioximates showed high electrocatalytic activity for hydrogen production from H(+) ions. This is the first example of the hydrogen evolution reaction electrocatalyzed by a clathrochelate iron complex, which catalyzes the hydrogen production at low overpotential.

Spatial Heterogeneities and Onset of Passivation Breakdown at Lithium Anode Interfaces

DOE PAGES

Leung, Kevin; Jungjohann, Katherine L.

2017-09-08

Effective passivation of lithium metal surfaces, and prevention of battery-shorting lithium dendrite growth, are critical for implementing lithium metal anodes for batteries with increased power densities. Nanoscale surface heterogeneities can be “hot spots” where anode passivation breaks down. Motivated by the observation of lithium dendrites in pores and grain boundaries in all-solid batteries, we examine lithium metal surfaces covered with Li 2O and/or LiF thin films with grain boundaries in them. Electronic structure calculations show that at >0.25 V computed equilibrium overpotential Li 2O grain boundaries with sufficiently large pores can accommodate Li0 atoms which aid e– leakage and passivationmore » breakdown. Strain often accompanies Li insertion; applying an ~1.7% strain already lowers the computed overpotential to 0.1 V. Lithium metal nanostructures as thin as 12 Å are thermodynamically favored inside cracks in Li 2O films, becoming “incipient lithium filaments”. LiF films are more resistant to lithium metal growth. Finally, the models used herein should in turn inform passivating strategies in all-solid-state batteries.« less

N-doped graphene layers encapsulated NiFe alloy nanoparticles derived from MOFs with superior electrochemical performance for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Feng, Yi; Yu, Xin-Yao; Paik, Ungyu

2016-09-01

Water splitting, an efficient approach for hydrogen production, is often hindered by unfavorable kinetics of oxygen evolution reaction (OER). In order to reduce the overpotential, noble metal oxides-based electrocatalysts like RuO2 and IrO2 are usually utilized. However, due to their scarcity, the development of cost-effective non-precious OER electrocatalysts with high efficiency and good stability is urgently required. Herein, we report a facile one-step annealing of metal-organic frameworks (MOFs) strategy to synthesize N-doped graphene layers encapsulated NiFe alloy nanoparticles (NiFe@C). Through tuning the nanoparticle size and calcination temperature, NiFe@C with an average size of around 16 nm obtained at 700 °C exhibits superior OER performance with an overpotential of only 281 mV at 10 mA cm-2 and high durability. The facile synthesis method and excellent electrochemical performance show great potential of NiFe@C in replacing the precious metal-based electrocatalysts in the OER.

Free-Standing Air Cathodes Based on 3D Hierarchically Porous Carbon Membranes: Kinetic Overpotential of Continuous Macropores in Li-O2 Batteries.

PubMed

Xu, Shu-Mao; Liang, Xiao; Ren, Zhi-Chu; Wang, Kai-Xue; Chen, Jie-Sheng

2018-06-04

Free-standing macroporous air electrodes with enhanced interfacial contact, rapid mass transport, and tailored deposition space for large amounts of Li 2 O 2 are essential for improving the rate performance of Li-O 2 batteries. An ordered mesoporous carbon membrane with continuous macroporous channels was prepared by inversely topological transformation from ZnO nanorod array. Utilized as a free-standing air cathode for Li-O 2 battery, the hierarchically porous carbon membrane shows superior rate performance. However, the increased cross-sectional area of the continuous macropores on the cathode surface leads to a kinetic overpotential with large voltage hysteresis and linear voltage variation against Butler-Volmer behavior. The kinetics were investigated based on the rate-determining step of second electron transfer accompanied by migration of Li + in solid or quasi-solid intermediates. These discoveries shed light on the design of the air cathode for Li-O 2 batteries with high-rate performance. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

DOE PAGES

Kim, Jaemin; Shih, Pei-Chieh; Tsao, Kai-Chieh; ...

2017-07-27

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge to produce hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y 2Ru 2O 7-δ) electrocatalyst that has significantly enhanced performance toward OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1 M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y 2Ru 2O 7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band centermore » energy for the overlap between Ru 4d and O 2p orbitals and is therefore more stable Ru–O bond than RuO 2, highlighting the effect of yttrium on the enhancement in stability. Finally, the Y 2Ru 2O 7-δ pyrochlore is also free of expensive iridium metal and thus is a cost-effective candidate for practical applications.« less

Embedding covalency into metal catalysts for efficient electrochemical conversion of CO2.

PubMed

Lim, Hyung-Kyu; Shin, Hyeyoung; Goddard, William A; Hwang, Yun Jeong; Min, Byoung Koun; Kim, Hyungjun

2014-08-13

CO2 conversion is an essential technology to develop a sustainable carbon economy for the present and the future. Many studies have focused extensively on the electrochemical conversion of CO2 into various useful chemicals. However, there is not yet a solution of sufficiently high enough efficiency and stability to demonstrate practical applicability. In this work, we use first-principles-based high-throughput screening to propose silver-based catalysts for efficient electrochemical reduction of CO2 to CO while decreasing the overpotential by 0.4-0.5 V. We discovered the covalency-aided electrochemical reaction (CAER) mechanism in which p-block dopants have a major effect on the modulating reaction energetics by imposing partial covalency into the metal catalysts, thereby enhancing their catalytic activity well beyond modulations arising from d-block dopants. In particular, sulfur or arsenic doping can effectively minimize the overpotential with good structural and electrochemical stability. We expect this work to provide useful insights to guide the development of a feasible strategy to overcome the limitations of current technology for electrochemical CO2 conversion.

2D Covalent Metals: A New Materials Domain of Electrochemical CO2 Conversion with Broken Scaling Relationship.

PubMed

Shin, Hyeyoung; Ha, Yoonhoo; Kim, Hyungjun

2016-10-04

Toward a sustainable carbon cycle, electrochemical conversion of CO 2 into valuable fuels has drawn much attention. However, sluggish kinetics and a substantial overpotential, originating from the strong correlation between the adsorption energies of intermediates and products, are key obstacles of electrochemical CO 2 conversion. Here we show that 2D covalent metals with a zero band gap can overcome the intrinsic limitation of conventional metals and metal alloys and thereby substantially decrease the overpotential for CO 2 reduction because of their covalent characteristics. From first-principles-based high-throughput screening results on 61 2D covalent metals, we find that the strong correlation between the adsorption energies of COOH and CO can be entirely broken. This leads to the computational design of CO 2 -to-CO and CO 2 -to-CH 4 conversion catalysts in addition to hydrogen-evolution-reaction catalysts. Toward efficient electrochemical catalysts for CO 2 reduction, this work suggests a new materials domain having two contradictory properties in a single material: covalent nature and electrical conductance.

Ganoderma-Like MoS2 /NiS2 with Single Platinum Atoms Doping as an Efficient and Stable Hydrogen Evolution Reaction Catalyst.

PubMed

Guan, Yongxin; Feng, Yangyang; Wan, Jing; Yang, Xiaohui; Fang, Ling; Gu, Xiao; Liu, Ruirui; Huang, Zhengyong; Li, Jian; Luo, Jun; Li, Changming; Wang, Yu

2018-05-27

Herein, a unique ganoderma-like MoS 2 /NiS 2 hetero-nanostructure with isolated Pt atoms anchored is reported. This novel ganoderma-like heterostructure can not only efficiently disperse and confine the few-layer MoS 2 nanosheets to fully expose the edge sites of MoS 2 , and provide more opportunity to capture the Pt atoms, but also tune the electronic structure to modify the catalytic activity. Because of the favorable dispersibility and exposed large specific surface area, single Pt atoms can be easily anchored on MoS 2 nanosheets with ultrahigh loading of 1.8 at% (the highest is 1.3 at% to date). Owing to the ganoderma-like structure and platinum atoms doping, this catalyst shows Pt-like catalytic activity for the hydrogen evolution reaction with an ultralow overpotential of 34 mV and excellent durability of only 2% increase in overpotential for 72 h under the constant current density of 10 mA cm -2 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

RGO modified Ni doped FeOOH for enhanced electrochemical and photoelectrochemical water oxidation

NASA Astrophysics Data System (ADS)

Zhang, Xiaofan; Zhang, Bingyan; Liu, Shuangshuang; Kang, Hongwei; Kong, Weiqian; Zhang, Shouren; Shen, Yan; Yang, Baocheng

2018-04-01

Ni,Fe-based (oxy)hydroxides have been one of the most active catalysts for the oxygen evolution reaction. In this article, reduced graphene oxide supported Ni doped FeOOH (RGO/Ni:FeOOH) was prepared for electrochemical and photoelectrochemical (PEC) water oxidation. The RGO/Ni:FeOOH exhibited a lower over-potential (260 mV at 10 mA cm-2) and smaller Tafel slope (32.3 mV dec-1) than that of the FeOOH and Ni:FeOOH. Such significant enhancement is attributed to Ni doping and RGO, which reduce the over-potential, improve the conductivity and enlarge surface areas. Besides, RGO/Ni:FeOOH decorated the TiO2 nanorods (NRs) was also fabricated for photoelectrochemical (PEC) water oxidation, which exhibited a higher photocurrent density and lower onset potential than that of TiO2 NRs the bare under illumination due to the synergistic effect of RGO and Ni:FeOOH. These results demonstrate the RGO/Ni:FeOOH has great promising as a co-catalyst to improve the PEC performance.

Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics

NASA Astrophysics Data System (ADS)

Zhang, Jian; Wang, Tao; Liu, Pan; Liao, Zhongquan; Liu, Shaohua; Zhuang, Xiaodong; Chen, Mingwei; Zschech, Ehrenfried; Feng, Xinliang

2017-05-01

Various platinum-free electrocatalysts have been explored for hydrogen evolution reaction in acidic solutions. However, in economical water-alkali electrolysers, sluggish water dissociation kinetics (Volmer step) on platinum-free electrocatalysts results in poor hydrogen-production activities. Here we report a MoNi4 electrocatalyst supported by MoO2 cuboids on nickel foam (MoNi4/MoO2@Ni), which is constructed by controlling the outward diffusion of nickel atoms on annealing precursor NiMoO4 cuboids on nickel foam. Experimental and theoretical results confirm that a rapid Tafel-step-decided hydrogen evolution proceeds on MoNi4 electrocatalyst. As a result, the MoNi4 electrocatalyst exhibits zero onset overpotential, an overpotential of 15 mV at 10 mA cm-2 and a low Tafel slope of 30 mV per decade in 1 M potassium hydroxide electrolyte, which are comparable to the results for platinum and superior to those for state-of-the-art platinum-free electrocatalysts. Benefiting from its scalable preparation and stability, the MoNi4 electrocatalyst is promising for practical water-alkali electrolysers.

Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential.

PubMed

Wang, Jun; Yu, Liang; Hu, Lin; Chen, Gang; Xin, Hongliang; Feng, Xiaofeng

2018-05-15

Electrochemical reduction of N 2 to NH 3 provides an alternative to the Haber-Bosch process for sustainable, distributed production of NH 3 when powered by renewable electricity. However, the development of such process has been impeded by the lack of efficient electrocatalysts for N 2 reduction. Here we report efficient electroreduction of N 2 to NH 3 on palladium nanoparticles in phosphate buffer solution under ambient conditions, which exhibits high activity and selectivity with an NH 3 yield rate of ~4.5 μg mg -1 Pd h -1 and a Faradaic efficiency of 8.2% at 0.1 V vs. the reversible hydrogen electrode (corresponding to a low overpotential of 56 mV), outperforming other catalysts including gold and platinum. Density functional theory calculations suggest that the unique activity of palladium originates from its balanced hydrogen evolution activity and the Grotthuss-like hydride transfer mechanism on α-palladium hydride that lowers the free energy barrier of N 2 hydrogenation to *N 2 H, the rate-limiting step for NH 3 electrosynthesis.

N-doped graphene layers encapsulated NiFe alloy nanoparticles derived from MOFs with superior electrochemical performance for oxygen evolution reaction

PubMed Central

Feng, Yi; Yu, Xin-Yao; Paik, Ungyu

2016-01-01

Water splitting, an efficient approach for hydrogen production, is often hindered by unfavorable kinetics of oxygen evolution reaction (OER). In order to reduce the overpotential, noble metal oxides-based electrocatalysts like RuO2 and IrO2 are usually utilized. However, due to their scarcity, the development of cost-effective non-precious OER electrocatalysts with high efficiency and good stability is urgently required. Herein, we report a facile one-step annealing of metal-organic frameworks (MOFs) strategy to synthesize N-doped graphene layers encapsulated NiFe alloy nanoparticles (NiFe@C). Through tuning the nanoparticle size and calcination temperature, NiFe@C with an average size of around 16 nm obtained at 700 °C exhibits superior OER performance with an overpotential of only 281 mV at 10 mA cm−2 and high durability. The facile synthesis method and excellent electrochemical performance show great potential of NiFe@C in replacing the precious metal-based electrocatalysts in the OER. PMID:27658968

Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities

PubMed Central

Lu, Xunyu; Zhao, Chuan

2015-01-01

Large-scale industrial application of electrolytic splitting of water has called for the development of oxygen evolution electrodes that are inexpensive, robust and can deliver large current density (>500 mA cm−2) at low applied potentials. Here we show that an efficient oxygen electrode can be developed by electrodepositing amorphous mesoporous nickel–iron composite nanosheets directly onto macroporous nickel foam substrates. The as-prepared oxygen electrode exhibits high catalytic activity towards water oxidation in alkaline solutions, which only requires an overpotential of 200 mV to initiate the reaction, and is capable of delivering current densities of 500 and 1,000 mA cm−2 at overpotentials of 240 and 270 mV, respectively. The electrode also shows prolonged stability against bulk water electrolysis at large current. Collectively, the as-prepared three-dimensional structured electrode is the most efficient oxygen evolution electrode in alkaline electrolytes reported to the best of our knowledge, and can potentially be applied for industrial scale water electrolysis. PMID:25776015

Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Electrolyte: Evidence for Surface Proton Transfer Effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yu; Lu, Fang; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR) pathway, as a key high-performance reaction pathway in energy conversion, has been sought after in numerous investigations on metal surfaces over the last decades. Although the surfaces of the most noble metals, including platinum and palladium, demonstrate the fullpotential- range 4e-ORR, this is not the case, for gold (Au) surfaces. The 4e-ORR is only operative on Au surfaces with {100} subfacets, e.g. Au(100), in alkaline solution, however restricted to a certain potential region at low overpotentials, while reverting to a 2e-ORR at high overpotentials. This ORR on Au(100) has been a long-standing puzzle of electrocatalysis.more » Hereby we review the ORR studies on Au, along with the studies of water effects on Au catalysts, and present our electrochemical results with monofacet Au nanocrystals. Finally, combining with theoretical calculations we demonstrate that surface proton transfer from co-adsorbed water plays the key role in determining the ORR mechanism on Au surfaces in base.« less

Cobalt Phosphide Hollow Polyhedron as Efficient Bifunctional Electrocatalysts for the Evolution Reaction of Hydrogen and Oxygen.

PubMed

Liu, Mengjia; Li, Jinghong

2016-01-27

The development of efficient and low-cost hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalysts for renewable-energy conversion techniques is highly desired. A kind of hollow polyhedral cobalt phosphide (CoP hollow polyhedron) is developed as efficient bifunctional electrocatalysts for HER and OER templated by Co-centered metal-organic frameworks. The as-prepared CoP hollow polyhedron, which have large specific surface area and high porosity providing rich catalytic active sites, show excellent electrocatalytic performances for both HER and OER in acidic and alkaline media, respectively, with onset overpotentials of 35 and 300 mV, Tafel slopes of 59 and 57 mV dec(-1), and a current density of 10 mA cm(-2) at overpotentials of 159 and 400 mV for HER and OER, respectively, which are remarkably superior to those of particulate CoP (CoP particles) and comparable to those of commercial noble-metal catalysts. In addition, the CoP hollow polyhedron also show good durability after long-term operations.

Spatial Heterogeneities and Onset of Passivation Breakdown at Lithium Anode Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leung, Kevin; Jungjohann, Katherine L.

Effective passivation of lithium metal surfaces, and prevention of battery-shorting lithium dendrite growth, are critical for implementing lithium metal anodes for batteries with increased power densities. Nanoscale surface heterogeneities can be “hot spots” where anode passivation breaks down. Motivated by the observation of lithium dendrites in pores and grain boundaries in all-solid batteries, we examine lithium metal surfaces covered with Li 2O and/or LiF thin films with grain boundaries in them. Electronic structure calculations show that at >0.25 V computed equilibrium overpotential Li 2O grain boundaries with sufficiently large pores can accommodate Li0 atoms which aid e– leakage and passivationmore » breakdown. Strain often accompanies Li insertion; applying an ~1.7% strain already lowers the computed overpotential to 0.1 V. Lithium metal nanostructures as thin as 12 Å are thermodynamically favored inside cracks in Li 2O films, becoming “incipient lithium filaments”. LiF films are more resistant to lithium metal growth. Finally, the models used herein should in turn inform passivating strategies in all-solid-state batteries.« less

Vertical distribution of overpotentials and irreversible charge losses in lithium ion battery electrodes.

PubMed

Klink, Stefan; Schuhmann, Wolfgang; La Mantia, Fabio

2014-08-01

Porous lithium ion battery electrodes are characterized using a vertical distribution of cross-currents. In an appropriate simplification, this distribution can be described by a transmission line model (TLM) consisting of infinitely thin electrode layers. To investigate the vertical distribution of currents, overpotentials, and irreversible charge losses in a porous graphite electrode in situ, a multi-layered working electrode (MWE) was developed as the experimental analogue of a TLM. In this MWE, each layer is in ionic contact but electrically insulated from the other layers by a porous separator. It was found that the negative graphite electrodes get lithiated and delithiated stage-by-stage and layer-by-layer. Several mass-transport- as well as non-mass-transport-limited processes could be identified. Local current densities can reach double the average, especially on the outermost layer at the beginning of each intercalation stage. Furthermore, graphite particles close to the counter electrode act as "electrochemical sieve" reducing the impurities present in the electrolyte such as water. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Electrolyte: Evidence for Surface Proton Transfer Effects

DOE PAGES

Zhang, Yu; Lu, Fang; Liu, Shizhong; ...

2018-04-01

Four-electron oxygen reduction reaction (4e-ORR) pathway, as a key high-performance reaction pathway in energy conversion, has been sought after in numerous investigations on metal surfaces over the last decades. Although the surfaces of the most noble metals, including platinum and palladium, demonstrate the fullpotential- range 4e-ORR, this is not the case, for gold (Au) surfaces. The 4e-ORR is only operative on Au surfaces with {100} subfacets, e.g. Au(100), in alkaline solution, however restricted to a certain potential region at low overpotentials, while reverting to a 2e-ORR at high overpotentials. This ORR on Au(100) has been a long-standing puzzle of electrocatalysis.more » Hereby we review the ORR studies on Au, along with the studies of water effects on Au catalysts, and present our electrochemical results with monofacet Au nanocrystals. Finally, combining with theoretical calculations we demonstrate that surface proton transfer from co-adsorbed water plays the key role in determining the ORR mechanism on Au surfaces in base.« less

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Jaemin; Shih, Pei-Chieh; Tsao, Kai-Chieh

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge for the production of hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y2Ru2O7-δ) electrocatalyst that has significantly enhanced performance towards OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1-M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y2Ru2O7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band center energy for the overlap betweenmore » Ru 4d and O 2p orbitals and therefore more stable Ru-O bond than RuO2, highlighting the effect of yttrium on the enhancement in stability. The Y2Ru2O7-δ pyrochlore is also free of expensive iridium metal, thus a cost-effective candidate for practical applications.« less

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Jaemin; Shih, Pei-Chieh; Tsao, Kai-Chieh

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge to produce hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y 2Ru 2O 7-δ) electrocatalyst that has significantly enhanced performance toward OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1 M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y 2Ru 2O 7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band centermore » energy for the overlap between Ru 4d and O 2p orbitals and is therefore more stable Ru–O bond than RuO 2, highlighting the effect of yttrium on the enhancement in stability. Finally, the Y 2Ru 2O 7-δ pyrochlore is also free of expensive iridium metal and thus is a cost-effective candidate for practical applications.« less

Investigation of different anode materials for aluminium rechargeable batteries

NASA Astrophysics Data System (ADS)

Muñoz-Torrero, David; Leung, Puiki; García-Quismondo, Enrique; Ventosa, Edgar; Anderson, Marc; Palma, Jesús; Marcilla, Rebeca

2018-01-01

In order to shed some light into the importance of the anodic reaction in reversible aluminium batteries, we investigate here the electrodeposition of aluminium in an ionic liquid electrolyte (BMImCl-AlCl3) using different substrates. We explore the influence of the type of anodic material (aluminium, stainless steel and carbon) and its 3D geometry on the reversibility of the anodic reaction by cyclic voltammetry (CV) and galvanostatic charge-discharge. The shape of the CVs confirms that electrodeposition of aluminium was feasible in the three materials but the highest peak currents and smallest peak separation in the CV of the aluminium anode suggested that this material was the most promising. Interestingly, carbon-based substrates appeared as an interesting alternative due to the high peak currents in CV, moderate overpotentials and dual role as anode and cathode. 3D substrates such as fiber-based carbon paper and aluminium mesh showed significantly smaller overpotentials and higher efficiencies for Al reaction suggesting that the use of 3D substrates in full batteries might result in enhanced power. This is corroborated by polarization testing of full Al-batteries.

Molecular metal–Nx centres in porous carbon for electrocatalytic hydrogen evolution

PubMed Central

Liang, Hai-Wei; Brüller, Sebastian; Dong, Renhao; Zhang, Jian; Feng, Xinliang; Müllen, Klaus

2015-01-01

Replacement of precious platinum with efficient and low-cost catalysts for electrocatalytic hydrogen evolution at low overpotentials holds tremendous promise for clean energy devices. Here we report a novel type of robust cobalt–nitrogen/carbon catalyst for the hydrogen evolution reaction (HER) that is prepared by the pyrolysis of cobalt–N4 macrocycles or cobalt/o-phenylenediamine composites and using silica colloids as a hard template. We identify the well-dispersed molecular CoNx sites on the carbon support as the active sites responsible for the HER. The CoNx/C catalyst exhibits extremely high turnover frequencies per cobalt site in acids, for example, 0.39 and 6.5 s−1 at an overpotential of 100 and 200 mV, respectively, which are higher than those reported for other scalable non-precious metal HER catalysts. Our results suggest the great promise of developing new families of non-precious metal HER catalysts based on the controlled conversion of homogeneous metal complexes into solid-state carbon catalysts via economically scalable protocols. PMID:26250525

Single crystalline Co3O4 nanocrystals exposed with different crystal planes for Li-O2 batteries.

PubMed

Su, Dawei; Dou, Shixue; Wang, Guoxiu

2014-08-29

Single crystalline Co3O4 nanocrystals exposed with different crystal planes were synthesised, including cubic Co3O4 nanocrystals enclosed by {100} crystal planes, pseudo octahedral Co3O4 enclosed by {100} and {110} crystal planes, Co3O4 nanosheets exposed by {110} crystal planes, hexagonal Co3O4 nanoplatelets exposed with {111} crystal planes, and Co3O4 nanolaminar exposed with {112} crystal planes. Well single crystalline features of these Co3O4 nanocrystals were confirmed by FESEM and HRTEM analyses. The electrochemical performance for Li-O2 batteries shows that Co3O4 nanocrystals can significantly reduce the discharge-charge over-potential via the effect on the oxygen evolution reaction (OER). From the comparison on their catalytic performances, we found that the essential factor to promote the oxygen evolution reactions is the surface crystal planes of Co3O4 nanocrystals, namely, crystal planes-dependent process. The correlation between different Co3O4 crystal planes and their effect on reducing charge-discharge over-potential was established: {100} < {110} < {112} < {111}.

Morphological Evolution of Nanocluster Aggregates and Single Crystals in Alkaline Zinc Electrodeposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Desai, D; Turney, DE; Anantharaman, B

2014-04-24

The morphology of Zn electrodeposits is studied on carbon-coated transmission electron microscopy grids. At low over-potentials (eta = -50 mV), the morphology develops by aggregation at two distinct length scales: similar to 5 nm diameter monocrystalline nanoclusters form similar to 50 nm diameter polycrystalline aggregates, and the aggregates form a branched network. Epitaxial (00 (0) over bar2) growth above an overpotential of vertical bar eta(c)vertical bar > 125 mV leads to the formation of hexagonal single crystals up to 2 mu m in diameter. Potentiostatic current transients were used to calculate the nucleation rate from Scharifker et al.'s model. Themore » exp(eta) dependence of the nucleation rates indicates that atomistic nucleation theory explains the nucleation process better than Volmer-Weber theory. A kinetic model is provided using the rate equations of vapor solidification to simulate the evolution of the different morphologies. On solving these equations, we show that aggregation is attributed to cluster impingement and cluster diffusion while single-crystal formation is attributed to direct attachment.« less

Efficient Transport Networks in a Dual Electron/Lithium-Conducting Polymeric Composite for Electrochemical Applications.

PubMed

McDonald, Michael B; Hammond, Paula T

2018-05-09

In this work, an all-functional polymer material composed of the electrically conductive poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonic acid) (PEDOT:PSS) and lithium-conducting poly(ethylene oxide) (PEO) was developed to form a dual conductor for three-dimensional electrodes in electrochemical applications. The composite exhibits enhanced ionic conductivity (∼10 -4 S cm -1 ) and, counterintuitively, electronic conductivity (∼45 S cm -1 ) with increasing PEO proportion, optimal at a monomer ratio of 20:1 PEO:PEDOT. Microscopy reveals a unique morphology, where PSS interacts favorably with PEO, destabilizing PEDOT to associate into highly branched, interconnected networks that allow for more efficient electronic transport despite relatively low concentrations. Thermal and X-ray techniques affirm that the PSS-PEO domain suppresses crystallinity, explaining the high ionic conductivity. Electrochemical experiments in lithium cell environments indicate stability as a function of cycling and improved overpotential due to dual transport characteristics despite known issues with both individual components.

Electrocatalytic performances of g-C3N4-LaNiO3 composite as bi-functional catalysts for lithium-oxygen batteries

PubMed Central

Wu, Yixin; Wang, Taohuan; Zhang, Yidie; Xin, Sen; He, Xiaojun; Zhang, Dawei; Shui, Jianglan

2016-01-01

A low cost and non-precious metal composite material g-C3N4-LaNiO3 (CNL) was synthesized as a bifunctional electrocatalyst for the air electrode of lithium-oxygen (Li-O2) batteries. The composition strategy changed the electron structure of LaNiO3 and g-C3N4, ensures high Ni3+/Ni2+ ratio and more absorbed hydroxyl on the surface of CNL that can promote the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The composite catalyst presents higher activities than the individual components g-C3N4 and LaNiO3 for both ORR and OER. In non-aqueous Li-O2 batteries, CNL shows higher capacity, lower overpotentials and better cycling stability than XC-72 carbon and LaNiO3 catalysts. Our results suggest that CNL composite is a promising cathode catalyst for Li-O2 batteries. PMID:27074882

An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Mahmood, Javeed; Li, Feng; Jung, Sun-Min; Okyay, Mahmut Sait; Ahmad, Ishfaq; Kim, Seok-Jin; Park, Noejung; Jeong, Hu Young; Baek, Jong-Beom

2017-05-01

The hydrogen evolution reaction (HER) is a crucial step in electrochemical water splitting and demands an efficient, durable and cheap catalyst if it is to succeed in real applications. For an energy-efficient HER, a catalyst must be able to trigger proton reduction with minimal overpotential and have fast kinetics. The most efficient catalysts in acidic media are platinum-based, as the strength of the Pt-H bond is associated with the fastest reaction rate for the HER. The use of platinum, however, raises issues linked to cost and stability in non-acidic media. Recently, non-precious-metal-based catalysts have been reported, but these are susceptible to acid corrosion and are typically much inferior to Pt-based catalysts, exhibiting higher overpotentials and lower stability. As a cheaper alternative to platinum, ruthenium possesses a similar bond strength with hydrogen (˜65 kcal mol-1), but has never been studied as a viable alternative for a HER catalyst. Here, we report a Ru-based catalyst for the HER that can operate both in acidic and alkaline media. Our catalyst is made of Ru nanoparticles dispersed within a nitrogenated holey two-dimensional carbon structure (Ru@C2N). The Ru@C2N electrocatalyst exhibits high turnover frequencies at 25 mV (0.67 H2 s-1 in 0.5 M H2SO4 solution; 0.75 H2 s-1 in 1.0 M KOH solution) and small overpotentials at 10 mA cm-2 (13.5 mV in 0.5 M H2SO4 solution; 17.0 mV in 1.0 M KOH solution) as well as superior stability in both acidic and alkaline media. These performances are comparable to, or even better than, the Pt/C catalyst for the HER.

Assessing the utility of bipolar membranes for use in photoelectrochemical water-splitting cells.

PubMed

Vargas-Barbosa, Nella M; Geise, Geoffrey M; Hickner, Michael A; Mallouk, Thomas E

2014-11-01

Membranes are important in water-splitting solar cells because they prevent crossover of hydrogen and oxygen. Here, bipolar membranes (BPMs) were tested as separators in water electrolysis cells. Steady-state membrane and solution resistances, electrode overpotentials, and pH gradients were measured at current densities relevant to solar photoelectrolysis. Under forward bias conditions, electrodialysis of phosphate buffer ions creates a pH gradient across a BPM. Under reverse bias, the BPM can maintain a constant buffer pH on both sides of the cell, but a large membrane potential develops. Thus, the BPM does not present a viable solution for electrolysis in buffered electrolytes. However, the membrane potential is minimized when the anode and cathode compartments of the cell contain strongly basic and acidic electrolytes, respectively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced CO2 electroreduction efficiency through secondary coordination effects on a pincer iridium catalyst.

PubMed

Ahn, Steven T; Bielinski, Elizabeth A; Lane, Elizabeth M; Chen, Yanqiao; Bernskoetter, Wesley H; Hazari, Nilay; Palmore, G Tayhas R

2015-04-07

An iridium(III) trihydride complex supported by a pincer ligand with a hydrogen bond donor in the secondary coordination sphere promotes the electrocatalytic reduction of CO2 to formate in water/acetonitrile with excellent Faradaic efficiency and low overpotential. Preliminary mechanistic experiments indicate formate formation is facile while product release is a kinetically difficult step.

Highly active catalyst derived from a 3D foam of Fe(PO3)2/Ni2P for extremely efficient water oxidation

PubMed Central

Zhou, Haiqing; Yu, Fang; Sun, Jingying; He, Ran; Chen, Shuo; Chu, Ching-Wu; Ren, Zhifeng

2017-01-01

Commercial hydrogen production by electrocatalytic water splitting will benefit from the realization of more efficient and less expensive catalysts compared with noble metal catalysts, especially for the oxygen evolution reaction, which requires a current density of 500 mA/cm2 at an overpotential below 300 mV with long-term stability. Here we report a robust oxygen-evolving electrocatalyst consisting of ferrous metaphosphate on self-supported conductive nickel foam that is commercially available in large scale. We find that this catalyst, which may be associated with the in situ generated nickel–iron oxide/hydroxide and iron oxyhydroxide catalysts at the surface, yields current densities of 10 mA/cm2 at an overpotential of 177 mV, 500 mA/cm2 at only 265 mV, and 1,705 mA/cm2 at 300 mV, with high durability in alkaline electrolyte of 1 M KOH even after 10,000 cycles, representing activity enhancement by a factor of 49 in boosting water oxidation at 300 mV relative to the state-of-the-art IrO2 catalyst. PMID:28507120

Reduced SnO2 Porous Nanowires with a High Density of Grain Boundaries as Catalysts for Efficient Electrochemical CO2 -into-HCOOH Conversion.

PubMed

Kumar, Bijandra; Atla, Veerendra; Brian, J Patrick; Kumari, Sudesh; Nguyen, Tu Quang; Sunkara, Mahendra; Spurgeon, Joshua M

2017-03-20

Electrochemical conversion of CO 2 into energy-dense liquids, such as formic acid, is desirable as a hydrogen carrier and a chemical feedstock. SnO x is one of the few catalysts that reduce CO 2 into formic acid with high selectivity but at high overpotential and low current density. We show that an electrochemically reduced SnO 2 porous nanowire catalyst (Sn-pNWs) with a high density of grain boundaries (GBs) exhibits an energy conversion efficiency of CO 2 -into-HCOOH higher than analogous catalysts. HCOOH formation begins at lower overpotential (350 mV) and reaches a steady Faradaic efficiency of ca. 80 % at only -0.8 V vs. RHE. A comparison with commercial SnO 2 nanoparticles confirms that the improved CO 2 reduction performance of Sn-pNWs is due to the density of GBs within the porous structure, which introduce new catalytically active sites. Produced with a scalable plasma synthesis technology, the catalysts have potential for application in the CO 2 conversion industry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shape-Dependent Electrocatalytic Reduction of CO2 to CO on Triangular Silver Nanoplates.

PubMed

Liu, Subiao; Tao, Hongbiao; Zeng, Li; Liu, Qi; Xu, Zhenghe; Liu, Qingxia; Luo, Jing-Li

2017-02-15

Electrochemical reduction of CO 2 (CO 2 RR) provides great potential for intermittent renewable energy storage. This study demonstrates a predominant shape-dependent electrocatalytic reduction of CO 2 to CO on triangular silver nanoplates (Tri-Ag-NPs) in 0.1 M KHCO 3 . Compared with similarly sized Ag nanoparticles (SS-Ag-NPs) and bulk Ag, Tri-Ag-NPs exhibited an enhanced current density and significantly improved Faradaic efficiency (96.8%) and energy efficiency (61.7%), together with a considerable durability (7 days). Additionally, CO starts to be observed at an ultralow overpotential of 96 mV, further confirming the superiority of Tri-Ag-NPs as a catalyst for CO 2 RR toward CO formation. Density functional theory calculations reveal that the significantly enhanced electrocatalytic activity and selectivity at lowered overpotential originate from the shape-controlled structure. This not only provides the optimum edge-to-corner ratio but also dominates at the facet of Ag(100) where it requires lower energy to initiate the rate-determining step. This study demonstrates a promising approach to tune electrocatalytic activity and selectivity of metal catalysts for CO 2 RR by creating optimal facet and edge site through shape-control synthesis.

High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei

2017-01-18

The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkalinemore » solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.« less

MnMoO4 nanosheet array: an efficient electrocatalyst for hydrogen evolution reaction with enhanced activity over a wide pH range.

PubMed

Wen, Lulu; Sun, Yiqiang; Zhang, Tao; Bai, Yu; Li, Xinyang; Lyu, Xianjun; Cai, Weiping; Li, Yue

2018-08-17

We report the preparation of MnMoO 4 nanosheet array on nickel foam (MnMoO 4 NSA/NF) as an excellent 3D hydrogen evolution reaction (HER) electrocatalyst with good catalytic performance applied under basic, acidic and neutral conditions. In 0.5 M H 2 SO 4 , this MnMoO 4 NSA/NF electrode needs an overpotential of 89 mV to drive current densities of 10 mA cm -2 , to achieve the same current density, it demands overpotentials of 105 mV in 1.0 M KOH, 161 mV in 1.0 M PBS (pH = 7), respectively. After continuous CV scanning for 1000 cycles under different pH conditions, it also demonstrates an excellent stability with ignorable activity decrease. Such preeminent HER performance may be derived from the synergistic effect between manganese (Mn) and molybdenum (Mo) atoms, exposure of more active sites on the nanosheets and effective electron transport along the nanosheets. This MnMoO 4 NSA/NF electrocatalyst provides us a highly efficient material for water splitting devices for industrial hydrogen production.

Electronic π-Delocalization Boosts Catalytic Water Oxidation by Cu(II) Molecular Catalysts Heterogenized on Graphene Sheets.

PubMed

Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Moonshiram, Dooshaye; Picón, Antonio; Monge, Pere; Batista, Victor S; Llobet, Antoni

2017-09-20

A molecular water oxidation catalyst based on the copper complex of general formula [(L py )Cu II ] 2- , 2 2- , (L py is 4-pyrenyl-1,2-phenylenebis(oxamidate) ligand) has been rationally designed and prepared to support a more extended π-conjugation through its structure in contrast with its homologue, the [(L)Cu II ] 2- water oxidation catalyst, 1 2- (L is o-phenylenebis(oxamidate)). The catalytic performance of both catalysts has been comparatively studied in homogeneous phase and in heterogeneous phase by π-stacking anchorage to graphene-based electrodes. In the homogeneous system, the electronic perturbation provided by the pyrene functionality translates into a 150 mV lower overpotential for 2 2- with respect to 1 2- and an impressive increase in the k cat from 6 to 128 s -1 . Upon anchorage, π-stacking interactions with the graphene sheets provide further π-delocalization that improves the catalytic performance of both catalysts. In this sense, 2 2- turned out to be the most active catalyst due to the double influence of both the pyrene and the graphene, displaying an overpotential of 538 mV, a k cat of 540 s -1 and producing more than 5300 TONs.

Enhanced Activity and Acid pH Stability of Prussian Blue-type Oxygen Evolution Electrocatalysts Processed by Chemical Etching.

PubMed

Han, Lijuan; Tang, Pengyi; Reyes-Carmona, Álvaro; Rodríguez-García, Bárbara; Torréns, Mabel; Morante, Joan Ramon; Arbiol, Jordi; Galan-Mascaros, Jose Ramon

2016-12-14

The development of upscalable oxygen evolving electrocatalysts from earth-abundant metals able to operate in neutral or acidic environments and low overpotentials remains a fundamental challenge for the realization of artificial photosynthesis. In this study, we report a highly active phase of heterobimetallic cyanide-bridged electrocatalysts able to promote water oxidation under neutral, basic (pH < 13), and acidic conditions (pH > 1). Cobalt-iron Prussian blue-type thin films, formed by chemical etching of Co(OH) 1.0 (CO 3 ) 0.5 ·nH 2 O nanocrystals, yield a dramatic enhancement of the catalytic performance toward oxygen production, when compared with previous reports for analogous materials. Electrochemical, spectroscopic, and structural studies confirm the excellent performance, stability, and corrosion resistance, even when compared with state-of-the-art metal oxide catalysts under moderate overpotentials and in a remarkably large pH range, including acid media where most cost-effective water oxidation catalysts are not useful. The origin of the superior electrocatalytic activity toward water oxidation appears to be in the optimized interfacial matching between catalyst and electrode surface obtained through this fabrication method.

Standard electrode potential, Tafel equation, and the solvation thermodynamics.

PubMed

Matyushov, Dmitry V

2009-06-21

Equilibrium in the electronic subsystem across the solution-metal interface is considered to connect the standard electrode potential to the statistics of localized electronic states in solution. We argue that a correct derivation of the Nernst equation for the electrode potential requires a careful separation of the relevant time scales. An equation for the standard metal potential is derived linking it to the thermodynamics of solvation. The Anderson-Newns model for electronic delocalization between the solution and the electrode is combined with a bilinear model of solute-solvent coupling introducing nonlinear solvation into the theory of heterogeneous electron transfer. We therefore are capable of addressing the question of how nonlinear solvation affects electrochemical observables. The transfer coefficient of electrode kinetics is shown to be equal to the derivative of the free energy, or generalized force, required to shift the unoccupied electronic level in the bulk. The transfer coefficient thus directly quantifies the extent of nonlinear solvation of the redox couple. The current model allows the transfer coefficient to deviate from the value of 0.5 of the linear solvation models at zero electrode overpotential. The electrode current curves become asymmetric in respect to the change in the sign of the electrode overpotential.

CuO-Functionalized Silicon Photoanodes for Photoelectrochemical Water Splitting Devices.

PubMed

Shi, Yuanyuan; Gimbert-Suriñach, Carolina; Han, Tingting; Berardi, Serena; Lanza, Mario; Llobet, Antoni

2016-01-13

One main difficulty for the technological development of photoelectrochemical (PEC) water splitting (WS) devices is the fabrication of active, stable and cost-effective photoelectrodes that ensure high performance. Here, we report the development of a CuO/Silicon based photoanode, which shows an onset potential for the water oxidation of 0.53 V vs SCE at pH 9, that is, an overpotential of 75 mV, and high stability above 10 h. These values account for a photovoltage of 420 mV due to the absorbed photons by silicon, as proven by comparing with analogous CuO/FTO electrodes that are not photoactive. The photoanodes have been fabricated by sputtering a thin film of Cu(0) on commercially available n-type Si wafers, followed by a photoelectrochemical treatment in basic pH conditions. The resulting CuO/Cu layer acts as (1) protective layer to avoid the corrosion of nSi, (2) p-type hole conducting layer for efficient charge separation and transportation, and (3) electrocatalyst to reduce the overpotential of the water oxidation reaction. The low cost, low toxicity, and good performance of CuO-based coatings can be an attractive solution to functionalize unstable materials for solar energy conversion.

Dendrite-Suppressed Lithium Plating from a Liquid Electrolyte via Wetting of Li 3N

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Kyusung; Goodenough, John B.

Lithium metal is an ultimate anode material to provide the highest energy density for a given cathode by providing a higher capacity and cell voltage. However, lithium is not used as the anode in commercial lithium-ion batteries because electrochemical dendrite formation and growth during charge can induce a cell short circuit that ignites the flammable liquid electrolyte. Plating of lithium through a bed of Li 3N particles is shown to transform dendrite growth into a 3D lithium network formed by wetting the particle surfaces; plating through a Li 3N particle is without dendrite nucleation. The Li 3N particles create amore » higher overpotential during Li deposition than that with dendrite growth in galvanostatic charge/discharge tests. The characteristic overpotential increase is correlated with the morphological changes and a more isotropic growth behavior. The Li 3N-modified Li electrode shows a stable cycling performance at 0.5 and 1.0 mA cm -2 for more than 100 cycles. In this paper, the origin of the bonding responsible for wetting of the Li 3N particles by lithium and for plating through a Li 3N particle is discussed.« less

Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pei, Allen; Zheng, Guangyuan; Shi, Feifei

Lithium metal has re-emerged as an exciting anode for high energy lithium-ion batteries due to its high specific capacity of 3860 mAh g -1 and lowest electrochemical potential of all known materials. However, lithium has been plagued by the issues of dendrite formation, high chemical reactivity with electrolyte, and infinite relative volume expansion during plating and stripping, which present safety hazards and low cycling efficiency in batteries with lithium metal electrodes. There have been a lot of recent studies on Li metal although little work has focused on the initial nucleation and growth behavior of Li metal, neglecting a criticalmore » fundamental scientific foundation of Li plating. Here, we study experimentally the morphology of lithium in the early stages of nucleation and growth on planar copper electrodes in liquid organic electrolyte. We elucidate the dependence of lithium nuclei size, shape, and areal density on current rate, consistent with classical nucleation and growth theory. We found that the nuclei size is proportional to the inverse of overpotential and the number density of nuclei is proportional to the cubic power of overpotential. Finally, based on this understanding, we propose a strategy to increase the uniformity of electrodeposited lithium on the electrode surface.« less

Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal

DOE PAGES

Pei, Allen; Zheng, Guangyuan; Shi, Feifei; ...

2017-01-10

Lithium metal has re-emerged as an exciting anode for high energy lithium-ion batteries due to its high specific capacity of 3860 mAh g -1 and lowest electrochemical potential of all known materials. However, lithium has been plagued by the issues of dendrite formation, high chemical reactivity with electrolyte, and infinite relative volume expansion during plating and stripping, which present safety hazards and low cycling efficiency in batteries with lithium metal electrodes. There have been a lot of recent studies on Li metal although little work has focused on the initial nucleation and growth behavior of Li metal, neglecting a criticalmore » fundamental scientific foundation of Li plating. Here, we study experimentally the morphology of lithium in the early stages of nucleation and growth on planar copper electrodes in liquid organic electrolyte. We elucidate the dependence of lithium nuclei size, shape, and areal density on current rate, consistent with classical nucleation and growth theory. We found that the nuclei size is proportional to the inverse of overpotential and the number density of nuclei is proportional to the cubic power of overpotential. Finally, based on this understanding, we propose a strategy to increase the uniformity of electrodeposited lithium on the electrode surface.« less

Dendrite-Suppressed Lithium Plating from a Liquid Electrolyte via Wetting of Li 3N

DOE PAGES

Park, Kyusung; Goodenough, John B.

2017-07-10

Lithium metal is an ultimate anode material to provide the highest energy density for a given cathode by providing a higher capacity and cell voltage. However, lithium is not used as the anode in commercial lithium-ion batteries because electrochemical dendrite formation and growth during charge can induce a cell short circuit that ignites the flammable liquid electrolyte. Plating of lithium through a bed of Li 3N particles is shown to transform dendrite growth into a 3D lithium network formed by wetting the particle surfaces; plating through a Li 3N particle is without dendrite nucleation. The Li 3N particles create amore » higher overpotential during Li deposition than that with dendrite growth in galvanostatic charge/discharge tests. The characteristic overpotential increase is correlated with the morphological changes and a more isotropic growth behavior. The Li 3N-modified Li electrode shows a stable cycling performance at 0.5 and 1.0 mA cm -2 for more than 100 cycles. In this paper, the origin of the bonding responsible for wetting of the Li 3N particles by lithium and for plating through a Li 3N particle is discussed.« less

Exploring As-Cast PbCaSn-Mg Anodes for Improved Performance in Copper Electrowinning

NASA Astrophysics Data System (ADS)

Yuwono, Jodie A.; Clancy, Marie; Chen, Xiaobo; Birbilis, Nick

2018-06-01

Lead calcium tin (PbCaSn) alloys are the common anodes used in copper electrowinning (Cu EW). Given a large amount of energy consumed in Cu EW process, anodes with controlled oxygen evolution reaction (OER) kinetics and a lower OER overpotential are advantageous for reducing the energy consumption. To date, magnesium (Mg) has never been studied as an alloying element for EW anodes. As-cast PbCaSn anodes with the addition of Mg were examined herein, revealing an improved performance compared to that of the industrial standard PbCaSn anode. The alloy performances in the early stages of anode life and passivation were established from electrochemical studies which were designed to simulate industrial Cu EW process. The 24-hour polarization testing revealed that the Mg alloying depolarizes the anode potential up to 80 mV; thus, resulting in a higher Cu EW efficiency. In addition, scanning electron microscopy and X-ray photoelectron spectroscopy revealed that the alteration of the alloy microstructure and the corresponding interfacial reactions contribute to the changes of the anode electrochemical performances. The present study reveals for the first time the potency of Mg alloying in reducing the overpotential of PbCaSn anode.

Preparation of NiCoP Hollow Quasi-Polyhedra and Their Electrocatalytic Properties for Hydrogen Evolution in Alkaline Solution.

PubMed

Li, Yapeng; Liu, Jindou; Chen, Chen; Zhang, Xiaohua; Chen, Jinhua

2017-02-22

Double metal phosphide (NiCoP) with hollow quasi-polyhedron structure was prepared by acidic etching and precipitation of ZIF-67 polyhedra and further phosphorization treatment with NaH 2 PO 2 . The morphology and microstructure of NiCoP quasi-polyhedron and its precursors were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and a micropore and chemisorption analyzer. Electrocatalytic properties were examined by typical electrochemical methods, such as linear sweep voltammetry, cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy in 1.0 M KOH aqueous solution. Results reveal that, compared with CoP hollow polyhedra, NiCoP hollow quasi-polyhedra exhibit better electrochemical properties for hydrogen evolution with a low onset overpotential of 74 mV and a small Tafel slope of 42 mV dec -1 . When the current density is 10 mA cm -2 , the corresponding overpotential is merely 124 mV, and 93% of its electrocatalytic activity can be maintained for 12 h. This indicates that NiCoP with hollow quasi-polyhedron structure, bimetallic merit, and low cost may be a good candidate as electrocatalyst in the practical application of hydrogen evolution.

Full cell simulation and the evaluation of the buffer system on air-cathode microbial fuel cell

NASA Astrophysics Data System (ADS)

Ou, Shiqi; Kashima, Hiroyuki; Aaron, Douglas S.; Regan, John M.; Mench, Matthew M.

2017-04-01

This paper presents a computational model of a single chamber, air-cathode MFC. The model considers losses due to mass transport, as well as biological and electrochemical reactions, in both the anode and cathode half-cells. Computational fluid dynamics and Monod-Nernst analysis are incorporated into the reactions for the anode biofilm and cathode Pt catalyst and biofilm. The integrated model provides a macro-perspective of the interrelation between the anode and cathode during power production, while incorporating microscale contributions of mass transport within the anode and cathode layers. Model considerations include the effects of pH (H+/OH- transport) and electric field-driven migration on concentration overpotential, effects of various buffers and various amounts of buffer on the pH in the whole reactor, and overall impacts on the power output of the MFC. The simulation results fit the experimental polarization and power density curves well. Further, this model provides insight regarding mass transport at varying current density regimes and quantitative delineation of overpotentials at the anode and cathode. Overall, this comprehensive simulation is designed to accurately predict MFC performance based on fundamental fluid and kinetic relations and guide optimization of the MFC system.

Mn-doped NiP2 nanosheets as an efficient electrocatalyst for enhanced hydrogen evolution reaction at all pH values

NASA Astrophysics Data System (ADS)

Wang, Xiaodeng; Zhou, Hongpeng; Zhang, Dingke; Pi, Mingyu; Feng, Jiajia; Chen, Shijian

2018-05-01

Developing stable and high-efficiency hydrogen generation electrocatalysts, particularly for the cathode hydrogen evolution reaction (HER), is an urgent challenge in energy conversion technologies. In this work, we have successfully synthesized Mn-doped NiP2 nanosheets on carbon cloth (Mn-NiP2 NSs/CC), which behaves as a higher efficient three dimensional HER electrocatalyst with better stability at all pH values than pure NiP2. Electrochemical tests demonstrate that the catalytic activity of NiP2 is enhanced by Mn doping. In 0.5 M H2SO4, this Mn-NiP2 NSs/CC catalyst drives 10 mA cm-2 at an overpotential of 69 mV, which is 20 mV smaller than pure NiP2. To achieve the same current density, it demands overpotentials of 97 and 107 mV in 1.0 M KOH and phosphate-buffered saline (PBS), respectively. Compared with pure NiP2, higher HER electrocatalytic performance for Mn-NiP2 NSs/CC can be attributed to its lower thermo-neutral hydrogen adsorption free energy, which is supported by density functional theory calculations.

Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal.

PubMed

Pei, Allen; Zheng, Guangyuan; Shi, Feifei; Li, Yuzhang; Cui, Yi

2017-02-08

Lithium metal has re-emerged as an exciting anode for high energy lithium-ion batteries due to its high specific capacity of 3860 mAh g -1 and lowest electrochemical potential of all known materials. However, lithium has been plagued by the issues of dendrite formation, high chemical reactivity with electrolyte, and infinite relative volume expansion during plating and stripping, which present safety hazards and low cycling efficiency in batteries with lithium metal electrodes. There have been a lot of recent studies on Li metal although little work has focused on the initial nucleation and growth behavior of Li metal, neglecting a critical fundamental scientific foundation of Li plating. Here, we study experimentally the morphology of lithium in the early stages of nucleation and growth on planar copper electrodes in liquid organic electrolyte. We elucidate the dependence of lithium nuclei size, shape, and areal density on current rate, consistent with classical nucleation and growth theory. We found that the nuclei size is proportional to the inverse of overpotential and the number density of nuclei is proportional to the cubic power of overpotential. Based on this understanding, we propose a strategy to increase the uniformity of electrodeposited lithium on the electrode surface.

Tin, Bismuth, and Tin-Bismuth Alloy Electrodeposition from Chlorometalate Salts in Deep Eutectic Solvents.

PubMed

Vieira, Luciana; Burt, Jennifer; Richardson, Peter W; Schloffer, Daniel; Fuchs, David; Moser, Alwin; Bartlett, Philip N; Reid, Gillian; Gollas, Bernhard

2017-06-01

The electrodeposition of tin, bismuth, and tin-bismuth alloys from Sn II and Bi III chlorometalate salts in the choline chloride/ethylene glycol (1:2 molar ratio) deep eutectic solvent was studied on glassy carbon and gold by cyclic voltammetry, rotating disc voltammetry, and chronoamperometry. The Sn II -containing electrolyte showed one voltammetric redox process corresponding to Sn II /Sn 0 . The diffusion coefficient of [SnCl 3 ] - , detected as the dominating species by Raman spectroscopy, was determined from Levich and Cottrell analyses. The Bi III -containing electrolyte showed two voltammetric reduction processes, both attributed to Bi III /Bi 0 . Dimensionless current/time transients revealed that the electrodeposition of both Sn and Bi on glassy carbon proceeded by 3D-progressive nucleation at a low overpotential and changed to instantaneous at higher overpotentials. The nucleation rate of Bi on glassy carbon was considerably smaller than that of Sn. Elemental Sn and Bi were electrodeposited on Au-coated glass slides from their respective salt solutions, as were Sn-Bi alloys from a 2:1 Sn II /Bi III solution. The biphasic Sn-Bi alloys changed from a Bi-rich composition to a Sn-rich composition by making the deposition potential more negative.

Use of a small overpotential approximation to analyze Geobacter sulfurreducens biofilm impedance

NASA Astrophysics Data System (ADS)

Babauta, Jerome T.; Beyenal, Haluk

2017-07-01

The electrochemical impedance of Geobacter sulfurreducens biofilms reflects the extracellular electron transfer mechanisms determining the rate of current output. Binned into two characteristic parameters, conductance and capacitance, biofilm impedance has received significant attention. The goal of this study was to evaluate a small overpotential approximation for extracellular electron transfer in G. sulfurreducens biofilms. Our motivation was to determine whether conductance over biofilm growth behaved linearly with respect to limiting current. Biofilm impedance was tracked during growth using electrochemical impedance spectroscopy (EIS) and electrochemical quartz crystal microbalance (eQCM). We showed that normalization of the biofilm impedance is useful for characterizing the changes during growth. When the conductance and capacitance were compared to the biofilm current, we found that: 1) conductance had a linear response and 2) constant phase elements (CPE) had a saturating response that coincided with the limiting current. We provided a framework using a simple iV relationship that predicted the conductance-current slope to be 9.57 V-1. CPEs showed more variability across biofilm replicates than conductance values. Although G. sulfurreducens biofilms were used here, other electrochemically active biofilms exhibiting catalytic waves could be studied using the same methods.

In situ growth of NiFe alloy nanoparticles embedded into N-doped bamboo-like carbon nanotube as a bifunctional electrocatalyst for Zn-air battery.

PubMed

Bin, Duan; Yang, Beibei; Li, Chao; Liu, Yao; Zhang, Xiao; Wang, Yong-Gang; Xia, Yongyao

2018-06-26

Developing low-cost catalysts for electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with superior performance in alkaline solution is of significance for large-scale application in aqueous zinc-air batteries (ZABs). Herein, we describe in situ design of embedded NiFe nanoparticles into the N-doped bamboo-like carbon nanotube (NBCNT) with high catalytic performance and stability. The obtained NiFe@NBCNT hybrid exhibits a high electrochemical activity and stability with an unexpectedly low overpotential of ~195 mV for OER at 10 mA cm-2, and an onset potential at 1.03 V for ORR, superior to the state-of-the-art Pt/C and RuO2 catalysts. Additionally, compared to the mixture Pt/C and RuO2 cathode, the ZAB based on the NiFe@NBCNT cathode displays lower overpotential (0.80 V), higher stable round-trip efficiency (58.3%) and improved power density for 200 cycles at 10 mA cm-2. Apparently, the obtained results indicate that NiFe@NBCNT hybird is proven to be one of the best non-noble metal catalysts for achieving commercial implementation of rechargeable ZABs.

Intensive Study on the Catalytical Behavior of N-Methylphenothiazine as a Soluble Mediator to Oxidize the Li2O2 Cathode of the Li-O2 Battery.

PubMed

Feng, Ningning; Mu, Xiaowei; Zhang, Xueping; He, Ping; Zhou, Haoshen

2017-02-01

Aprotic Li-O 2 batteries have attracted worldwide interest owing to their ultrahigh theoretical energy density. However, the practical Li-O 2 batteries still suffer from high charge overpotential and low energy efficiency resulting from the sluggish kinetics in electrochemically oxidizing the insulating lithium peroxide (Li 2 O 2 ). Recently, dissolved redox mediators in the electrolyte have enabled the effective catalytic oxidation of Li 2 O 2 at the liquid-solid interface. Here, we report that the incorporation of N-methylphenothiazine (MPT), as a redox shuttle in Li-O 2 batteries, provides a dramatic reduction in charge overpotential to 0.67 V and an improved round-trip efficiency close to 76%. Moreover, the efficacy of MPT in Li-O 2 cells was further investigated by various characterizations. On charging, MPT + cations are first generated electrochemically at the cathode surface and subsequently oxidize the solid discharge products Li 2 O 2 through a chemical reaction. Furthermore, the presence of MPT has been demonstrated to improve the cycling stability of the cells and suppress side reactions arising from carbon and electrolytes at high potentials.

Single Crystalline Co3O4 Nanocrystals Exposed with Different Crystal Planes for Li-O2 Batteries

PubMed Central

Su, Dawei; Dou, Shixue; Wang, Guoxiu

2014-01-01

Single crystalline Co3O4 nanocrystals exposed with different crystal planes were synthesised, including cubic Co3O4 nanocrystals enclosed by {100} crystal planes, pseudo octahedral Co3O4 enclosed by {100} and {110} crystal planes, Co3O4 nanosheets exposed by {110} crystal planes, hexagonal Co3O4 nanoplatelets exposed with {111} crystal planes, and Co3O4 nanolaminar exposed with {112} crystal planes. Well single crystalline features of these Co3O4 nanocrystals were confirmed by FESEM and HRTEM analyses. The electrochemical performance for Li-O2 batteries shows that Co3O4 nanocrystals can significantly reduce the discharge-charge over-potential via the effect on the oxygen evolution reaction (OER). From the comparison on their catalytic performances, we found that the essential factor to promote the oxygen evolution reactions is the surface crystal planes of Co3O4 nanocrystals, namely, crystal planes-dependent process. The correlation between different Co3O4 crystal planes and their effect on reducing charge-discharge over-potential was established: {100} < {110} < {112} < {111}. PMID:25169737

Uniaxial Magnetization Performance of Textured Fe Nanowire Arrays Electrodeposited by a Pulsed Potential Deposition Technique

NASA Astrophysics Data System (ADS)

Neetzel, C.; Ohgai, T.; Yanai, T.; Nakano, M.; Fukunaga, H.

2017-11-01

Textured ferromagnetic Fe nanowire arrays were electrodeposited using a rectangular-pulsed potential deposition technique into anodized aluminum oxide nanochannels. During the electrodeposition of Fe nanowire arrays at a cathodic potential of - 1.2 V, the growth rate of the nanowires was ca. 200 nm s-1. The aspect ratio of Fe nanowires with a diameter of 30 ± 5 nm reached ca. 2000. The long axis of Fe nanowires corresponded with the <200> direction when a large overpotential during the on-time pulse was applied, whereas it orientated to the <110> direction under the potentiostatic condition with a small overpotential. By shifting the on-time cathode potential up to - 1.8 V, the texture coefficient for the (200) plane, TC200, reached up to 1.94. Perpendicular magnetization performance was observed in Fe nanowire arrays. With increasing TC200, the squareness of Fe nanowire arrays increased up to 0.95 with the coercivity maintained at 1.4 kOe at room temperature. This research result has opened a novel possibility of Fe nanowire arrays that can be applied for a new permanent magnetic material without rare-earth metals.

Identification of optimal solar fuel electrocatalysts via high throughput in situ optical measurements

DOE PAGES

Shinde, Aniketa; Guevarra, Dan; Haber, Joel A.; ...

2014-10-21

For many solar fuel generator designs involve illumination of a photoabsorber stack coated with a catalyst for the oxygen evolution reaction (OER). In this design, impinging light must pass through the catalyst layer before reaching the photoabsorber(s), and thus optical transmission is an important function of the OER catalyst layer. Many oxide catalysts, such as those containing elements Ni and Co, form oxide or oxyhydroxide phases in alkaline solution at operational potentials that differ from the phases observed in ambient conditions. To characterize the transparency of such catalysts during OER operation, 1031 unique compositions containing the elements Ni, Co, Ce,more » La, and Fe were prepared by a high throughput inkjet printing technique. Moreover, the catalytic current of each composition was recorded at an OER overpotential of 0.33 V with simultaneous measurement of the spectral transmission. By combining the optical and catalytic properties, the combined catalyst efficiency was calculated to identify the optimal catalysts for solar fuel applications within the material library. Our measurements required development of a new high throughput instrument with integrated electrochemistry and spectroscopy measurements, which enables various spectroelectrochemistry experiments.« less

Controllable Synthesis of Ni xSe (0.5 ≤ x ≤ 1) Nanocrystals for Efficient Rechargeable Zinc-Air Batteries and Water Splitting.

PubMed

Zheng, Xuerong; Han, Xiaopeng; Liu, Hui; Chen, Jianjun; Fu, Dongju; Wang, Jihui; Zhong, Cheng; Deng, Yida; Hu, Wenbin

2018-04-25

The development of earth-abundant, highly active, and corrosion-resistant electrocatalysts to promote the oxygen reduction reaction (ORR) and oxygen and hydrogen evolution reactions (OER/HER) for rechargeable metal-air batteries and water-splitting devices is urgently needed. In this work, Ni x Se (0.5 ≤ x ≤ 1) nanocrystals with different crystal structures and compositions have been controllably synthesized and investigated as potential electrocatalysts for multifunctional ORR, OER, and HER in alkaline conditions. A novel hot-injection process at ambient pressure was developed to control the phase and composition of a series of Ni x Se by simply adjusting the added molar ratio of the nickel resource to triethylenetetramine. Electrochemical analysis reveals that Ni 0.5 Se nanocrystalline exhibits superior OER activity compared to its counterparts and is comparable to RuO 2 in terms of the low overpotential required to reach a current density of 10 mA cm -2 (330 mV), which may benefit from the pyrite-type crystal structure and Se enrichment in Ni 0.5 Se. For the ORR and HER, Ni 0.75 Se nanoparticles achieve the best performance including lower overpotentials and larger apparent current densities. Further investigations demonstrate that Ni 0.75 Se could not only provide an enhanced electrochemical active area but also facilitate electron transfer during the electrocatalytic process, thus contributing to the remarkable catalytic activity. As a practical application, the Ni 0.75 Se electrode enables rechargeable Zn-air battery with a considerable performance including a long cycling lifetime (200 cycles), high specific capacity (609 mA h g -1 based on the consumed Zn), and low overpotential (0.75 V) at 10 mA cm -2 . Meanwhile, the water-splitting cell setup with an anode of Ni 0.5 Se for the HER and a cathode of Ni 0.75 Se for the OER exhibits a considerable performance with low decay in activity of 12.9% under continuous polarization for 10 h. These results suggest the promising potential of nickel selenide nanocrystals as earth-abundant and high-performance electrocatalysts for metal-air batteries and alkaline water splitting.

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI) 2 in Diglyme: Implications for Multivalent Electrolytes

DOE PAGES

Baskin, Artem; Prendergast, David

2016-02-05

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitalsmore » are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI) 2)/diglyme) and its singly charged ion pair, MgTFSI +. In particular, we found that both stable (MgTFSI) + and (MgTFSI) 0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI) + ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baskin, Artem; Prendergast, David

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitalsmore » are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI) 2)/diglyme) and its singly charged ion pair, MgTFSI +. In particular, we found that both stable (MgTFSI) + and (MgTFSI) 0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI) + ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.« less

Light-driven water oxidation for solar fuels

PubMed Central

Young, Karin J.; Martini, Lauren A.; Milot, Rebecca L.; III, Robert C. Snoeberger; Batista, Victor S.; Schmuttenmaer, Charles A.; Crabtree, Robert H.; Brudvig, Gary W.

2014-01-01

Light-driven water oxidation is an essential step for conversion of sunlight into storable chemical fuels. Fujishima and Honda reported the first example of photoelectrochemical water oxidation in 1972. In their system, TiO2 was irradiated with ultraviolet light, producing oxygen at the anode and hydrogen at a platinum cathode. Inspired by this system, more recent work has focused on functionalizing nanoporous TiO2 or other semiconductor surfaces with molecular adsorbates, including chromophores and catalysts that absorb visible light and generate electricity (i.e., dye-sensitized solar cells) or trigger water oxidation at low overpotentials (i.e., photocatalytic cells). The physics involved in harnessing multiple photochemical events for multielectron reactions, as required in the four-electron water oxidation process, has been the subject of much experimental and computational study. In spite of significant advances with regard to individual components, the development of highly efficient photocatalytic cells for solar water splitting remains an outstanding challenge. This article reviews recent progress in the field with emphasis on water-oxidation photoanodes inspired by the design of functionalized thin film semiconductors of typical dye-sensitized solar cells. PMID:25364029

Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction

NASA Astrophysics Data System (ADS)

Yang, Hong Bin; Hung, Sung-Fu; Liu, Song; Yuan, Kaidi; Miao, Shu; Zhang, Liping; Huang, Xiang; Wang, Hsin-Yi; Cai, Weizheng; Chen, Rong; Gao, Jiajian; Yang, Xiaofeng; Chen, Wei; Huang, Yanqiang; Chen, Hao Ming; Li, Chang Ming; Zhang, Tao; Liu, Bin

2018-02-01

Electrochemical reduction of CO2 to chemical fuel offers a promising strategy for managing the global carbon balance, but presents challenges for chemistry due to the lack of effective electrocatalyst. Here we report atomically dispersed nickel on nitrogenated graphene as an efficient and durable electrocatalyst for CO2 reduction. Based on operando X-ray absorption and photoelectron spectroscopy measurements, the monovalent Ni(i) atomic center with a d9 electronic configuration was identified as the catalytically active site. The single-Ni-atom catalyst exhibits high intrinsic CO2 reduction activity, reaching a specific current of 350 A gcatalyst-1 and turnover frequency of 14,800 h-1 at a mild overpotential of 0.61 V for CO conversion with 97% Faradaic efficiency. The catalyst maintained 98% of its initial activity after 100 h of continuous reaction at CO formation current densities as high as 22 mA cm-2.

Controllable synthesis of hierarchical nickel cobalt sulfide with enhanced electrochemical activity

NASA Astrophysics Data System (ADS)

Tie, Jinjin; Han, Jiaxi; Diao, Guiqiang; Liu, Jiwen; Xie, Zhuopeng; Cheng, Gao; Sun, Ming; Yu, Lin

2018-03-01

The composition of nickel cobalt sulfide has great influence on its electrochemical performance. Herein, the nickel cobalt sulfide with different composition and mixed phase were synthesized by one-step solvothermal method through changing the molar ratio of Ni to Co in the reaction system. The electrochemical measurements showed that the nickel cobalt sulfide with a theoretical molar ratio of Ni/Co to be 1.5:1.5 (NCS-2) demonstrates the superior pseudocapacitive performance with a high specific capacitance (6.47 F cm-2 at 10 mA cm-2) and a favorable Coulombic efficiency (∼99%). Whereas, when applied as the catalyst for hydrogen evolution reaction in 1 M KOH aqueous electrolyte, the nickel cobalt sulfide with a theoretical molar ratio of Ni/Co is 1:2 (NCS-1) displays better catalytic activity, and it requires a relatively lower overpotential of 282 mV to deliver the current density of 10 mA cm-2.

Retuning the Catalytic Bias and Overpotential of a [NiFe]-Hydrogenase via a Single Amino Acid Exchange at the Electron Entry/Exit Site

PubMed Central

2017-01-01

The redox chemistry of the electron entry/exit site in Escherichia coli hydrogenase-1 is shown to play a vital role in tuning biocatalysis. Inspired by nature, we generate a HyaA-R193L variant to disrupt a proposed Arg–His cation−π interaction in the secondary coordination sphere of the outermost, “distal”, iron–sulfur cluster. This rewires the enzyme, enhancing the relative rate of H2 production and the thermodynamic efficiency of H2 oxidation catalysis. On the basis of Fourier transformed alternating current voltammetry measurements, we relate these changes in catalysis to a shift in the distal [Fe4S4]2+/1+ redox potential, a previously experimentally inaccessible parameter. Thus, metalloenzyme chemistry is shown to be tuned by the second coordination sphere of an electron transfer site distant from the catalytic center. PMID:28697596

Study of Stable Cathodes and Electrolytes for High Specific Density Lithium-Air Battery

NASA Technical Reports Server (NTRS)

Hernandez-Lugo, Dionne M.; Wu, James; Bennett, William; Ming, Yu; Zhu, Yu

2015-01-01

Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.

There is an urgent need to develop technologies that use renewable energy to convert waste products such as carbon dioxide into hydrocarbon fuels. Carbon dioxide can be electrochemically reduced to hydrocarbons over copper catalysts, although higher efficiency is required. We have developed oxidized copper catalysts displaying lower overpotentials for carbon dioxide electroreduction and record selectivity towards ethylene (60%) through facile and tunable plasma treatments. Herein we provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. Operando X-ray absorption spectroscopy and cross-sectional scanning transmission electron microscopy show that copper oxides aremore » surprisingly resistant to reduction and copper + species remain on the surface during the reaction. Furthermore, our results demonstrate that the roughness of oxide-derived copper catalysts plays only a partial role in determining the catalytic performance, while the presence of copper + is key for lowering the onset potential and enhancing ethylene selectivity.« less

AC impedance study of degradation of porous nickel battery electrodes

NASA Technical Reports Server (NTRS)

Lenhart, Stephen J.; Macdonald, D. D.; Pound, B. G.

1987-01-01

AC impedance spectra of porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (nonporous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low.

Precise tuning in platinum-nickel/nickel sulfide interface nanowires for synergistic hydrogen evolution catalysis

PubMed Central

Wang, Pengtang; Zhang, Xu; Zhang, Jin; Wan, Sheng; Guo, Shaojun; Lu, Gang; Yao, Jianlin; Huang, Xiaoqing

2017-01-01

Comprising abundant interfaces, multicomponent heterostructures can integrate distinct building blocks into single entities and yield exceptional functionalities enabled by the synergistic components. Here we report an efficient approach to construct one-dimensional metal/sulfide heterostructures by directly sulfuring highly composition-segregated platinum-nickel nanowires. The heterostructures possess a high density of interfaces between platinum-nickel and nickel sulfide components, which cooperate synergistically towards alkaline hydrogen evolution reaction. The platinum-nickel/nickel sulfide heterostructures can deliver a current density of 37.2 mA cm−2 at an overpotential of 70 mV, which is 9.7 times higher than that of commercial Pt/C. The heterostructures also offer enhanced stability revealed by long-term chronopotentiometry measurements. The present work highlights a potentially powerful interface-engineering strategy for designing multicomponent heterostructures with advanced performance in hydrogen evolution reaction and beyond. PMID:28239145

Immobilization of a molecular catalyst on carbon nanotubes for highly efficient electro-catalytic water oxidation.

PubMed

Li, Fusheng; Li, Lin; Tong, Lianpeng; Daniel, Quentin; Göthelid, Mats; Sun, Licheng

2014-11-21

Electrochemically driven water oxidation has been performed using a molecular water oxidation catalyst immobilized on hybrid carbon nanotubes and nano-material electrodes. A high turnover frequency (TOF) of 7.6 s(-1) together with a high catalytic current density of 2.2 mA cm(-2) was successfully obtained at an overpotential of 480 mV after 1 h of bulk electrolysis.

Use of vitreous carbon as a working electrode in coulometric titration of potassium hydrogen phthalate.

PubMed

Jennings, V J; Dodson, A; Tedds, G

1973-07-01

The use of a vitreous carbon electrode as a cathode in the amperostatic coulometric titration of aqueous potassium hydrogen phthalate solution is described. It is shown that 10 mg of the phthalate can be titrated with a precision better than 0.5%. Current-voltage curves for platinum and vitreous carbon cathodes show that there is an overpotential on the latter relative to the former.

Validating and improving a zero-dimensional stack voltage model of the Vanadium Redox Flow Battery

NASA Astrophysics Data System (ADS)

König, S.; Suriyah, M. R.; Leibfried, T.

2018-02-01

Simple, computationally efficient battery models can contribute significantly to the development of flow batteries. However, validation studies for these models on an industrial-scale stack level are rarely published. We first extensively present a simple stack voltage model for the Vanadium Redox Flow Battery. For modeling the concentration overpotential, we derive mass transfer coefficients from experimental results presented in the 1990s. The calculated mass transfer coefficient of the positive half-cell is 63% larger than of the negative half-cell, which is not considered in models published to date. Further, we advance the concentration overpotential model by introducing an apparent electrochemically active electrode surface which differs from the geometric electrode area. We use the apparent surface as fitting parameter for adapting the model to experimental results of a flow battery manufacturer. For adapting the model, we propose a method for determining the agreement between model and reality quantitatively. To protect the manufacturer's intellectual property, we introduce a normalization method for presenting the results. For the studied stack, the apparent electrochemically active surface of the electrode is 41% larger than its geometrical area. Hence, the current density in the diffusion layer is 29% smaller than previously reported for a zero-dimensional model.

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

Optimizing conditions for utilization of an H 2 oxidation catalyst with outer coordination sphere functionalities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Arnab; Ginovska, Bojana; Raugei, Simone

2016-01-01

Hydrogenase enzymes use abundant metals such as nickel and iron to efficiently interconvert H2 and protons. In this work, we demonstrate that a Ni-based catalyst can exceed the rates of enzymes with only slightly higher overpotentials using [Ni(PCy2Narginine2)2]7, containing an amino acid-based outer coordination sphere. Under conditions of high pressure, elevated temperature, and aqueous acidic solutions, conditions similar to those found in fuel cells, this electrocatalyst exhibits the fastest H2 oxidation reported to date for any homogeneous catalyst (TOF 1.1×106 s-1) operating at a moderate overpotential (240 mV). Control experiments demonstrate that both the appended outer coordination sphere and watermore » are important to achieve this impressive catalytic performance. This work was funded by the Office of Science Early Career Research Program through the US Department of Energy, Office of Science, Office of Basic Energy Sciences (AD, WJS), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (JASR) located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the US Department of Energy.« less

Crystal Phase and Architecture Engineering of Lotus-Thalamus-Shaped Pt-Ni Anisotropic Superstructures for Highly Efficient Electrochemical Hydrogen Evolution.

PubMed

Zhang, Zhicheng; Liu, Guigao; Cui, Xiaoya; Chen, Bo; Zhu, Yihan; Gong, Yue; Saleem, Faisal; Xi, Shibo; Du, Yonghua; Borgna, Armando; Lai, Zhuangchai; Zhang, Qinghua; Li, Bing; Zong, Yun; Han, Yu; Gu, Lin; Zhang, Hua

2018-06-07

The rational design and synthesis of anisotropic 3D nanostructures with specific composition, morphology, surface structure, and crystal phase is of significant importance for their diverse applications. Here, the synthesis of well-crystalline lotus-thalamus-shaped Pt-Ni anisotropic superstructures (ASs) via a facile one-pot solvothermal method is reported. The Pt-Ni ASs with Pt-rich surface are composed of one Ni-rich "core" with face-centered cubic (fcc) phase, Ni-rich "arms" with hexagonal close-packed phase protruding from the core, and facet-selectively grown Pt-rich "lotus seeds" with fcc phase on the end surfaces of the "arms." Impressively, these unique Pt-Ni ASs exhibit superior electrocatalytic activity and stability toward the hydrogen evolution reaction under alkaline conditions compared to commercial Pt/C and previously reported electrocatalysts. The obtained overpotential is as low as 27.7 mV at current density of 10 mA cm -2 , and the turnover frequency reaches 18.63 H 2 s -1 at the overpotential of 50 mV. This work provides a new strategy for the synthesis of highly anisotropic superstructures with a spatial heterogeneity to boost their promising application in catalytic reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Importance of Electrode Material in the Electrochemical Treatment of Wastewater Containing Organic Pollutants

NASA Astrophysics Data System (ADS)

Panizza, Marco

Electrochemical oxidation is a promising method for the treatment of wastewaters containing organic compounds. As a general rule, the electrochemical incineration of organics at a given electrode can take place at satisfactory rates and without electrode deactivation only at high anodic potentials in the region of the water discharge due to the participation of the intermediates of oxygen evolution. The nature of the electrode material strongly influences both the selectivity and the efficiency of the process. In particular, anodes with low oxygen evolution overpotential (i.e., good catalysts for oxygen evolution reactions), such as graphite, IrO2, RuO2, and Pt only permit the partial oxidation of organics, while anodes with high oxygen evolution overpotential (i.e., anodes that are poor catalysts for oxygen evolution reactions), such as SnO2, PbO2, and boron-doped diamond (BDD) favor the complete oxidation of organics to CO2 and so are ideal electrodes for wastewater treatment.However, the application of SnO2 and PbO2 anodes may be limited by their short service life and the risk of lead contamination, while BDD electrodes exhibit good chemical and electrochemical stability, a long life, and a wide potential window for water discharge, and are thus promising anodes for industrial-scale wastewater treatment.

Metallic Ni3S2 Films Grown by Atomic Layer Deposition as an Efficient and Stable Electrocatalyst for Overall Water Splitting.

PubMed

Ho, Thi Anh; Bae, Changdeuck; Nam, Hochul; Kim, Eunsoo; Lee, Seung Yong; Park, Jong Hyeok; Shin, Hyunjung

2018-04-18

We describe the direct preparation of crystalline Ni 3 S 2 thin films via atomic layer deposition (ALD) techniques at temperatures as low as 250 °C without postthermal treatments. A new ALD chemistry is proposed using bis(1-dimethylamino-2-methyl-2-butoxy) nickel(II) [Ni(dmamb) 2 ] and H 2 S as precursors. Homogeneous and conformal depositions of Ni 3 S 2 films were achieved on 4 in. wafers (both metal and oxide substrates, including Au and SiO 2 ). The resulting crystalline Ni 3 S 2 layers exhibited highly efficient and stable performance as electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline solutions, with a low overpotential of 300 mV and a high turnover frequency for HER and an overpotential of 400 mV for OER (at a current density of 10 mA/cm 2 ). Using our Ni 3 S 2 films as both the cathode and the anode, two-electrode full-cell electrolyzers were constructed, which showed stable operation for 100 h at a current density of 10 mA/cm 2 . The proposed ALD electrocatalysts on planar surfaces exhibited the best performance among Ni 3 S 2 materials for overall water splitting recorded to date.

Low Substrate Loading Limits Methanogenesis and Leads to High Coulombic Efficiency in Bioelectrochemical Systems

PubMed Central

Sleutels, Tom H. J. A.; Molenaar, Sam D.; Heijne, Annemiek Ter; Buisman, Cees J. N.

2016-01-01

A crucial aspect for the application of bioelectrochemical systems (BESs) as a wastewater treatment technology is the efficient oxidation of complex substrates by the bioanode, which is reflected in high Coulombic efficiency (CE). To achieve high CE, it is essential to give a competitive advantage to electrogens over methanogens. Factors that affect CE in bioanodes are, amongst others, the type of wastewater, anode potential, substrate concentration and pH. In this paper, we focus on acetate as a substrate and analyze the competition between methanogens and electrogens from a thermodynamic and kinetic point of view. We reviewed experimental data from earlier studies and propose that low substrate loading in combination with a sufficiently high anode overpotential plays a key-role in achieving high CE. Low substrate loading is a proven strategy against methanogenic activity in large-scale reactors for sulfate reduction. The combination of low substrate loading with sufficiently high overpotential is essential because it results in favorable growth kinetics of electrogens compared to methanogens. To achieve high current density in combination with low substrate concentrations, it is essential to have a high specific anode surface area. New reactor designs with these features are essential for BESs to be successful in wastewater treatment in the future. PMID:27681899

Electrode redox reactions with polarizable molecules.

PubMed

Matyushov, Dmitry V

2018-04-21

A theory of redox reactions involving electron transfer between a metal electrode and a polarizable molecule in solution is formulated. Both the existence of molecular polarizability and its ability to change due to electron transfer distinguish this problem from classical theories of interfacial electrochemistry. When the polarizability is different between the oxidized and reduced states, the statistics of thermal fluctuations driving the reactant over the activation barrier becomes non-Gaussian. The problem of electron transfer is formulated as crossing of two non-parabolic free energy surfaces. An analytical solution for these free energy surfaces is provided and the activation barrier of electrode electron transfer is given in terms of two reorganization energies corresponding to the oxidized and reduced states of the molecule in solution. The new non-Gaussian theory is, therefore, based on two theory parameters in contrast to one-parameter Marcus formulation for electrode reactions. The theory, which is consistent with the Nernst equation, predicts asymmetry between the cathodic and anodic branches of the electrode current. They show different slopes at small electrode overpotentials and become curved at larger overpotentials. However, the curvature of the Tafel plot is reduced compared to the Marcus-Hush model and approaches the empirical Butler-Volmer form with different transfer coefficients for the anodic and cathodic currents.

Electrode redox reactions with polarizable molecules

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.

2018-04-01

A theory of redox reactions involving electron transfer between a metal electrode and a polarizable molecule in solution is formulated. Both the existence of molecular polarizability and its ability to change due to electron transfer distinguish this problem from classical theories of interfacial electrochemistry. When the polarizability is different between the oxidized and reduced states, the statistics of thermal fluctuations driving the reactant over the activation barrier becomes non-Gaussian. The problem of electron transfer is formulated as crossing of two non-parabolic free energy surfaces. An analytical solution for these free energy surfaces is provided and the activation barrier of electrode electron transfer is given in terms of two reorganization energies corresponding to the oxidized and reduced states of the molecule in solution. The new non-Gaussian theory is, therefore, based on two theory parameters in contrast to one-parameter Marcus formulation for electrode reactions. The theory, which is consistent with the Nernst equation, predicts asymmetry between the cathodic and anodic branches of the electrode current. They show different slopes at small electrode overpotentials and become curved at larger overpotentials. However, the curvature of the Tafel plot is reduced compared to the Marcus-Hush model and approaches the empirical Butler-Volmer form with different transfer coefficients for the anodic and cathodic currents.

Full cell simulation and the evaluation of the buffer system on air-cathode microbial fuel cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ou, Shiqi; Kashima, Hiroyuki; Aaron, Douglas S.

This paper presents a computational model of a single chamber, air-cathode MFC. The model considers losses due to mass transport, as well as biological and electrochemical reactions, in both the anode and cathode half-cells. Computational fluid dynamics and Monod-Nernst analysis are incorporated into the reactions for the anode biofilm and cathode Pt catalyst and biofilm. The integrated model provides a macro-perspective of the interrelation between the anode and cathode during power production, while incorporating microscale contributions of mass transport within the anode and cathode layers. Model considerations include the effects of pH (H +/OH – transport) and electric field-driven migrationmore » on concentration overpotential, effects of various buffers and various amounts of buffer on the pH in the whole reactor, and overall impacts on the power output of the MFC. The simulation results fit the experimental polarization and power density curves well. Further, this model provides insight regarding mass transport at varying current density regimes and quantitative delineation of overpotentials at the anode and cathode. Altogether, this comprehensive simulation is designed to accurately predict MFC performance based on fundamental fluid and kinetic relations and guide optimization of the MFC system.« less

High-Performance Na-O2 Batteries Enabled by Oriented NaO2 Nanowires as Discharge Products.

PubMed

Khajehbashi, S Mohammad B; Xu, Lin; Zhang, Guobin; Tan, Shuangshuang; Zhao, Yan; Wang, Lai-Sen; Li, Jiantao; Luo, Wen; Peng, Dong-Liang; Mai, Liqiang

2018-06-13

Na-O 2 batteries are emerging rechargeable batteries due to their high theoretical energy density and abundant resources, but they suffer from sluggish kinetics due to the formation of large-size discharge products with cubic or irregular particle shapes. Here, we report the unique growth of discharge products of NaO 2 nanowires inside Na-O 2 batteries that significantly boosts the performance of Na-O 2 batteries. For this purpose, a high-spin Co 3 O 4 electrocatalyst was synthesized via the high-temperature oxidation of pure cobalt nanoparticles in an external magnetic field. The discharge products of NaO 2 nanowires are 10-20 nm in diameter and ∼10 μm in length, characteristics that provide facile pathways for electron and ion transfer. With these nanowires, Na-O 2 batteries have surpassed 400 cycles with a fixed capacity of 1000 mA h g -1 , an ultra-low over-potential of ∼60 mV during charging, and near-zero over-potential during discharging. This strategy not only provides a unique way to control the morphology of discharge products to achieve high-performance Na-O 2 batteries but also opens up the opportunity to explore growing nanowires in novel conditions.

Discharge, Relaxation, and Charge Model for the Lithium Trivanadate Electrode: Reactions, Phase Change, and Transport

DOE PAGES

Brady, Nicholas W.; Zhang, Qing; Knehr, K. W.; ...

2016-10-26

The electrochemical behavior of lithium trivanadate (LiV 3O 8) during lithiation, delithiation, and voltage recovery experiments is simulated using a crystal-scale model that accounts for solid-state diffusion, charge-transfer kinetics, and phase transformations. The kinetic expression for phase change was modeled using an approach inspired by the Avrami formulation for nucleation and growth. Numerical results indicate that the solid-state diffusion coefficient of lithium in LiV 3O 8 is ~ 10 -13 cm 2 s -1 and the equilibrium compositions in the two phase region (~2.5 V) are Li 2.5V 3O 8:Li 4V 3O 8. Agreement between the simulated and experimental resultsmore » is excellent. Relative to the lithiation curves, the experimental delithiation curves show significantly less overpotential and at low levels of lithiation (end of charge). Simulations are only able to capture this result by assuming that the solid-state mass-transfer resistance is less during delithiation. The proposed rationale for this difference is that the (100) face is inactive during lithiation, but active during delithiation. Finally, by assuming non-instantaneous phase-change kinetics, estimates are made for the overpotential due to imperfect phase change (supersaturation).« less

Low Substrate Loading Limits Methanogenesis and Leads to High Coulombic Efficiency in Bioelectrochemical Systems.

PubMed

Sleutels, Tom H J A; Molenaar, Sam D; Heijne, Annemiek Ter; Buisman, Cees J N

2016-01-05

A crucial aspect for the application of bioelectrochemical systems (BESs) as a wastewater treatment technology is the efficient oxidation of complex substrates by the bioanode, which is reflected in high Coulombic efficiency (CE). To achieve high CE, it is essential to give a competitive advantage to electrogens over methanogens. Factors that affect CE in bioanodes are, amongst others, the type of wastewater, anode potential, substrate concentration and pH. In this paper, we focus on acetate as a substrate and analyze the competition between methanogens and electrogens from a thermodynamic and kinetic point of view. We reviewed experimental data from earlier studies and propose that low substrate loading in combination with a sufficiently high anode overpotential plays a key-role in achieving high CE. Low substrate loading is a proven strategy against methanogenic activity in large-scale reactors for sulfate reduction. The combination of low substrate loading with sufficiently high overpotential is essential because it results in favorable growth kinetics of electrogens compared to methanogens. To achieve high current density in combination with low substrate concentrations, it is essential to have a high specific anode surface area. New reactor designs with these features are essential for BESs to be successful in wastewater treatment in the future.

Full cell simulation and the evaluation of the buffer system on air-cathode microbial fuel cell

DOE PAGES

Ou, Shiqi; Kashima, Hiroyuki; Aaron, Douglas S.; ...

2017-02-23

This paper presents a computational model of a single chamber, air-cathode MFC. The model considers losses due to mass transport, as well as biological and electrochemical reactions, in both the anode and cathode half-cells. Computational fluid dynamics and Monod-Nernst analysis are incorporated into the reactions for the anode biofilm and cathode Pt catalyst and biofilm. The integrated model provides a macro-perspective of the interrelation between the anode and cathode during power production, while incorporating microscale contributions of mass transport within the anode and cathode layers. Model considerations include the effects of pH (H +/OH – transport) and electric field-driven migrationmore » on concentration overpotential, effects of various buffers and various amounts of buffer on the pH in the whole reactor, and overall impacts on the power output of the MFC. The simulation results fit the experimental polarization and power density curves well. Further, this model provides insight regarding mass transport at varying current density regimes and quantitative delineation of overpotentials at the anode and cathode. Altogether, this comprehensive simulation is designed to accurately predict MFC performance based on fundamental fluid and kinetic relations and guide optimization of the MFC system.« less

Tin, Bismuth, and Tin–Bismuth Alloy Electrodeposition from Chlorometalate Salts in Deep Eutectic Solvents

PubMed Central

Vieira, Luciana; Burt, Jennifer; Richardson, Peter W.; Schloffer, Daniel; Fuchs, David; Moser, Alwin; Bartlett, Philip N.; Reid, Gillian

2017-01-01

Abstract The electrodeposition of tin, bismuth, and tin–bismuth alloys from SnII and BiIII chlorometalate salts in the choline chloride/ethylene glycol (1:2 molar ratio) deep eutectic solvent was studied on glassy carbon and gold by cyclic voltammetry, rotating disc voltammetry, and chronoamperometry. The SnII‐containing electrolyte showed one voltammetric redox process corresponding to SnII/Sn0. The diffusion coefficient of [SnCl3]−, detected as the dominating species by Raman spectroscopy, was determined from Levich and Cottrell analyses. The BiIII‐containing electrolyte showed two voltammetric reduction processes, both attributed to BiIII/Bi0. Dimensionless current/time transients revealed that the electrodeposition of both Sn and Bi on glassy carbon proceeded by 3D‐progressive nucleation at a low overpotential and changed to instantaneous at higher overpotentials. The nucleation rate of Bi on glassy carbon was considerably smaller than that of Sn. Elemental Sn and Bi were electrodeposited on Au‐coated glass slides from their respective salt solutions, as were Sn–Bi alloys from a 2:1 SnII/BiIII solution. The biphasic Sn–Bi alloys changed from a Bi‐rich composition to a Sn‐rich composition by making the deposition potential more negative. PMID:28638772

Growth kinetics of disk-shaped copper islands in electrochemical deposition.

PubMed

Guo, Lian; Zhang, Shouliang; Searson, Peter

2009-05-01

The ability to independently dictate the shape and crystal orientation of islands in electrocrystallization remains a significant challenge. The main reason for this is that the complex interplay between the substrate, nucleation, and surface chemistry is not fully understood. Here we report on the kinetics of island growth for copper on ruthenium oxide. The small nucleation overpotential leads to enhanced lateral growth and the formation of hexagonal disk-shaped islands. The amorphous substrate allows the nuclei to achieve the thermodynamically favorable orientation, i.e., a 111 surface normal. Island growth follows power law kinetics in both lateral and vertical directions. At shorter times, the two growth exponents are equal to 1/2 whereas at longer times lateral growth slows down while vertical growth speeds up. We propose a growth mechanism, wherein the lateral growth of disk-shaped islands is initiated by attachment of Cu adatoms on the ruthenium oxide surface onto the island periphery while vertical growth is initiated by two-dimensional nucleation on the top terrace and followed by lateral step propagation. These results indicate three criteria for enhanced lateral growth in electrodeposition: (i) a substrate that leads to a small nucleation overpotential, (ii) fast adatom surface diffusion on substrate to promote lateral growth, and (iii) preferential anion adsorption to stabilize the basal plane.

A theory of single-electron non-adiabatic tunneling through a small metal nanoparticle with due account of the strong interaction of valence electrons with phonons of the condensed matter environment.

PubMed

Medvedev, Igor G

2011-11-07

A theory of electrochemical behavior of small metal nanoparticles (NPs) which is governed both by the charging effect and the effect of the solvent reorganization on the dynamic of the electron transfer (ET) is considered under ambient conditions. The exact expression for the rate constant of ET from an electrode to NP which is valid for all values of the reorganization free energy E(r), bias voltage, and overpotential is obtained in the non-adiabatic limit. The tunnel current/overpotential relations are studied and calculated for different values of the bias voltage and E(r). The effect of E(r) on the full width at half maximum of the charging peaks is investigated at different values of the bias voltage. The differential conductance/bias voltage and the tunnel current/bias voltage dependencies are also studied and calculated. It is shown that, at room temperature, the pronounced Coulomb blockade oscillations in the differential conductance/bias voltage curves and the noticeable Coulomb staircase in the tunnel current/bias voltage relations are observed only at rather small values of E(r) in the case of the strongly asymmetric tunneling contacts.

Fe/N/C composite in Li-O2 battery: studies of catalytic structure and activity toward oxygen evolution reaction.

PubMed

Shui, Jiang-Lan; Karan, Naba K; Balasubramanian, Mahalingam; Li, Shu-You; Liu, Di-Jia

2012-10-10

Atomically dispersed Fe/N/C composite was synthesized and its role in controlling the oxygen evolution reaction during Li-O(2) battery charging was studied by use of a tetra(ethylene glycol) dimethyl ether-based electrolyte. Li-O(2) cells using Fe/N/C as the cathode catalyst showed lower overpotentials than α-MnO(2)/carbon catalyst and carbon-only material. Gases evolved during the charge step contained only oxygen for Fe/N/C cathode catalyst, whereas CO(2) was also detected in the case of α-MnO(2)/C or carbon-only material; this CO(2) was presumably generated from electrolyte decomposition. Our results reiterate the catalytic effect in reducing overpotentials, which not only enhances battery efficiency but also improves its lifespan by reducing or eliminating electrolyte decomposition. The structure of the Fe/N/C catalyst was characterized by transmission electron microscopy, scanning transmission electron microscopy, inductively coupled plasma optical emission spectroscopy, and X-ray absorption spectroscopy. Iron was found to be uniformly distributed within the carbon matrix, and on average, Fe was coordinated by 3.3 ± 0.6 and 2.2 ± 0.3 low Z elements (C/N/O) at bond distances of ~1.92 and ~2.09 Å, respectively.

An iron-iron hydrogenase mimic with appended electron reservoir for efficient proton reduction in aqueous media

PubMed Central

Becker, René; Amirjalayer, Saeed; Li, Ping; Woutersen, Sander; Reek, Joost N. H.

2016-01-01

The transition from a fossil-based economy to a hydrogen-based economy requires cheap and abundant, yet stable and efficient, hydrogen production catalysts. Nature shows the potential of iron-based catalysts such as the iron-iron hydrogenase (H2ase) enzyme, which catalyzes hydrogen evolution at rates similar to platinum with low overpotential. However, existing synthetic H2ase mimics generally suffer from low efficiency and oxygen sensitivity and generally operate in organic solvents. We report on a synthetic H2ase mimic that contains a redox-active phosphole ligand as an electron reservoir, a feature that is also crucial for the working of the natural enzyme. Using a combination of (spectro)electrochemistry and time-resolved infrared spectroscopy, we elucidate the unique redox behavior of the catalyst. We find that the electron reservoir actively partakes in the reduction of protons and that its electron-rich redox states are stabilized through ligand protonation. In dilute sulfuric acid, the catalyst has a turnover frequency of 7.0 × 104 s−1 at an overpotential of 0.66 V. This catalyst is tolerant to the presence of oxygen, thereby paving the way for a new generation of synthetic H2ase mimics that combine the benefits of the enzyme with synthetic versatility and improved stability. PMID:26844297

Self-supported three-dimensional Cu/Cu2O-CuO/rGO nanowire array electrodes for an efficient hydrogen evolution reaction.

PubMed

Ye, Lin; Wen, Zhenhai

2018-06-14

We report the fabrication of self-supported Cu/Cu2O-CuO/rGO nanowire arrays on commercial porous copper foam, which exhibit excellent activity and durability for electrochemical hydrogen evolution, presenting a small onset potential of 84 mV and a low overpotential of 105 mV at a current density of 10 mA cm-2.

Improving the intrinsic electrocatalytic hydrogen evolution activity of few-layer NiPS3 by cobalt doping.

PubMed

Li, Kai; Rakov, Dmitrii; Zhang, Wei; Xu, Ping

2017-07-18

Here we demonstrate the improvement of the intrinsic electrocatalytic hydrogen evolution activity of NiPS 3 by proper cobalt doping. The optimized Ni 0.95 Co 0.05 PS 3 nanosheets display a geometric catalytic current density of -10 mA cm -2 at an overpotential of 71 mV vs. RHE and a Tafel slope of 77 mV dec -1 in 1.0 M KOH.

Polypyrrole-derived nitrogen and oxygen co-doped mesoporous carbons as efficient metal-free electrocatalyst for hydrazine oxidation.

PubMed

Meng, Yuying; Zou, Xiaoxin; Huang, Xiaoxi; Goswami, Anandarup; Liu, Zhongwu; Asefa, Tewodros

2014-10-08

We demonstrate that polypyrrole-derived nitrogen and oxygen co-doped mesoporous carbons can serve as efficient, metal-free electrocatalysts for hydrazine oxidation reaction, with low overpotential and high current density. The materials' structures and the nature and type of their included dopants, which can be controlled by varying the synthetic conditions, can affect the electrocatalytic properties of the materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic, Organometallic and Bioorganic Catalysts for Electrochemical Reduction of CO2

PubMed Central

Schlager, Stefanie; Portenkirchner, Engelbert; Sariciftci, Niyazi Serdar

2017-01-01

Abstract A broad review of homogeneous and heterogeneous catalytic approaches toward CO2 reduction using organic, organometallic, and bioorganic systems is provided. Electrochemical, bioelectrochemical and photoelectrochemical approaches are discussed in terms of their faradaic efficiencies, overpotentials and reaction mechanisms. Organometallic complexes as well as semiconductors and their homogeneous and heterogeneous catalytic activities are compared to enzymes. In both cases, their immobilization on electrodes is discussed and compared to homogeneous catalysts in solution. PMID:28383174

Mechanism and Kinetics of Li2S Precipitation in Lithium-Sulfur Batteries.

PubMed

Fan, Frank Y; Carter, W Craig; Chiang, Yet-Ming

2015-09-16

The kinetics of Li2 S electrodeposition onto carbon in lithium-sulfur batteries are characterized. Electrodeposition is found to be dominated by a 2D nucleation and growth process with rate constants that depend strongly on the electrolyte solvent. Nucleation is found to require a greater overpotential than growth, which results in a morphology that is dependent on the discharge rate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High‐Performance Lithium‐Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt

PubMed Central

Ahn, Su Mi; Suk, Jungdon; Kim, Do Youb; Kim, Hwan Kyu

2017-01-01

Abstract To fabricate a sustainable lithium‐oxygen (Li‐O2) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO3) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO3 exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV‐DEMS study confirms that the TMS‐LiNO3 electrolyte efficiently produces NO2 −, which initiates a redox shuttle reaction. Interestingly, this NO2 −/NO2 redox reaction derived from the LiNO3 salt is not very effective in solvents other than TMS. Compared with other common Li‐O2 solvents, TMS seems optimum solvent for the efficient use of LiNO3 salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO2 −/NO2 redox reaction, which results in a high‐performance Li‐O2 battery. PMID:29051863

Oxygen Vacancy Engineering of Co3 O4 Nanocrystals through Coupling with Metal Support for Water Oxidation.

PubMed

Zhang, Jun-Jun; Wang, Hong-Hui; Zhao, Tian-Jian; Zhang, Ke-Xin; Wei, Xiao; Jiang, Zhi-Dong; Hirano, Shin-Ichi; Li, Xin-Hao; Chen, Jie-Sheng

2017-07-21

Oxygen vacancies can help to capture oxygen-containing species and act as active centers for oxygen evolution reaction (OER). Unfortunately, effective methods for generating a high amount of oxygen vacancies on the surface of various nanocatalysts are rather limited. Here, we described an effective way to generate oxygen-vacancy-rich surface of transition metal oxides, exemplified with Co 3 O 4 , simply by constructing highly coupled interface of ultrafine Co 3 O 4 nanocrystals and metallic Ti. Impressively, the amounts of oxygen vacancy on the surface of Co 3 O 4 /Ti surpassed the reported values of the Co 3 O 4 modified even under highly critical conditions. The Co 3 O 4 /Ti electrode could provide a current density of 23 mA cm -2 at an OER overpotential of 570 mV, low Tafel slope, and excellent durability in neutral medium. Because of the formation of a large amount of oxygen vacancies as the active centers for OER on the surface, the TOF value of the Co 3 O 4 @Ti electrode was optimized to be 3238 h -1 at an OER overpotential of 570 mV, which is 380 times that of the state-of-the-art non-noble nanocatalysts in the literature. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Importance of Nanometric Passivating Films on Cathodes forLi - Air Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adams, Brian D.; Black, Robert; Radtke, Claudio

2014-12-23

Recently, there has been a transition from fully carbonaceous positive electrodes for the aprotic lithium oxygen battery to alternative materials and the use of redox mediator additives, in an attempt to lower the large electrochemical overpotentials associated with the charge reaction. However, the stabilizing or catalytic effect of these materials can become complicated due to the presence of major side-reactions observed during dis(charge). Here, we isolate the charge reaction from the discharge by utilizing electrodes prefilled with commercial lithium peroxide with a crystallite size of about 200-800 nm. Using a combination of S/TEM, online mass spectrometry, XPS, and electrochemical methodsmore » to probe the nature of surface films on carbon and conductive Ti-based nanoparticles, we show that oxygen evolution from lithium peroxide is strongly dependent on their surface properties. Insulating TiO2 surface layers on TiC and TiN - even as thin as 3 nm*can completely inhibit the charge reaction under these conditions. On the other hand, TiC, which lacks this oxide film, readily facilitates oxidation of the bulk Li2O2 crystallites, at a much lower overpotential relative to carbon. Since oxidation of lithium oxygen battery cathodes is inevitable in these systems, precise control of the surface chemistry at the nanoscale becomes of upmost importance.« less

Durability of Pt-Co Alloy Polymer Electrolyte Fuel Cell Cathode Catalysts under Accelerated Stress Tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Papadias, D. D.; Ahluwalia, R. K.; Kariuki, N.

The durability of Pt-Co alloy cathode catalysts supported on high surface area carbon is investigated by subjecting them to accelerated stress tests (ASTs). The catalysts had different initial Co contents and nanoparticle morphologies: a “spongy” porous morphology for the high-Co (H) content catalyst, and a fully alloyed crystalline morphology for the medium-Co (M) and low-Co (L) content catalysts. The specific activity of the catalysts depends on their initial Co content, morphology and nanoparticle size, and remained higher than 1000 μA/cm 2-Pt after 27–50% Co loss. The H-catalyst electrode showed the smallest kinetic overpotentials (η c s) due to higher initialmore » Pt loading than the other two electrodes, but it had the fastest increase in ηcs with AST cycling due to lower Co retention; the L-catalyst electrode showed higher η c s due to a lower initial Pt loading, but had a smaller increase in η c s with aging due to higher Co retention; the M-catalyst electrode showed a similar increase in η c s with aging, but this increase was due to the combined effects of Co dissolution and electrochemically active surface area (ECSA) loss. In conclusion, the modeled increase in mass transfer overpotentials with aging correlates with the initial Pt loading, ECSA loss and the initial catalyst morphology« less

A lyophilized and thermal two step synthesis of CoFe alloy nanoparticles embedded in N-doped carbon nanosheets/carbon nanotubes for highly-efficient oxygen evolution reaction.

PubMed

Liu, Yang; Li, Feng; Yang, Haidong; Li, Jing; Ma, Ping; Zhu, Yan; Ma, Jiantai

2018-05-22

There is a vital need to explore highly-efficient and stable nonprecious-metal catalysts for oxygen evolution reaction (OER) to reduce the overpotential and further improve the energy conversion efficiency. Herein, we report a unique and cost-effective lyophilized and thermal two step procedure to synthesize high-performance CoFe alloy nanoparticles embedded in N-doped carbon nanosheets interspersed with carbon nanotubes (CoFe-N-CN/CNTs) hybrid. The lyophilization step during catalysts preparation is beneficial to uniform the dispersion of carbon-like precursors and avoid the agglomeration of metal particles. Meanwhile, the inserted CNTs and doped N in this hybrid provide better electrical conductivity, more chemically active sites, improved mass transport capability and effective gas adsorption/release channels. And all these lead to a high specific surface area of 240.67 m2 g-1, favorable stability and remarkable OER activities with an overpotential of only 285 mV at the current density of 10 mA cm-2 and a Tafel slope of 51.09 mV dec-1 in 1.0 M KOH electrolyte, which is even superior to commercial IrO2 catalysts. The CoFe-N-CN/CNTs hybrid thus exhibits great potential as a highly efficient and earth-abundant anode OER electrocatalyst. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photocatalytic water splitting—The untamed dream: A review of recent advances

DOE PAGES

Jafari, Tahereh; Moharreri, Ehsan; Amin, Alireza Shirazi; ...

2016-07-09

Here, photocatalytic water splitting using sunlight is a promising technology capable of providing high energy yield without pollutant byproducts. Herein, we review various aspects of this technology including chemical reactions, physiochemical conditions and photocatalyst types such as metal oxides, sulfides, nitrides, nanocomposites, and doped materials followed by recent advances in computational modeling of photoactive materials. As the best-known catalyst for photocatalytic hydrogen and oxygen evolution, TiO 2 is discussed in a separate section, along with its challenges such as the wide band gap, large overpotential for hydrogen evolution, and rapid recombination of produced electron-hole pairs. Various approaches are addressed tomore » overcome these shortcomings, such as doping with different elements, heterojunction catalysts, noble metal deposition, and surface modification. Development of a photocatalytic corrosion resistant, visible light absorbing, defect-tuned material with small particle size is the key to complete the sunlight to hydrogen cycle efficiently. Computational studies have opened new avenues to understand and predict the electronic density of states and band structure of advanced materials and could pave the way for the rational design of efficient photocatalysts for water splitting. Future directions are focused on developing innovative junction architectures, novel synthesis methods and optimizing the existing active materials to enhance charge transfer, visible light absorption, reducing the gas evolution overpotential and maintaining chemical and physical stability« less

Durability of Pt-Co Alloy Polymer Electrolyte Fuel Cell Cathode Catalysts under Accelerated Stress Tests

DOE PAGES

Papadias, D. D.; Ahluwalia, R. K.; Kariuki, N.; ...

2018-03-17

The durability of Pt-Co alloy cathode catalysts supported on high surface area carbon is investigated by subjecting them to accelerated stress tests (ASTs). The catalysts had different initial Co contents and nanoparticle morphologies: a “spongy” porous morphology for the high-Co (H) content catalyst, and a fully alloyed crystalline morphology for the medium-Co (M) and low-Co (L) content catalysts. The specific activity of the catalysts depends on their initial Co content, morphology and nanoparticle size, and remained higher than 1000 μA/cm 2-Pt after 27–50% Co loss. The H-catalyst electrode showed the smallest kinetic overpotentials (η c s) due to higher initialmore » Pt loading than the other two electrodes, but it had the fastest increase in ηcs with AST cycling due to lower Co retention; the L-catalyst electrode showed higher η c s due to a lower initial Pt loading, but had a smaller increase in η c s with aging due to higher Co retention; the M-catalyst electrode showed a similar increase in η c s with aging, but this increase was due to the combined effects of Co dissolution and electrochemically active surface area (ECSA) loss. In conclusion, the modeled increase in mass transfer overpotentials with aging correlates with the initial Pt loading, ECSA loss and the initial catalyst morphology« less

A High Performance H2-Cl2 Fuel Cell for Space Power Applications

NASA Technical Reports Server (NTRS)

Anderson, Everett B.; Taylor, E. Jennings; Wilemski, Gerald; Gelb, Alan

1993-01-01

NASA has numerous airborne/spaceborne applications for which high power and energy density power sources are needed. The proton exchange membrane fuel cell (PEMFC) is an attractive candidate for such a power source. PEMFC's offer many advantages for airborne/spaceborne applications. They have high power and energy densities, convert fuel to electrical power with high efficiency at both part and full load, and can rapidly startup and shutdown. In addition, PEMFC's are lightweight and operate silently. A significant impediment to the attainment of very high power and energy densities by PEMFC's is their current exclusive reliance on oxygen as the oxidant. Conventional PEMFC's oxidize hydrogen at the anode and reduce oxygen at the cathode. The electrode kinetics of oxygen reduction are known to be highly irreversible, incurring large overpotential losses. In addition, the modest open circuit potential of 1.2V for the H2-O2 fuel cell is unattainable due to mixed potential effects at the oxygen electrode. Because of the high overpotential losses, cells using H2 and O2 are capable of achieving high current densities only at very low cell voltages, greatly curtailing their power output. Based on experimental work on chlorine reduction in a gas diffusion electrode, we believe significant increases in both the energy and power densities of PEMFC systems can be achieved by employing chlorine as an alternative oxidant.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Zhiyi; Chen, Guangxu; Li, Yanbin

Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces andmore » their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.« less

Bio-inspired cofacial Fe porphyrin dimers for efficient electrocatalytic CO2 to CO conversion: Overpotential tuning by substituents at the porphyrin rings

PubMed Central

Zahran, Zaki N.; Mohamed, Eman A.; Naruta, Yoshinori

2016-01-01

Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe−containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push−pull mechanism. Bio−inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe−Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe−Fe separation distance. PMID:27087483

Multilayer Ni/Fe thin films as oxygen evolution catalysts for solar fuel production

NASA Astrophysics Data System (ADS)

Biset-Peiró, M.; Murcia-López, S.; Fàbrega, C.; Morante, J. R.; Andreu, T.

2017-03-01

The slow kinetics and high overpotential of the oxygen evolution reaction is one of the main limiting factors to achieve the minimum required performances of the so-called photoelectrochemical water splitting systems. An oxygen evolution catalyst (OEC) becomes essential in order to perform this process with higher efficiency. Herein, we report the physical, optical and electrochemical characterization of multilayer Ni/Fe thin films as earth-abundant OEC, to avoid the use of platinum group metals (PGM). Uniform films of thicknesses ranging from 1 to 10 nm were fabricated by sequential and alternate thermal evaporation of Ni and Fe. It was found that the successive deposition allows the fabrication of a Ni terminated surface that does not need activation due to the Fe underlayer. The lowest overpotential achieved for NiFe was 370 mV at 10 mA cm-2 and a Tafel slope of 37 mV dec-1 with 1 nm thickness and 95% transmittance. Finally, NiFe OEC was implemented on top of Mo:BiVO4 photoanodes which resulted in a reduction of the open circuit potential of 0.2 V and up to five fold increase of the oxidation efficiency at 0.7 VRHE. The results presented facilitate the practical implementation of BiVO4 photoanodes in tandem configuration for bias free photoassisted water splitting.

Bio-inspired cofacial Fe porphyrin dimers for efficient electrocatalytic CO2 to CO conversion: Overpotential tuning by substituents at the porphyrin rings.

PubMed

Zahran, Zaki N; Mohamed, Eman A; Naruta, Yoshinori

2016-04-18

Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe-containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push-pull mechanism. Bio-inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe-Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe-Fe separation distance.

Bio-inspired cofacial Fe porphyrin dimers for efficient electrocatalytic CO2 to CO conversion: Overpotential tuning by substituents at the porphyrin rings

NASA Astrophysics Data System (ADS)

Zahran, Zaki N.; Mohamed, Eman A.; Naruta, Yoshinori

2016-04-01

Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe-containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push-pull mechanism. Bio-inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe-Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe-Fe separation distance.

High-Performance Lithium-Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt.

PubMed

Ahn, Su Mi; Suk, Jungdon; Kim, Do Youb; Kang, Yongku; Kim, Hwan Kyu; Kim, Dong Wook

2017-10-01

To fabricate a sustainable lithium-oxygen (Li-O 2 ) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO 3 ) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO 3 exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV-DEMS study confirms that the TMS-LiNO 3 electrolyte efficiently produces NO 2 - , which initiates a redox shuttle reaction. Interestingly, this NO 2 - /NO 2 redox reaction derived from the LiNO 3 salt is not very effective in solvents other than TMS. Compared with other common Li-O 2 solvents, TMS seems optimum solvent for the efficient use of LiNO 3 salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO 2 - /NO 2 redox reaction, which results in a high-performance Li-O 2 battery.

Iron oxide/carbon black (Fe2O3/CB) composite electrode for the detection of reduced nicotinamide cofactors using an amperometric method under a low overpotential.

PubMed

Kim, Yang Hee; Kim, Taeho; Ryu, Ji Heon; Yoo, Young Je

2010-01-15

An amperometric biosensor for the detection of the reduced nicotinamide cofactors NADH and NADPH was designed, based on the electrochemical oxidation of NAD(P)H with an iron oxide/carbon black composite (Fe(2)O(3)/CB) electrode. The electrode exhibited excellent performances in that it led to a substantial decrease in the overpotential of electrochemical NADH oxidation. Iron oxide plays a significant role as a catalyst for NADH oxidation and the reaction occurs at +0.00 V (vs. Ag/AgCl). The method of the sensor construction is very simple and the sensor performed well, giving high sensitivity, high stability, and a broad detection range. The sensitivity of this system is 2.54 microA mM(-1) and the limit of detection (S/N=3) is 10 microM. A linear range was observed between 10 microM and 1000 microM of NADH (R(2)=0.993), which is preferable to that of the previous studies. The Fe(2)O(3)/CB electrode also oxidizes NADPH under the same condition and can be applied as an NADPH sensor. Moreover, when the sensor system was integrated into a dehydrogenase-based sensor system, it also showed a good sensing performance. Copyright 2009 Elsevier B.V. All rights reserved.

Transition Metal Polypyridine Complexes: Studies of Mediation in Dye-Sensitized Solar Cells and Charge Separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elliott, C. Michael; Prieto, Amy L.

2017-02-08

The Elliott group has long been supported by DOE for studies of cobalt(II/III) trisbypiridine (DTB) mediator complexes in dye sensitized solar cells. Previous work demonstrated that Co(II/III) chemistry is sensitive to the environment, showing unprecedented electrode-surface and electrolyte dependant voltammetry. In electrolytes that have large lipophilic cations, voltammetry of the [Co(DTB) 3] 2+/3+ couple is nearly Nernstian in appearance on nominally oxide-free metal surfaces. In contrast, on semiconductor electrodes in electrolytes with small, hard cations such as Li +, the electron transfer rates are so slow that it is difficult to measure any Faradaic current even at overpotentials of ±1more » V. These studies are of direct relevance to the operation of cobalt-based mediators in solar cells. The research has also shown that these mediators are compatible with copper phenantroline based dyes, in contrast to I - due to the insolubility of CuI.« less

Efficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction

PubMed Central

Cummins, Dustin R.; Martinez, Ulises; Sherehiy, Andriy; Kappera, Rajesh; Martinez-Garcia, Alejandro; Schulze, Roland K.; Jasinski, Jacek; Zhang, Jing; Gupta, Ram K.; Lou, Jun; Chhowalla, Manish; Sumanasekera, Gamini; Mohite, Aditya D.; Sunkara, Mahendra K.; Gupta, Gautam

2016-01-01

Hydrogen evolution reaction is catalysed efficiently with precious metals, such as platinum; however, transition metal dichalcogenides have recently emerged as a promising class of materials for electrocatalysis, but these materials still have low activity and durability when compared with precious metals. Here we report a simple one-step scalable approach, where MoOx/MoS2 core-shell nanowires and molybdenum disulfide sheets are exposed to dilute aqueous hydrazine at room temperature, which results in marked improvement in electrocatalytic performance. The nanowires exhibit ∼100 mV improvement in overpotential following exposure to dilute hydrazine, while also showing a 10-fold increase in current density and a significant change in Tafel slope. In situ electrical, gate-dependent measurements and spectroscopic investigations reveal that hydrazine acts as an electron dopant in molybdenum disulfide, increasing its conductivity, while also reducing the MoOx core in the core-shell nanowires, which leads to improved electrocatalytic performance. PMID:27282871

Efficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction.

PubMed

Cummins, Dustin R; Martinez, Ulises; Sherehiy, Andriy; Kappera, Rajesh; Martinez-Garcia, Alejandro; Schulze, Roland K; Jasinski, Jacek; Zhang, Jing; Gupta, Ram K; Lou, Jun; Chhowalla, Manish; Sumanasekera, Gamini; Mohite, Aditya D; Sunkara, Mahendra K; Gupta, Gautam

2016-06-10

Hydrogen evolution reaction is catalysed efficiently with precious metals, such as platinum; however, transition metal dichalcogenides have recently emerged as a promising class of materials for electrocatalysis, but these materials still have low activity and durability when compared with precious metals. Here we report a simple one-step scalable approach, where MoOx/MoS2 core-shell nanowires and molybdenum disulfide sheets are exposed to dilute aqueous hydrazine at room temperature, which results in marked improvement in electrocatalytic performance. The nanowires exhibit ∼100 mV improvement in overpotential following exposure to dilute hydrazine, while also showing a 10-fold increase in current density and a significant change in Tafel slope. In situ electrical, gate-dependent measurements and spectroscopic investigations reveal that hydrazine acts as an electron dopant in molybdenum disulfide, increasing its conductivity, while also reducing the MoOx core in the core-shell nanowires, which leads to improved electrocatalytic performance.

Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene

DOE PAGES

Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.; ...

2016-06-30

There is an urgent need to develop technologies that use renewable energy to convert waste products such as carbon dioxide into hydrocarbon fuels. Carbon dioxide can be electrochemically reduced to hydrocarbons over copper catalysts, although higher efficiency is required. We have developed oxidized copper catalysts displaying lower overpotentials for carbon dioxide electroreduction and record selectivity towards ethylene (60%) through facile and tunable plasma treatments. Herein we provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. Operando X-ray absorption spectroscopy and cross-sectional scanning transmission electron microscopy show that copper oxides aremore » surprisingly resistant to reduction and copper + species remain on the surface during the reaction. Furthermore, our results demonstrate that the roughness of oxide-derived copper catalysts plays only a partial role in determining the catalytic performance, while the presence of copper + is key for lowering the onset potential and enhancing ethylene selectivity.« less

Assessing the Health of LiFePO4 Traction Batteries through Monotonic Echo State Networks

PubMed Central

Anseán, David; Otero, José; Couso, Inés

2017-01-01

A soft sensor is presented that approximates certain health parameters of automotive rechargeable batteries from on-vehicle measurements of current and voltage. The sensor is based on a model of the open circuit voltage curve. This last model is implemented through monotonic neural networks and estimate over-potentials arising from the evolution in time of the Lithium concentration in the electrodes of the battery. The proposed soft sensor is able to exploit the information contained in operational records of the vehicle better than the alternatives, this being particularly true when the charge or discharge currents are between moderate and high. The accuracy of the neural model has been compared to different alternatives, including data-driven statistical models, first principle-based models, fuzzy observers and other recurrent neural networks with different topologies. It is concluded that monotonic echo state networks can outperform well established first-principle models. The algorithms have been validated with automotive Li-FePO4 cells. PMID:29267219

Electrochemical Transport Phenomena in Hybrid Pseudocapacitors under Galvanostatic Cycling

DOE PAGES

d'Entremont, Anna L.; Girard, Henri -Louis; Wang, Hainan; ...

2015-11-18

Here, this study aims to provide insights into the electrochemical transport and interfacial phenomena in hybrid pseudocapacitors under galvanostatic cycling. Pseudocapacitors are promising electrical energy storage devices for applications requiring large power density. They also involve complex, coupled, and multiscale physical phenomena that are difficult to probe experimentally. The present study performed detailed numerical simulations for a hybrid pseudocapacitor with planar electrodes and binary, asymmetric electrolyte under various cycling conditions, based on a first-principles continuum model accounting simultaneously for charge storage by electric double layer (EDL) formation and by faradaic reactions with intercalation. Two asymptotic regimes were identified corresponding tomore » (i) dominant faradaic charge storage at low current and low frequency or (ii) dominant EDL charge storage at high current and high frequency. Analytical expressions for the intercalated ion concentration and surface overpotential were derived for both asymptotic regimes. Features of typical experimentally measured cell potential were physically interpreted. These insights could guide the optimization of hybrid pseudocapacitors.« less

Preparation of Cobalt-Based Electrodes by Physical Vapor Deposition on Various Nonconductive Substrates for Electrocatalytic Water Oxidation.

PubMed

Wu, Yizhen; Wang, Le; Chen, Mingxing; Jin, Zhaoxia; Zhang, Wei; Cao, Rui

2017-12-08

Artificial photosynthesis requires efficient anodic electrode materials for water oxidation. Cobalt metal thin films are prepared through facile physical vapor deposition (PVD) on various nonconductive substrates, including regular and quartz glass, mica sheet, polyimide, and polyethylene terephthalate (PET). Subsequent surface electrochemical modification by cyclic voltammetry (CV) renders these films active for electrocatalytic water oxidation, reaching a current density of 10 mA cm -2 at a low overpotential of 330 mV in 1.0 m KOH solution. These electrodes are robust with unchanged activity throughout prolonged chronopotentiometry measurements. This work is thus significant to show that the combination of PVD and CV is very valuable and convenient to fabricate active electrodes on various nonconductive substrates, particularly with flexible polyimide and PET substrates. This efficient, safe and convenient method can potentially be expanded to many other electrochemical applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring local redox processes in LiNi0.5Mn1.5O4 battery cathode material by in operando EPR spectroscopy.

PubMed

Niemöller, Arvid; Jakes, Peter; Eurich, Svitlana; Paulus, Anja; Kungl, Hans; Eichel, Rüdiger-A; Granwehr, Josef

2018-01-07

Despite the multitude of analytical methods available to characterize battery cathode materials, identifying the factors responsible for material aging is still challenging. We present the first investigation of transient redox processes in a spinel cathode during electrochemical cycling of a lithium ion battery by in operando electron paramagnetic resonance (EPR). The battery contains a LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathode, which is a material whose magnetic interactions are well understood. The evolution of the EPR signal in combination with electrochemical measurements shows the impact of Mn 3+ on the Li + motion inside the spinel. Moreover, state of charge dependent linewidth variations confirm the formation of a solid solution for slow cycling, which is taken over by mixed models of solid solution and two-phase formation for fast cycling due to kinetic restrictions and overpotentials. Long-term measurements for 480 h showed the stability of the investigated LNMO, but also small amounts of cathode degradation products became visible. The results point out how local, exchange mediated magnetic interactions in cathode materials are linked with battery performance and can be used for material characterization.

The effects of minor elements in La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes on oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Oishi, Junya; Otomo, Junichiro; Oshima, Yoshito; Koyama, Michihisa

2015-03-01

It is known that the minor elements affect the performance of solid oxide fuel cell (SOFC). In this study, we focus on the influence of minor elements on the SOFC cathode properties. The Ca, Ba, Al, and Si, which originate from raw materials and production processes for SOFC cathodes, are investigated as minor elements that may have effect on the properties of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode. To examine the effects of minor elements on the cathode properties, Ca, Ba, Al, and Si with a controlled concentration are added to the LSCF reference sample. Conductivity relaxation measurements are conducted to determine the chemical diffusion coefficient (Dchem) and surface exchange coefficient (ktr), which governs the overpotential characteristics of the LSCF cathode. The results show that Al and Si have negative effects on both Dchem and ktr while Ca and Ba do not alter Dchem and show weakly positive effects on ktr. The effects of Ca and Ba for the cathode properties are discussed on the basis of XPS measurements.

Monitoring local redox processes in LiNi0.5Mn1.5O4 battery cathode material by in operando EPR spectroscopy

NASA Astrophysics Data System (ADS)

Niemöller, Arvid; Jakes, Peter; Eurich, Svitlana; Paulus, Anja; Kungl, Hans; Eichel, Rüdiger-A.; Granwehr, Josef

2018-01-01

Despite the multitude of analytical methods available to characterize battery cathode materials, identifying the factors responsible for material aging is still challenging. We present the first investigation of transient redox processes in a spinel cathode during electrochemical cycling of a lithium ion battery by in operando electron paramagnetic resonance (EPR). The battery contains a LiNi0.5Mn1.5O4 (LNMO) spinel cathode, which is a material whose magnetic interactions are well understood. The evolution of the EPR signal in combination with electrochemical measurements shows the impact of Mn3+ on the Li+ motion inside the spinel. Moreover, state of charge dependent linewidth variations confirm the formation of a solid solution for slow cycling, which is taken over by mixed models of solid solution and two-phase formation for fast cycling due to kinetic restrictions and overpotentials. Long-term measurements for 480 h showed the stability of the investigated LNMO, but also small amounts of cathode degradation products became visible. The results point out how local, exchange mediated magnetic interactions in cathode materials are linked with battery performance and can be used for material characterization.

Fast electron transfer through a single molecule natively structured redox protein

NASA Astrophysics Data System (ADS)

Della Pia, Eduardo Antonio; Chi, Qijin; MacDonald, J. Emyr; Ulstrup, Jens; Jones, D. Dafydd; Elliott, Martin

2012-10-01

The electron transfer properties of proteins are normally measured as molecularly averaged ensembles. Through these and related measurements, proteins are widely regarded as macroscopically insulating materials. Using scanning tunnelling microscopy (STM), we present new measurements of the conductance through single-molecules of the electron transfer protein cytochrome b562 in its native conformation, under pseudo-physiological conditions. This is achieved by thiol (SH) linker pairs at opposite ends of the molecule through protein engineering, resulting in defined covalent contact between a gold surface and a platinum-iridium STM tip. Two different orientations of the linkers were examined: a long-axis configuration (SH-LA) and a short-axis configuration (SH-SA). In each case, the molecular conductance could be `gated' through electrochemical control of the heme redox state. Reproducible and remarkably high conductance was observed in this relatively complex electron transfer system, with single-molecule conductance values peaking around 18 nS and 12 nS for the SH-SA and SH-LA cytochrome b562 molecules near zero electrochemical overpotential. This strongly points to the important role of the heme co-factor bound to the natively structured protein. We suggest that the two-step model of protein electron transfer in the STM geometry requires a multi-electron transfer to explain such a high conductance. The model also yields a low value for the reorganisation energy, implying that solvent reorganisation is largely absent.The electron transfer properties of proteins are normally measured as molecularly averaged ensembles. Through these and related measurements, proteins are widely regarded as macroscopically insulating materials. Using scanning tunnelling microscopy (STM), we present new measurements of the conductance through single-molecules of the electron transfer protein cytochrome b562 in its native conformation, under pseudo-physiological conditions. This is achieved by thiol (SH) linker pairs at opposite ends of the molecule through protein engineering, resulting in defined covalent contact between a gold surface and a platinum-iridium STM tip. Two different orientations of the linkers were examined: a long-axis configuration (SH-LA) and a short-axis configuration (SH-SA). In each case, the molecular conductance could be `gated' through electrochemical control of the heme redox state. Reproducible and remarkably high conductance was observed in this relatively complex electron transfer system, with single-molecule conductance values peaking around 18 nS and 12 nS for the SH-SA and SH-LA cytochrome b562 molecules near zero electrochemical overpotential. This strongly points to the important role of the heme co-factor bound to the natively structured protein. We suggest that the two-step model of protein electron transfer in the STM geometry requires a multi-electron transfer to explain such a high conductance. The model also yields a low value for the reorganisation energy, implying that solvent reorganisation is largely absent. Electronic supplementary information (ESI) available: Experimental methods, DNA and protein sequences, additional STM statistical analysis and images, electrochemical data and It-z data analysis. See DOI: 10.1039/c2nr32131a

Efficient Electrocatalytic Water Oxidation at Neutral and High pH by Adventitious Nickel at Nanomolar Concentrations.

PubMed

Roger, Isolda; Symes, Mark D

2015-11-04

Electrolytic water oxidation using earth-abundant elements is a key challenge in the quest to develop cheap, large surface area arrays for solar-to-hydrogen conversion. There have been numerous studies in this area in recent years, but there remains an imperative to demonstrate that the current densities reported are indeed due to the species under consideration and not due to the presence of adventitious (yet possibly highly active) contaminants at low levels. Herein, we show that adventitious nickel at concentrations as low as 17 nM can act as a water oxidation catalyst in mildly basic aqueous solutions, achieving stable (tens of hours) current densities of 1 mA cm(-2) at overpotentials as low as 540 mV at pH 9.2 and 400 mV at pH 13. This nickel was not added to the electrolysis baths deliberately, but it was found to be present in the electrolytes as an impurity by ICP-MS. The presence of nickel on anodes from extended-time bulk electrolysis experiments was confirmed by XPS. In showing that such low levels of nickel can perform water oxidation at overpotentials comparable to many recently reported water oxidation catalysts, this work serves to raise the burden of proof required of new materials in this field: contamination by adventitious metal ions at trace loadings must be excluded as a possible cause of any observed water oxidation activity.

Bio-inspired co-catalysts bonded to a silicon photocathode for solar hydrogen evolution

NASA Astrophysics Data System (ADS)

Hou, Yidong; Abrams, Billie L.; Vesborg, Peter C. K.; Bjørketun, Mårten E.; Herbst, Konrad; Bech, Lone; Seger, Brian; Pedersen, Thomas; Hansen, Ole; Rossmeisl, Jan; Dahl, Søren; Nørskov, Jens K.; Chorkendorff, Ib

2011-10-01

The production of fuels directly or indirectly from sunlight represents one of the major challenges to the development of a sustainable energy system. Hydrogen is the simplest fuel to produce and while platinum and other noble metals are efficient catalysts for photoelectrochemical hydrogen evolution, earth-abundant alternatives are needed for largescale use. We show that bio-inspired molecular clusters based on molybdenum sulfides and tungsten sulfides mimic nature's enzymes for hydrogen evolution, molybdenum sulfides evolve hydrogen at a slightly higher overpotential than platinum when deposited on various supports. It will be demonstrated how this overpotential can be eliminated by depositing the same type of hydrogen evolution catalyst on p-type Si which can harvest the red part of the solar spectrum. Such a system could constitute the cathode part of a tandem dream device where the red part of the spectrum is utilized for hydrogen evolution while the blue part is reserved for the more difficult oxygen evolution. The samples have been illuminated with a simulated red part of the solar spectrum i.e. long wavelength (" > 620 nm) part of simulated AM 1.5G radiation. The current densities at the reversible potential match the requirement of a photoelectrochemical hydrogen production system with a solar-to-hydrogen efficiency in excess of 10%. The experimental observations are supported by DFT calculations of the Mo3S4 cluster adsorbed on the hydrogen-terminated silicon surface providing insights into the nature of the active site.

Water electrolysis with a conducting carbon cloth: subthreshold hydrogen generation and superthreshold carbon quantum dot formation.

PubMed

Biswal, Mandakini; Deshpande, Aparna; Kelkar, Sarika; Ogale, Satishchandra

2014-03-01

A conducting carbon cloth, which has an interesting turbostratic microstructure and functional groups that are distinctly different from other ordered forms of carbon, such as graphite, graphene, and carbon nanotubes, was synthesized by a simple one-step pyrolysis of cellulose fabric. This turbostratic disorder and surface chemical functionalities had interesting consequences for water splitting and hydrogen generation when such a cloth was used as an electrode in the alkaline electrolysis process. Importantly, this work also gives a new twist to carbon-assisted electrolysis. During electrolysis, the active sites in the carbon cloth allow slow oxidation of its surface to transform the surface groups from COH to COOH and so forth at a voltage as low as 0.2 V in a two-electrode system, along with platinum as the cathode, instead of 1.23 V (plus overpotential), which is required for platinum, steel, or even graphite anodes. The quantity of subthreshold hydrogen evolved was 24 mL cm(-2)  h(-1) at 1 V. Interestingly, at a superthreshold potential (>1.23 V+overpotential), another remarkable phenomenon was found. At such voltages, along with the high rate and quantity of hydrogen evolution, rapid exfoliation of the tiny nanoscale (5-7 nm) units of carbon quantum dots (CQDs) are found in copious amounts due to an enhanced oxidation rate. These CQDs show bright-blue fluorescence under UV light. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene Composites with Cobalt Sulfide: Efficient Trifunctional Electrocatalysts for Oxygen Reversible Catalysis and Hydrogen Production in the Same Electrolyte.

PubMed

Wang, Nan; Li, Ligui; Zhao, Dengke; Kang, Xiongwu; Tang, Zhenghua; Chen, Shaowei

2017-09-01

Nitrogen and sulfur-codoped graphene composites with Co 9 S 8 (NS/rGO-Co) are synthesized by facile thermal annealing of graphene oxides with cobalt nitrate and thiourea in an ammonium atmosphere. Significantly, in 0.1 m KOH aqueous solution the best sample exhibits an oxygen evolution reaction (OER) activity that is superior to that of benchmark RuO 2 catalysts, an oxygen reduction reaction (ORR) activity that is comparable to that of commercial Pt/C, and an overpotential of only -0.193 V to reach 10 mA cm -2 for hydrogen evolution reaction (HER). With this single catalyst for oxygen reversible electrocatalysis, a potential difference of only 0.700 V is observed in 0.1 m KOH solution between the half-wave potential in ORR and the potential to reach 10 mA cm -2 in OER; in addition, an overpotential of only 450 mV is needed to reach 10 mA cm -2 for full water splitting in the same electrolyte. The present trifunctional catalytic activities are markedly better than leading results reported in recent literature, where the remarkable trifunctional activity is attributed to the synergetic effects between N,S-codoped rGO, and Co 9 S 8 nanoparticles. These results highlight the significance of deliberate structural engineering in the preparation of multifunctional electrocatalysts for versatile electrochemical reactions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NiFe layered double hydroxide/reduced graphene oxide nanohybrid as an efficient bifunctional electrocatalyst for oxygen evolution and reduction reactions

NASA Astrophysics Data System (ADS)

Zhan, Tianrong; Zhang, Yumei; Liu, Xiaolin; Lu, SiSi; Hou, Wanguo

2016-11-01

Highly active and low-cost bifunctional electrocatalysts for oxygen evolution and reduction reactions (OER and ORR) hold a heart position for the renewable energy technologies such as metal-air batteries and fuel cells. Here, we reported the synthesis of NiFe layered double hydroxide/reduced graphene oxide (NiFe-LDH/rGO) nanohybrid via the facile solvothermal method followed by chemical reduction. The template role of surfactant and the hybridization of rGO supplied the NiFe-LDH/rGO catalyst with a porous nanostructure and an enhanced conductivity, favoring both mass transport and charge communication of electrocatalytic reactions. The NiFe-LDH/rGO composite not only displayed highly efficient OER activity in alkaline solution with a low onset overpotential of 240 mV, but also only needed an overpotential of 250 mV to reach the 10 mA cm-2 current density. The NiFe-LDH/rGO nanohybrid also offered excellent ORR catalytic activity with onset potential at 0.796 V in alkaline media. The rotating-disk and rotating-ring-disk electrodes both revealed that the ORR on NiFe-LDH/rGO mainly involved a direct four-electron reaction pathways accompanying part of the two-electron process. The excellent bifunctional activity of the NiFe-LDH/rGO nanohybrid could be attributed to the synergistic effects of rGO and NiFe-LDH components due to the strongly coupled interactions.

Amorphous Ni(Fe)OxHy-coated nanocone arrays self-supported on stainless steel mesh as a promising oxygen-evolving anode for large scale water splitting

NASA Astrophysics Data System (ADS)

Shen, Junyu; Wang, Mei; Zhao, Liang; Zhang, Peili; Jiang, Jian; Liu, Jinxuan

2018-06-01

The development of highly efficient, robust, and cheap water oxidation electrodes is a major challenge in constructing industrially applicable electrolyzers for large-scale production of hydrogen from water. Herein we report a hierarchical stainless steel mesh electrode which features Ni(Fe)OxHy-coated self-supported nanocone arrays. Through a facile, mild, low-cost and readily scalable two-step fabrication procedure, the electrochemically active area of the optimized electrode is enlarged by a factor of 3.1 and the specific activity is enhanced by a factor of 250 at 265 mV overpotential compared with that of a corresponding pristine stainless steel mesh electrode. Moreover, the charge-transfer resistance is reduced from 4.47 Ω for the stainless steel mesh electrode to 0.13 Ω for the Ni(Fe)OxHy-coated nanocone array stainless steel mesh electrode. As a result, the cheap and easily fabricated electrode displays 280 and 303 mV low overpotentials to achieve high current densities of 500 and 1000 mA cmgeo-2, respectively, for oxygen evolution reaction in 1 M KOH. More importantly, the electrode exhibits a good stability over 340 h of chronopotentiometric test at 50 mA cmgeo-2 and only a slight attenuation (4.2%, ∼15 mV) in catalytic activity over 82 h electrolysis at a constant current density of 500 mA cmgeo-2.

Identifying the Active Surfaces of Electrochemically Tuned LiCoO 2 for Oxygen Evolution Reaction

DOE PAGES

Lu, Zhiyi; Chen, Guangxu; Li, Yanbin; ...

2017-04-18

Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces andmore » their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.« less

Sodium-Oxygen Batteries: A Comparative Review from Chemical and Electrochemical Fundamentals to Future Perspective.

PubMed

Yadegari, Hossein; Sun, Qian; Sun, Xueliang

2016-09-01

Alkali metal-oxygen (Li-O2 , Na-O2 ) batteries have attracted a great deal of attention recently due to their high theoretical energy densities, comparable to gasoline, making them attractive candidates for application in electrical vehicles. However, the limited cycling life and low energy efficiency (high charging overpotential) of these cells hinder their commercialization. The Li-O2 battery system has been extensively studied in this regard during the past decade. Compared to the numerous reports of Li-O2 batteries, the research on Na-O2 batteries is still in its infancy. Although, Na-O2 batteries show a number of attractive properties such as low charging overpotential and high round-trip energy efficiency, their cycling life is currently limited to a few tens of cycles. Therefore, understanding the chemistry behind Na-O2 cells is critical towards enhancing their performance and advancing their development. Chemical and electrochemical reactions of Na-O2 batteries are reviewed and compared with those of Li-O2 batteries in the present review, as well as recent works on the chemical composition and morphology of the discharge products in these batteries. Furthermore, the determining kinetics factors for controlling the chemical composition of the discharge products in Na-O2 cells are discussed and the potential research directions toward improving Na-O2 cells are proposed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancing Catalyzed Decomposition of Na2CO3 with Co2MnO x Nanowire-Decorated Carbon Fibers for Advanced Na-CO2 Batteries.

PubMed

Fang, Cong; Luo, Jianmin; Jin, Chengbin; Yuan, Huadong; Sheng, Ouwei; Huang, Hui; Gan, Yongping; Xia, Yang; Liang, Chu; Zhang, Jun; Zhang, Wenkui; Tao, Xinyong

2018-05-23

The metal-CO 2 batteries, especially Na-CO 2 , batteries come into sight owing to their high energy density, ability for CO 2 capture, and the abundance of sodium resource. Besides the sluggish electrochemical reactions at the gas cathodes and the instability of the electrolyte at a high voltage, the final discharge product Na 2 CO 3 is a solid and poor conductor of electricity, which may cause the high overpotential and poor cycle performance for the Na-CO 2 batteries. The promotion of decomposition of Na 2 CO 3 should be an efficient strategy to enhance the electrochemical performance. Here, we design a facile Na 2 CO 3 activation experiment to screen the efficient cathode catalyst for the Na-CO 2 batteries. It is found that the Co 2 MnO x nanowire-decorated carbon fibers (CMO@CF) can promote the Na 2 CO 3 decomposition at the lowest voltage among all these metal oxide-decorated carbon fiber structures. After assembling the Na-CO 2 batteries, the electrodes based on CMO@CF show lower overpotential and better cycling performance compared with the electrodes based on pristine carbon fibers and other metal oxide-modified carbon fibers. We believe this catalyst screening method and the freestanding structure of the CMO@CF electrode may provide an important reference for the development of advanced Na-CO 2 batteries.

Palladium nanoparticles functionalized graphene nanosheets for Li-O2 batteries: enhanced performance by tailoring the morphology of discharge product

NASA Astrophysics Data System (ADS)

Wang, Liangjun; Chen, Wei; SSL Team

Lithium oxygen (Li-O2) batteries represent a promising candidate for the next generation electric vehicle.1-3 Despite the attractive prospect, some issues including large overpotentials, poor recyclability and unstable electrolyte4-6 limit the wide applications of Li-O2 batteries. Due to the insoluble and non-conductive nature of discharge product Li2O2, it has been widely accepted that the performance of oxygen evolution reaction (OER) process is not only determined by the catalyst itself but also close linked to morphology and electronic conductivity of Li2O2 formed during oxygen reduction reaction (ORR) process. Herein, we report a strategy to improve the battery performance by tailoring the morphology of discharge product. By using graphene nanosheets (GNSs) functionalized with Pd nanoparticles (NPs) as cathode catalyst, the growth and morphology of the discharge products of Li2O2 can be effectively tailored, thereby leading to the improved Li-O2 battery performance. Surprisingly, on bare GNSs cathode, the discharge product showed widely observed large-sized toroidal morphology. While for Pd NPs functionalized GNSs, the discharge product was homogenously distributed on the cathode in the form of small nanoparticles with an average diameter of 25 nm. As a result, Pd NPs functionalized GNSs exhibited a high discharge capacity of 7690 mAh g-1. Meanwhile, the battery with tailored morphology exhibits lower charge overpotential.

Impact of Fe(III) as an effective electron-shuttle mediator for enhanced Cr(VI) reduction in microbial fuel cells: Reduction of diffusional resistances and cathode overpotentials.

PubMed

Wang, Qiang; Huang, Liping; Pan, Yuzhen; Quan, Xie; Li Puma, Gianluca

2017-01-05

The role of Fe(III) was investigated as an electron-shuttle mediator to enhance the reduction rate of the toxic heavy metal hexavalent chromium (Cr(VI)) in wastewaters, using microbial fuel cells (MFCs). The direct reduction of chromate (CrO 4 - ) and dichromate (Cr 2 O 7 2- ) anions in MFCs was hampered by the electrical repulsion between the negatively charged cathode and Cr(VI) functional groups. In contrast, in the presence of Fe(III), the conversion of Cr(VI) and the cathodic coulombic efficiency in the MFCs were 65.6% and 81.7%, respectively, 1.6 times and 1.4 folds as those recorded in the absence of Fe(III). Multiple analytical approaches, including linear sweep voltammetry, Tafel plot, cyclic voltammetry, electrochemical impedance spectroscopy and kinetic calculations demonstrated that the complete reduction of Cr(VI) occurred through an indirect mechanism mediated by Fe(III). The direct reduction of Cr(VI) with cathode electrons in the presence of Fe(III) was insignificant. Fe(III) played a critical role in decreasing both the diffusional resistance of Cr(VI) species and the overpotential for Cr(VI) reduction. This study demonstrated that the reduction of Cr(VI) in MFCs was effective in the presence of Fe(III), providing an alternative and environmentally benign approach for efficient remediation of Cr(VI) contaminated sites with simultaneous production of renewable energy. Copyright © 2016 Elsevier B.V. All rights reserved.

An Operando Investigation of (Ni–Fe–Co–Ce)O x System as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction

DOE PAGES

Favaro, Marco; Drisdell, Walter S.; Marcus, Matthew A.; ...

2016-12-27

The oxygen evolution reaction (OER) is a critical component of industrial processes such as electrowinning of metals and the chlor-alkali process. It also plays a central role in the development of a renewable energy field for generation a solar fuels by providing both the protons and electrons needed to generate fuels such as H 2 or reduced hydrocarbons from CO 2. To improve these processes, it is necessary to expand the fundamental understanding of catalytically active species at low overpotential, which will further the development of electrocatalysts with high activity and durability. In this context, performing experimental investigations of themore » electrocatalysts under realistic working regimes (i.e., under operando conditions) is of crucial importance. In this paper, we study a highly active quinary transition-metal-oxide-based OER electrocatalyst by means of operando ambient-pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy performed at the solid/liquid interface. We observe that the catalyst undergoes a clear chemical-structural evolution as a function of the applied potential with Ni, Fe, and Co oxyhydroxides comprising the active catalytic species. Finally, while CeO 2 is redox inactive under catalytic conditions, its influence on the redox processes of the transition metals boosts the catalytic activity at low overpotentials, introducing an important design principle for the optimization of electrocatalysts and tailoring of high-performance materials.« less

Screen-printed calcium-birnessite electrodes for water oxidation at neutral pH and an "electrochemical harriman series".

PubMed

Lee, Seung Y; González-Flores, Diego; Ohms, Jonas; Trost, Tim; Dau, Holger; Zaharieva, Ivelina; Kurz, Philipp

2014-12-01

A mild screen-printing method was developed to coat conductive oxide surfaces (here: fluorine-doped tin oxide) with micrometer-thick layers of presynthesized calcium manganese oxide (Ca-birnessite) particles. After optimization steps concerning the printing process and layer thickness, electrodes were obtained that could be used as corrosion-stable water-oxidizing anodes at pH 7 to yield current densities of 1 mA cm(-2) at an overpotential of less than 500 mV. Analyses of the electrode coatings of optimal thickness (≈10 μm) indicated that composition, oxide phase, and morphology of the synthetic Ca-birnessite particles were hardly affected by the screen-printing procedure. However, a more detailed analysis by X-ray absorption spectroscopy revealed small modifications of both the Mn redox state and the structure at the atomic level, which could affect functional properties such as proton conductivity. Furthermore, the versatile new screen-printing method was used for a comparative study of various transition-metal oxides concerning electrochemical water oxidation under "artificial leaf conditions" (neutral pH, fairly low overpotential and current density), for which a general activity ranking of RuO2 >Co3 O4 ≈(Ca)MnOx ≈NiO was observed. Within the group of screened manganese oxides, Ca-birnessite performed better than "Mn-only materials" such as Mn2 O3 and MnO2 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

FeS2 /CoS2 Interface Nanosheets as Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

PubMed

Li, Yuxuan; Yin, Jie; An, Li; Lu, Min; Sun, Ke; Zhao, Yong-Qin; Gao, Daqiang; Cheng, Fangyi; Xi, Pinxian

2018-05-28

Electrochemical water splitting to produce hydrogen and oxygen, as an important reaction for renewable energy storage, needs highly efficient and stable catalysts. Herein, FeS 2 /CoS 2 interface nanosheets (NSs) as efficient bifunctional electrocatalysts for overall water splitting are reported. The thickness and interface disordered structure with rich defects of FeS 2 /CoS 2 NSs are confirmed by atomic force microscopy and high-resolution transmission electron microscopy. Furthermore, extended X-ray absorption fine structure spectroscopy clarifies that FeS 2 /CoS 2 NSs with sulfur vacancies, which can further increase electrocatalytic performance. Benefiting from the interface nanosheets' structure with abundant defects, the FeS 2 /CoS 2 NSs show remarkable hydrogen evolution reaction (HER) performance with a low overpotential of 78.2 mV at 10 mA cm -2 and a superior stability for 80 h in 1.0 m KOH, and an overpotential of 302 mV at 100 mA cm -2 for the oxygen evolution reaction (OER). More importantly, the FeS 2 /CoS 2 NSs display excellent performance for overall water splitting with a voltage of 1.47 V to achieve current density of 10 mA cm -2 and maintain the activity for at least 21 h. The present work highlights the importance of engineering interface nanosheets with rich defects based on transition metal dichalcogenides for boosting the HER and OER performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile Synthesis of Single Crystal Vanadium Disulfide Nanosheets by Chemical Vapor Deposition for Efficient Hydrogen Evolution Reaction.

PubMed

Yuan, Jiangtan; Wu, Jingjie; Hardy, Will J; Loya, Philip; Lou, Minhan; Yang, Yingchao; Najmaei, Sina; Jiang, Menglei; Qin, Fan; Keyshar, Kunttal; Ji, Heng; Gao, Weilu; Bao, Jiming; Kono, Junichiro; Natelson, Douglas; Ajayan, Pulickel M; Lou, Jun

2015-10-07

A facile chemical vapor deposition method to prepare single-crystalline VS2 nanosheets for the hydrogen evolution reaction is reported. The electrocatalytic hydrogen evolution reaction (HER) activities of VS2 show an extremely low overpotential of -68 mV at 10 mA cm(-2), small Tafel slopes of ≈34 mV decade(-1), as well as high stability, demonstrating its potential as a candidate non-noble-metal catalyst for the HER. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A mathematical model for predicting cyclic voltammograms of electronically conductive polypyrrole

NASA Technical Reports Server (NTRS)

Yeu, Taewhan; Nguyen, Trung V.; White, Ralph E.

1988-01-01

Polypyrrole is an attractive polymer for use as a high-energy-density secondary battery because of its potential as an inexpensive, lightweight, and noncorrosive electrode material. A mathematical model to simulate cyclic voltammograms for polypyrrole is presented. The model is for a conductive porous electrode film on a rotating disk electrode (RDE) and is used to predict the spatial and time dependence of concentration, overpotential, and stored charge profiles within a polypyrrole film. The model includes both faradic and capacitance charge components in the total current density expression.

A mathematical model for predicting cyclic voltammograms of electronically conductive polypyrrole

NASA Technical Reports Server (NTRS)

Yeu, Taewhan; Nguyen, Trung V.; White, Ralph E.

1987-01-01

Polypyrrole is an attractive polymer for use as a high-energy-density secondary battery because of its potential as an inexpensive, lightweight, and noncorrosive electrode material. A mathematical model to simulate cyclic voltammograms for polypyrrole is presented. The model is for a conductive porous electrode film on a rotating disk electrode (RDE) and is used to predict the spatial and time dependence of concentration, overpotential, and stored charge profiles within a polypyrrole film. The model includes both faradic and capacitance charge components in the total current density expression.

In situ growth of well-ordered NiFe-MOF-74 on Ni foam by Fe2+ induction as an efficient and stable electrocatalyst for water oxidation.

PubMed

Xing, Jiale; Guo, Kailu; Zou, Zehua; Cai, Minmin; Du, Jing; Xu, Cailing

2018-06-06

Well-ordered NiFe-MOF-74 is in situ grown on Ni foam by the induction of Fe2+ and directly used as an OER electrocatalyst. Benefited from the intrinsic open porous structure of MOF-74, the in situ formed MOF arrays and the synergistic effect of Ni and Fe, outstanding water oxidation activity is obtained in alkaline electrolytes with an overpotential of 223 mV at 10 mA cm-2.

A plug flow reactor model of a vanadium redox flow battery considering the conductive current collectors

NASA Astrophysics Data System (ADS)

König, S.; Suriyah, M. R.; Leibfried, T.

2017-08-01

A lumped-parameter model for vanadium redox flow batteries, which use metallic current collectors, is extended into a one-dimensional model using the plug flow reactor principle. Thus, the commonly used simplification of a perfectly mixed cell is no longer required. The resistances of the cell components are derived in the in-plane and through-plane directions. The copper current collector is the only component with a significant in-plane conductance, which allows for a simplified electrical network. The division of a full-scale flow cell into 10 layers in the direction of fluid flow represents a reasonable compromise between computational effort and accuracy. Due to the variations in the state of charge and thus the open circuit voltage of the electrolyte, the currents in the individual layers vary considerably. Hence, there are situations, in which the first layer, directly at the electrolyte input, carries a multiple of the last layer's current. The conventional model overestimates the cell performance. In the worst-case scenario, the more accurate 20-layer model yields a discharge capacity 9.4% smaller than that computed with the conventional model. The conductive current collector effectively eliminates the high over-potentials in the last layers of the plug flow reactor models that have been reported previously.

Designer interphases for the lithium-oxygen electrochemical cell

PubMed Central

Choudhury, Snehashis; Wan, Charles Tai-Chieh; Al Sadat, Wajdi I.; Tu, Zhengyuan; Lau, Sampson; Zachman, Michael J.; Kourkoutis, Lena F.; Archer, Lynden A.

2017-01-01

An electrochemical cell based on the reversible oxygen reduction reaction: 2Li+ + 2e− + O2 ↔ Li2O2, provides among the most energy dense platforms for portable electrical energy storage. Such Lithium-Oxygen (Li-O2) cells offer specific energies competitive with fossil fuels and are considered promising for electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these problems lead to as many practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in-situ formation of solid-electrolyte interphases (SEIs) based on bromide ionomers tethered to a Li anode that take advantage of three powerful processes for overcoming the most stubborn of these challenges. The ionomer SEIs are shown to protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Bromine species liberated during the anchoring reaction also function as redox mediators at the cathode, reducing the charge overpotential. Finally, the ionomer SEI forms a stable interphase with Li, which protects the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates, but also react spontaneously with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a promising platform for addressing three major technical barriers to practical Li-O2 cells. PMID:28439557

Core-shell Li2S@Li3PS4 nanoparticles incorporated into graphene aerogel for lithium-sulfur batteries with low potential barrier and overpotential

NASA Astrophysics Data System (ADS)

Jiao, Zheng; Chen, Lu; Si, Jian; Xu, Chuxiong; Jiang, Yong; Zhu, Ying; Yang, Yaqing; Zhao, Bing

2017-06-01

Lithium sulfide as a promising cathode material not only have a high theoretical specific capacity, but also can be paired with Li-free anode material to avoid potential safety issues. However, how to prepare high electrochemical performance material is still challenge. Herein, we present a facile way to obtain high crystal quality Li2S nanomaterials with average particle size of about 55 nm and coated with Li3PS4 to form the nano-scaled core-shell Li2S@Li3PS4 composite. Then nano-Li2S@Li3PS4/graphene aerogel is prepared by a simple liquid infiltration-evaporation coating process and used directly as a composite cathode without metal substrate for lithium-sulfur batteries. Electrochemical tests demonstrate that the composite delivers a high discharge capacity of 934.4 mAh g-1 in the initial cycle and retains 485.5 mAh g-1 after 100 cycles at 0.1 C rate. In addition, the composite exhibits much lower potential barrier (∼2.40 V) and overpotential compared with previous reports, indicating that Li2S needs only a little energy to be activated. The excellent electrochemical performances could be attributed to the tiny particle size of Li2S and the superionic conducting Li3PS4 coating layer, which can shorten Li-ion and electron diffusion paths, improve the ionic conductivity, as well as retarding polysulfides dissolution into the electrolyte to some extent.

Effect of the asymmetry of the coupling of the redox molecule to the electrodes in the one-level electrochemical bridged tunneling contact on the Coulomb blockade and the operation of molecular transistor.

PubMed

Medvedev, Igor G

2014-09-28

Effect of the asymmetry of the redox molecule (RM) coupling to the working electrodes on the Coulomb blockade and the operation of molecular transistor is considered under ambient conditions for the case of the non-adiabatic tunneling through the electrochemical contact having a one-level RM. The expressions for the tunnel current, the positions of the peaks of the tunnel current/overpotential dependencies, and their full widths at the half maximum are obtained for arbitrary values of the parameter d describing the coupling asymmetry of the tunneling contact and the effect of d on the different characteristics of the tunneling contact is studied. The tunnel current/overpotential and the differential conductance/bias voltage dependencies are calculated and interpreted. In particular, it is shown that the effect of the Coulomb blockade on the tunnel current and the differential conductance has a number of new features in the case of the large coupling asymmetry. It is also shown that, for rather large values of the solvent reorganization energy, the coupling asymmetry enhanced strongly amplification and rectification of the tunnel current in the most of the regions of the parameter space specifying the tunneling contact. The regions of the parameter space where both strong amplification and strong rectification take place are also revealed. The obtained results allow us to prove the possibility of the realization of the effective electrochemical transistor based on the one-level RM.

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme

PubMed Central

Reda, Torsten; Plugge, Caroline M.; Abram, Nerilie J.; Hirst, Judy

2008-01-01

Carbon dioxide (CO2) is a kinetically and thermodynamically stable molecule. It is easily formed by the oxidation of organic molecules, during combustion or respiration, but is difficult to reduce. The production of reduced carbon compounds from CO2 is an attractive proposition, because carbon-neutral energy sources could be used to generate fuel resources and sequester CO2 from the atmosphere. However, available methods for the electrochemical reduction of CO2 require excessive overpotentials (are energetically wasteful) and produce mixtures of products. Here, we show that a tungsten-containing formate dehydrogenase enzyme (FDH1) adsorbed to an electrode surface catalyzes the efficient electrochemical reduction of CO2 to formate. Electrocatalysis by FDH1 is thermodynamically reversible—only small overpotentials are required, and the point of zero net catalytic current defines the reduction potential. It occurs under thoroughly mild conditions, and formate is the only product. Both as a homogeneous catalyst and on the electrode, FDH1 catalyzes CO2 reduction with a rate more than two orders of magnitude faster than that of any known catalyst for the same reaction. Formate oxidation is more than five times faster than CO2 reduction. Thermodynamically, formate and hydrogen are oxidized at similar potentials, so formate is a viable energy source in its own right as well as an industrially important feedstock and a stable intermediate in the conversion of CO2 to methanol and methane. FDH1 demonstrates the feasibility of interconverting CO2 and formate electrochemically, and it is a template for the development of robust synthetic catalysts suitable for practical applications. PMID:18667702

Integrated Energy Aerogel of N,S-rGO/WSe2/NiFe-LDH for Both Energy Conversion and Storage.

PubMed

Xu, Xiaowei; Chu, Hang; Zhang, Zhuqing; Dong, Pei; Baines, Robert; Ajayan, Pulickel M; Shen, Jianfeng; Ye, Mingxin

2017-09-27

High-performance active materials for energy-storage and energy-conversion applications require a novel class of electrodes: ones with a structure conducive to conductivity, large specific surface area, high porosity, and mechanical robustness. Herein, we report the design and fabrication of a new ternary hybrid aerogel. The process entails an in situ assembly of 2D WSe 2 nanosheets and NiFe-LDH nanosheets on a 3D N,S-codoped graphene framework, accomplished by a facile hydrothermal method and electrostatic self-assembly technology. The obtained nanocomposite architecture maximizes synergistic effects among its three 2D-layer components. To assess the performance of this hybrid material, we deployed it as an advanced electrode in overall water splitting and in a supercapacitor. Results in both scenarios attest to its excellent electrochemical properties. Specifically, serving as a catalyst in an oxygen evolution reaction, our nanocomposite requires overpotentials of 1.48 and 1.59 V to obtain current densities of 10 and 100 mA cm -2 , respectively. The hybrid material also efficiently electrocatalyzes hydrogen evolution reactions in base solution, necessitating overpotentials of -50 and -237 mV for current densities of 1.0 and 100 mA cm -2 , respectively. The 3D hybrid, when applied to a symmetric supercapacitor device, achieves 125.6 F g -1 capacitance at 1 A g -1 current density. In summary, our study elucidates a new strategy to maximize efficiency via synergetic effects that is likely applicable to other 2D materials.

Extraction of nickel from NiFe-LDH into Ni2P@NiFe hydroxide as a bifunctional electrocatalyst for efficient overall water splitting† †Electronic supplementary information (ESI) available: Experimental and computational details and additional data. See DOI: 10.1039/c7sc04569g

PubMed Central

Zhang, Fang-Shuai; Wang, Jia-Wei; Luo, Jun; Liu, Rui-Rui

2017-01-01

The development of highly efficient, low-cost and stable electrocatalysts for overall water splitting is highly desirable for the storage of intermittent solar energy and wind energy sources. Herein, we show for the first time that nickel can be extracted from NiFe-layered double hydroxide (NiFe-LDH) to generate an Ni2P@FePOx heterostructure. The Ni2P@FePOx heterostructure was converted to an Ni2P@NiFe hydroxide heterostructure (P-NiFe) during water splitting, which displays high electrocatalytic performance for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1.0 M KOH solution, with an overpotential of 75 mV at 10 mA cm–2 for HER, and overpotentials of 205, 230 and 430 mV at 10, 100 and 1000 mA cm–2 for OER, respectively. Moreover, it could afford a stable current density of 10 mA cm–2 for overall water splitting at 1.51 V in 1.0 M KOH with long-term durability (100 h). This cell voltage is among the best reported values for bifunctional electrocatalysts. The results of theoretical calculations demonstrate that P-NiFe displays optimized adsorption energies for both HER and OER intermediates at the nickel active sites, thus dramatically enhancing its electrocatalytic activity. PMID:29675186

Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chung, Ding-wen; Balke, Nina; Kalinin, Sergei V

2011-01-01

A recently developed technique, electrochemical strain microscopy (ESM), utilizes the strong coupling between ionic current and anisotropic volumetric chemical expansion of lithium-ion electrode materials to dynamically probe the sub-one-hundred? nm inter-facial kinetic intercalation properties. A numerical technique based on the finite element method was developed to analyze the underlying physics that govern the ESM signal generation and establish relations to battery performance. The performed analysis demonstrates that the diffusion path within a thin film is tortuous and the extent of lithium diffusion into the electrode is dependent on the SPM-tip-imposed overpotential frequency. The detected surface actuation gives rise to themore » development of an electromechanical hysteresis loop whose shape is dependent on grain size and overpotential frequency. Shape and tilting angle of the loop are classified into low and high frequency regimes, separated by a transition frequency which is also a function of lithium diffusivity and grain size, f{sub T} = D//{sup 2}. Research shows that the crystallographic orientation of the surface actuated grain has a significant impact on the shape of the loop. The polycrystalline crystallographic orientation of the grains induces a diffusion path network in the electrode which impacts on the mechanical reliability of the battery. Simulations demonstrate that continuous battery cycling results in a cumulative capacity loss as a result of the hysteric non-reversible lithium intercalation. Furthermore, results suggest that ESM has the capability to infer the local out-of-plane lithium diffusivity and the out-of-plane contribution to Vegard tensor.« less

Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chung, Ding-Wen; Balke, Nina; Kalinin, Sergei V.

2011-08-03

A recently developed technique, electrochemical strain microscopy (ESM), utilizes the strong coupling between ionic current and anisotropic volumetric chemical expansion of lithium-ion electrode materials to dynamically probe the sub-one-hundred? nm inter-facial kinetic intercalation properties. A numerical technique based on the finite element method was developed to analyze the underlying physics that govern the ESM signal generation and establish relations to battery performance. The performed analysis demonstrates that the diffusion path within a thin film is tortuous and the extent of lithium diffusion into the electrode is dependent on the SPM-tip-imposed overpotential frequency. The detected surface actuation gives rise to themore » development of an electromechanical hysteresis loop whose shape is dependent on grain size and overpotential frequency. Shape and tilting angle of the loop are classified into low and high frequency regimes, separated by a transition frequency which is also a function of lithium diffusivity and grain size, f T = D/l₂. Research shows that the crystallographic orientation of the surface actuated grain has a significant impact on the shape of the loop. The polycrystalline crystallographic orientation of the grains induces a diffusion path network in the electrode which impacts on the mechanical reliability of the battery. Simulations demonstrate that continuous battery cycling results in a cumulative capacity loss as a result of the hysteric non-reversible lithium intercalation. Furthermore, results suggest that ESM has the capability to infer the local out-of-plane lithium diffusivity and the out-of-plane contribution to Vegard tensor.« less

One-pot fabrication of NiFe2O4 nanoparticles on α-Ni(OH)2 nanosheet for enhanced water oxidation

NASA Astrophysics Data System (ADS)

Chen, Hong; Yan, Junqing; Wu, Huan; Zhang, Yunxia; Liu, Shengzhong (Frank)

2016-08-01

Water splitting has been intensively investigated as a promising solution to resolve the future environmental and energy crises. The oxygen evolution reaction (OER) of the photo- and electric field-induced water splitting limits the development of other reactions, including hydrogen evolution reaction (HER). Fe, Ni and NiFe (hydro) oxide-based catalysts are generally acknowledged among the best candidates of OER catalysts for water splitting. Herein, we developed a one-pot simple hydrothermal process to assemble NiFe2O4 nanoparticles onto the α-Ni(OH)2 nanosheets. The first formed NiFe2O4 under high temperature and pressure environment induces and assists the α-Ni(OH)2 formation without any further additives, because the distance between the neighboring Ni atoms in the cubic NiFe2O4 is similar to that in the α-Ni(OH)2 {003} facets. We have synthesized a series of NiFe2O4/α-Ni(OH)2 compounds and find that the overpotential decreases with the increase of Ni(OH)2 content while the OER kinetics stays unchanged, suggesting that Ni(OH)2 plays a major role in overpotential while NiFe2O4 mainly affects the OER kinetics. The obtained NiFe2O4/α-Ni(OH)2 compounds is also found to be a promising co-catalyst for the photocatalytic water oxidation. In fact, it is even more active than the noble PtOx with acceptable stability for the oxygen generation.

Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

El-Sawy, Abdelhamid M.; Mosa, Islam M.; Su, Dong

Controlling active sites of metal-free catalysts is an important strategy to enhance activity of the oxygen evolution reaction (OER). We made many attempts have been made to develop metal-free catalysts, but the lack of understanding of active-sites at the atomic-level has slowed the design of highly active and stable metal-free catalysts. We also developed a sequential two-step strategy to dope sulfur into carbon nanotube–graphene nanolobes. This bidoping strategy introduces stable sulfur–carbon active-sites. Fluorescence emission of the sulfur K-edge by X-ray absorption near edge spectroscopy (XANES) and scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) mapping and spectra confirm thatmore » increasing the incorporation of heterocyclic sulfur into the carbon ring of CNTs not only enhances OER activity with an overpotential of 350 mV at a current density of 10 mA cm -2, but also retains 100% of stability after 75 h. Furthermore, the bidoped sulfur carbon nanotube–graphene nanolobes behave like the state-of-the-art catalysts for OER but outperform those systems in terms of turnover frequency (TOF) which is two orders of magnitude greater than (20% Ir/C) at 400 mV overpotential with very high mass activity 1000 mA cm -2 at 570 mV. Moreover, the sulfur bidoping strategy shows high catalytic activity for the oxygen reduction reaction (ORR). Stable bifunctional (ORR and OER) catalysts are low cost, and light-weight bidoped sulfur carbon nanotubes are potential candidates for next-generation metal-free regenerative fuel cells.« less

Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis

DOE PAGES

El-Sawy, Abdelhamid M.; Mosa, Islam M.; Su, Dong; ...

2015-12-03

Controlling active sites of metal-free catalysts is an important strategy to enhance activity of the oxygen evolution reaction (OER). We made many attempts have been made to develop metal-free catalysts, but the lack of understanding of active-sites at the atomic-level has slowed the design of highly active and stable metal-free catalysts. We also developed a sequential two-step strategy to dope sulfur into carbon nanotube–graphene nanolobes. This bidoping strategy introduces stable sulfur–carbon active-sites. Fluorescence emission of the sulfur K-edge by X-ray absorption near edge spectroscopy (XANES) and scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) mapping and spectra confirm thatmore » increasing the incorporation of heterocyclic sulfur into the carbon ring of CNTs not only enhances OER activity with an overpotential of 350 mV at a current density of 10 mA cm -2, but also retains 100% of stability after 75 h. Furthermore, the bidoped sulfur carbon nanotube–graphene nanolobes behave like the state-of-the-art catalysts for OER but outperform those systems in terms of turnover frequency (TOF) which is two orders of magnitude greater than (20% Ir/C) at 400 mV overpotential with very high mass activity 1000 mA cm -2 at 570 mV. Moreover, the sulfur bidoping strategy shows high catalytic activity for the oxygen reduction reaction (ORR). Stable bifunctional (ORR and OER) catalysts are low cost, and light-weight bidoped sulfur carbon nanotubes are potential candidates for next-generation metal-free regenerative fuel cells.« less

Composition-Graded MoWSx Hybrids with Tailored Catalytic Activity by Bipolar Electrochemistry.

PubMed

Tan, Shu Min; Pumera, Martin

2017-12-06

Among transition metal dichalcogenide (TMD)-based composites, TMD/graphene-related material and bichalcogen TMD composites have been widely studied for application toward energy production via the hydrogen evolution reaction (HER). However, scarcely any literature explored the possibility of bimetallic TMD hybrids as HER electrocatalysts. The use of harmful chemicals and harsh preparation conditions in conventional syntheses also detracts from the objective of sustainable energy production. Herein, we present the conservational alternative synthesis of MoWS x via one-step bipolar electrochemical deposition. Through bipolar electrochemistry, the simultaneous fabrication of composition-graded MoWS x hybrids, i.e., sulfur-deficient Mo x W (1-x) S 2 and Mo x W (1-x) S 3 (MoWS x /BPE cathodic and MoWS x /BPE anodic , respectively) under cathodic and anodic overpotentials, was achieved. The best-performing MoWS x /BPE cathodic and MoWS x /BPE anodic materials exhibited Tafel slopes of 45.7 and 50.5 mV dec -1 , together with corresponding HER overpotentials of 315 and 278 mV at -10 mA cm -2 . The remarkable HER activities of the composite materials were attributed to their small particle sizes, as well as the near-unity value of their surface Mo/W ratios, which resulted in increased exposed HER-active sites and differing active sites for the concurrent adsorption of protons and desorption of hydrogen gas. The excellent electrocatalytic performances achieved via the novel methodology adopted here encourage the empowerment of electrochemical deposition as the foremost fabrication approach toward functional electrocatalysts for sustainable energy generation.

Impedance Spectroscopic Investigation of Proton Conductivity in Nafion Using Transient Electrochemical Atomic Force Microscopy (AFM)

PubMed Central

Hink, Steffen; Wagner, Norbert; Bessler, Wolfgang G.; Roduner, Emil

2012-01-01

Spatially resolved impedance spectroscopy of a Nafion polyelectrolyte membrane is performed employing a conductive and Pt-coated tip of an atomic force microscope as a point-like contact and electrode. The experiment is conducted by perturbing the system by a rectangular voltage step and measuring the incurred current, followed by Fourier transformation and plotting the impedance against the frequency in a conventional Bode diagram. To test the potential and limitations of this novel method, we present a feasibility study using an identical hydrogen atmosphere at a well-defined relative humidity on both sides of the membrane. It is demonstrated that good quality impedance spectra are obtained in a frequency range of 0.2–1000 Hz. The extracted polarization curves exhibit a maximum current which cannot be explained by typical diffusion effects. Simulation based on equivalent circuits requires a Nernst element for restricted diffusion in the membrane which suggests that this effect is based on the potential dependence of the electrolyte resistance in the high overpotential region. PMID:24958175

Electrocatalytic Hydrogen Production by a Nickel(II) Complex with a Phosphinopyridyl Ligand.

PubMed

Tatematsu, Ryo; Inomata, Tomohiko; Ozawa, Tomohiro; Masuda, Hideki

2016-04-18

A novel nickel(II) complex [Ni(L)2 Cl]Cl with a bidentate phosphinopyridyl ligand 6-((diphenylphosphino)methyl)pyridin-2-amine (L) was synthesized as a metal-complex catalyst for hydrogen production from protons. The ligand can stabilize a low Ni oxidation state and has an amine base as a proton transfer site. The X-ray structure analysis revealed a distorted square-pyramidal Ni(II)  complex with two bidentate L ligands in a trans arrangement in the equatorial plane and a chloride anion at the apex. Electrochemical measurements with the Ni(II) complex in MeCN indicate a higher rate of hydrogen production under weak acid conditions using acetic acid as the proton source. The catalytic current increases with the stepwise addition of protons, and the turnover frequency is 8400 s(-1) in 0.1 m [NBu4 ][ClO4 ]/MeCN in the presence of acetic acid (290 equiv) at an overpotential of circa 590 mV. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Operando characterization of cathodic reactions in a liquid-state lithium-oxygen micro-battery by scanning transmission electron microscopy.

PubMed

Liu, Pan; Han, Jiuhui; Guo, Xianwei; Ito, Yoshikazu; Yang, Chuchu; Ning, Shoucong; Fujita, Takeshi; Hirata, Akihiko; Chen, Mingwei

2018-02-16

Rechargeable non-aqueous lithium-oxygen batteries with a large theoretical capacity are emerging as a high-energy electrochemical device for sustainable energy strategy. Despite many efforts made to understand the fundamental Li-O 2 electrochemistry, the kinetic process of cathodic reactions, associated with the formation and decomposition of a solid Li 2 O 2 phase during charging and discharging, remains debate. Here we report direct visualization of the charge/discharge reactions on a gold cathode in a non-aqueous lithium-oxygen micro-battery using liquid-cell aberration-corrected scanning transmission electron microscopy (STEM) combining with synchronized electrochemical measurements. The real-time and real-space characterization by time-resolved STEM reveals the electrochemical correspondence of discharge/charge overpotentials to the nucleation, growth and decomposition of Li 2 O 2 at a constant current density. The nano-scale operando observations would enrich our knowledge on the underlying reaction mechanisms of lithium-oxygen batteries during round-trip discharging and charging and shed lights on the strategies in improving the performances of lithium-oxygen batteries by tailoring the cathodic reactions.

Calcium-bismuth electrodes for large-scale energy storage (liquid metal batteries)

NASA Astrophysics Data System (ADS)

Kim, Hojong; Boysen, Dane A.; Ouchi, Takanari; Sadoway, Donald R.

2013-11-01

Calcium is an attractive electrode material for use in grid-scale electrochemical energy storage due to its low electronegativity, earth abundance, and low cost. The feasibility of combining a liquid Ca-Bi positive electrode with a molten salt electrolyte for use in liquid metal batteries at 500-700 °C was investigated. Exhibiting excellent reversibility up to current densities of 200 mA cm-2, the calcium-bismuth liquid alloy system is a promising positive electrode candidate for liquid metal batteries. The measurement of low self-discharge current suggests that the solubility of calcium metal in molten salt electrolytes can be sufficiently suppressed to yield high coulombic efficiencies >98%. The mechanisms giving rise to Ca-Bi electrode overpotentials were investigated in terms of associated charge transfer and mass transport resistances. The formation of low density Ca11Bi10 intermetallics at the electrode-electrolyte interface limited the calcium deposition rate capability of the electrodes; however, the co-deposition of barium into bismuth from barium-containing molten salts suppressed Ca-Bi intermetallic formation thereby improving the discharge capacity.

Electrocatalytic activity and operational stability of electrodeposited Pd-Co films towards ethanol oxidation in alkaline electrolytes

NASA Astrophysics Data System (ADS)

Tsui, Lok-kun; Zafferoni, Claudio; Lavacchi, Alessandro; Innocenti, Massimo; Vizza, Francesco; Zangari, Giovanni

2015-10-01

Direct alkaline ethanol fuel cells (DEFCs) are usually run with Pd anodic catalysts, but their performance can be improved by utilizing alloys of Pd and Co. The oxyphilic Co serves to supply ample -OH to the ethanol oxidation reaction, accelerating the rate limiting step at low overpotential under alkaline conditions. Pd-Co films with compositions between 20 and 80 at% Co can be prepared by electrodeposition from a NH3 complexing electrolyte. Cyclic voltammetry studies show that the ethanol oxidation peak exhibits increasing current density with increasing Co content, reaching a maximum at 77% Co. In contrast, potentiostatic measurements under conditions closer to fuel cell operating conditions show that a 50 at% Co alloy has the highest performance. Importantly, the Co-Pd film is also found to undergo phase and morphological transformations during ethanol oxidation, resulting in a change from a compact film to high surface area flake-like structures containing Co3O4 and CoOOH; such a transformation instead is not observed when operating at a constant potential of 0.7 VRHE.

Dynamic in-plane potential gradients for actively controlling electrochemical reactions: Part I. Characterization of 1- and 2-component alkanethiol monolayer gradients on thin gold films. Part II. Applications of in-plane potential gradients

NASA Astrophysics Data System (ADS)

Balss, Karin Maria

The research contained in this thesis is focused on the formation and characterization of surface composition gradients on thin gold films that are formed by applications of in-plane potential gradients. Injecting milliamp currents into thin Au films yields significant in-plane voltage drops so that, rather than assuming a single value of potential, an in-plane potential gradient is imposed on the film which depends on the resistivity of the film, the cross sectional area and the magnitude of the potential drop. Furthermore, the in-plane electric potential gradient means that, relative to a solution reference couple, electrochemical reactions occurs at defined spatial positions corresponding to the local potential, V(x) ˜ E0. The spatial gradient in electrochemical potential can then produce spatially dependent electrochemistry. Surface-chemical potential gradients can be prepared by arranging the spread of potentials to span an electrochemical wave mediating redox-associated adsorption or desorption. Examples of reactions that can be spatially patterned include the electrosorption of alkanethiols and over-potential metal deposition. The unique advantage of this method for patterning spatial compositions is the control of surface coverage in both space and time. The thesis is organized into two parts. In Part I, formation and characterization of 1- and 2-component alkanethiol monolayer gradients is investigated. Numerous surface science tools are employed to examine the distribution in coverage obtained by application of in-plane potential gradients. Macroscopic characterization was obtained by sessile water drop contact angle measurements and surface plasmon resonance imaging. Gradients were also imaged on micron length scales with pulsed-force mode atomic force microscopy. Direct chemical evidence of surface compositions in aromatic thiol surface coverage was obtained by surface-enhanced Raman spectroscopy. In Part II, the applications of in-plane potential gradients is discussed. Electrochemical reactions other than electrosorption of alkanethiols were demonstrated with over-potential deposition of copper onto gold films. One application of these patterns is to control the movement of supermolecular objects. As a first step towards this goal, biological cells were seeded onto gradient patterns containing adhesion promoters and inhibitors. The morphology and adhesion was investigated as a function of concentration along the gradient.

Mediated water electrolysis in biphasic systems.

PubMed

Scanlon, Micheál D; Peljo, Pekka; Rivier, Lucie; Vrubel, Heron; Girault, Hubert H

2017-08-30

The concept of efficient electrolysis by linking photoelectrochemical biphasic H 2 evolution and water oxidation processes in the cathodic and anodic compartments of an H-cell, respectively, is introduced. Overpotentials at the cathode and anode are minimised by incorporating light-driven elements into both biphasic reactions. The concepts viability is demonstrated by electrochemical H 2 production from water splitting utilising a polarised water-organic interface in the cathodic compartment of a prototype H-cell. At the cathode the reduction of decamethylferrocenium cations ([Cp 2 *Fe (III) ] + ) to neutral decamethylferrocene (Cp 2 *Fe (II) ) in 1,2-dichloroethane (DCE) solvent takes place at the solid electrode/oil interface. This electron transfer process induces the ion transfer of a proton across the immiscible water/oil interface to maintain electroneutrality in the oil phase. The oil-solubilised proton immediately reacts with Cp 2 *Fe (II) to form the corresponding hydride species, [Cp 2 *Fe (IV) (H)] + . Subsequently, [Cp 2 *Fe (IV) (H)] + spontaneously undergoes a chemical reaction in the oil phase to evolve hydrogen gas (H 2 ) and regenerate [Cp 2 *Fe (III) ] + , whereupon this catalytic Electrochemical, Chemical, Chemical (ECC') cycle is repeated. During biphasic electrolysis, the stability and recyclability of the [Cp 2 *Fe (III) ] + /Cp 2 *Fe (II) redox couple were confirmed by chronoamperometric measurements and, furthermore, the steady-state concentration of [Cp 2 *Fe (III) ] + monitored in situ by UV/vis spectroscopy. Post-biphasic electrolysis, the presence of H 2 in the headspace of the cathodic compartment was established by sampling with gas chromatography. The rate of the biphasic hydrogen evolution reaction (HER) was enhanced by redox electrocatalysis in the presence of floating catalytic molybdenum carbide (Mo 2 C) microparticles at the immiscible water/oil interface. The use of a superhydrophobic organic electrolyte salt was critical to ensure proton transfer from water to oil, and not anion transfer from oil to water, in order to maintain electroneutrality after electron transfer. The design, testing and successful optimisation of the operation of the biphasic electrolysis cell under dark conditions with Cp 2 *Fe (II) lays the foundation for the achievement of photo-induced biphasic water electrolysis at low overpotentials using another metallocene, decamethylrutheneocene (Cp 2 *Ru (II) ). Critically, Cp 2 *Ru (II) may be recycled at a potential more positive than that of proton reduction in DCE.

Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Li, Wenyuan

Oxide anodes for solid oxide fuel cells (SOFC) with the advantage of fuel flexibility, resistance to coarsening, small chemical expansion and etc. have been attracting increasing interest. Good performance has been reported with a few of perovskite structure anodes, such as (LaSr)(CrMn)O3. However, more improvements need to be made before meeting the application requirement. Understanding the oxidation mechanism is crucial for a directed optimization, but it is still on the early stage of investigation. In this study, reaction mechanism of oxide anodes is investigated on doped YCrO 3 with H2 fuel, in terms of the origin of electrochemical activity, rate-determining steps (RDS), extension of reactive zone, and the impact from overpotential under service condition to those properties. H2 oxidation on the YCs anodes is found to be limited by charge transfer and H surface diffusion. A model is presented to describe the elementary steps in H2 oxidation. From the reaction order results, it is suggested that any models without taking H into the charge transfer step are invalid. The nature of B site element determines the H2 oxidation kinetics primarily. Ni displays better adsorption ability than Co. However, H adsorption ability of such oxide anode is inferior to that of Ni metal anode. In addition, the charge transfer step is directly associated with the activity of electrons in the anode; therefore it can be significantly promoted by enhancement of the electron activity. It is found that A site Ca doping improves the polarization resistance about 10 times, by increasing the activity of electrons to promote the charge transfer process. For the active area in the oxide anode, besides the traditional three-phase boundary (3PB), the internal anode surface as two-phase boundary (2PB) is proven to be capable of catalytically oxidizing the H2 fuel also when the bulk lattice is activated depending on the B site elements. The contribution from each part is estimated by switching the electrolyte to change 3PB kinetics. Compared to Ni, Co doping activates the bulk oxygen more significantly, promoting the reaction at 2PB. The active surface reaction zone is found to be enlarged by the electrolyte with high oxygen activity (SSZ vs. YSZ) when charge transfer is one of the RDS. Due to the larger exchange current for charge transfer in 3PB with SSZ electrolyte, the adsorption gradient zone is broadened, leading to enhanced surface reaction kinetics. The potential application of such finding is demonstrated on SSZ/YSZ/SSZ sandwich, showing largely improved electrode performance, opening a wide door for the utilization of electrolytes that are too expensive, fragile or instable to be used before. The bulk path way in 2PB reaction can be affected by overpotential in terms of local vacancy concentration, built-in electrical field and stability. It is proven that an uneven distribution of lattice oxygen is established under operation conditions with overpotential by both qualitative analysis and analytic solution. An electrostatic field force is present besides the concentration gradient in the anode lattice to control the motion of oxygen ions. Compared to the usual estimation based on chemical diffusion mechanism, the real deviation of ionic defects concentration under polarization from the equilibrium state near electrode/electrolyte interface is smaller with the built-in electrical field. The overpotential is demonstrated to be able to open up or shut down the bulk pathway depending on the ionic defects of electrodes. The analysis on the bulk pathway in terms of local charged species and various potentials provides new insight in anion diffusion and electrode stability.

Simultaneous determination of hydroxylamine and phenol using a nanostructure-based electrochemical sensor.

PubMed

Moghaddam, Hadi Mahmoudi; Beitollahi, Hadi; Tajik, Somayeh; Malakootian, Mohammad; Maleh, Hassan Karimi

2014-11-01

The electrochemical oxidation of hydroxylamine on the surface of a carbon paste electrode modified with carbon nanotubes and 2,7-bis(ferrocenyl ethyl)fluoren-9-one is studied. The electrochemical response characteristics of the modified electrode toward hydroxylamine and phenol were investigated. The results showed an efficient catalytic activity of the electrode for the electro-oxidation of hydroxylamine, which leads to lowering its overpotential. The modified electrode exhibits an efficient electron-mediating behavior together with well-separated oxidation peaks for hydroxylamine and phenol. Also, the modified electrode was used for determination of hydroxylamine and phenol in some real samples.

Enabling catalytic oxidation of Li2O2 at the liquid-solid interface: the evolution of an aprotic Li-O2 battery.

PubMed

Feng, Ningning; He, Ping; Zhou, Haoshen

2015-02-01

We show that by using a suitable soluble redox mediator, the charging overpotential can be reduced and the round-trip efficiency can be improved in an aprotic Li-O2 battery. Not only do we explore a new redox couple, 10-methyl-10H-phenothiazine, as a soluble catalyst that improves the electrochemical performance, but we also propose possible challenges that need to be overcome for the future improvement of aprotic Li-O2 batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Porous Cobalt Phosphide Polyhedrons with Iron Doping as an Efficient Bifunctional Electrocatalyst.

PubMed

Li, Feng; Bu, Yunfei; Lv, Zijian; Mahmood, Javeed; Han, Gao-Feng; Ahmad, Ishfaq; Kim, Guntae; Zhong, Qin; Baek, Jong-Beom

2017-10-01

Iron (Fe)-doped porous cobalt phosphide polyhedrons are designed and synthesized as an efficient bifunctional electrocatalyst for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The synthesis strategy involves one-step route for doping foreign metallic element and forming porous cobalt phosphide polyhedrons. With varying doping levels of Fe, the optimized Fe-doped porous cobalt phosphide polyhedron exhibits significantly enhanced HER and OER performances, including low onset overpotentials, large current densities, as well as small Tafel slopes and good electrochemical stability during HER and OER. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mathematical Modeling of Electrochemical Flow Capacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoyt, NC; Wainright, JS; Savinell, RF

Electrochemical flow capacitors (EFCs) for grid-scale energy storage are a new technology that is beginning to receive interest. Prediction of the expected performance of such systems is important as modeling can be a useful avenue in the search for design improvements. Models based off of circuit analogues exist to predict EFC performance, but these suffer from deficiencies (e.g. a multitude of fitting constants that are required and the ability to analyze only one spatial direction at a time). In this paper mathematical models based off of three-dimensional macroscopic balances (similar to models for porous electrodes) are reported. Unlike existing three-dimensionalmore » porous electrode-based approaches for modeling slurry electrodes, advection (i.e., transport associated with bulk fluid motion) of the overpotential is included in order to account for the surface charge at the interface between flowing particles and the electrolyte. Doing so leads to the presence of overpotential boundary layers that control the performance of EFCs. These models were used to predict the charging behavior of an EFC under both flowing and non-flowing conditions. Agreement with experimental data was good, including proper prediction of the steady-state current that is achieved during charging of a flowing EFC. (C) The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. All rights reserved.« less

Engineering a nanotubular mesoporous cobalt phosphide electrocatalyst by the Kirkendall effect towards highly efficient hydrogen evolution reactions.

PubMed

Miao, Yue-E; Li, Fei; Zhou, Yu; Lai, Feili; Lu, Hengyi; Liu, Tianxi

2017-11-02

Tailoring the size and controlling the morphology of particular nano-architectures are considered as two promising strategies to improve the catalytic performance of metal nanocrystals towards hydrogen evolution reactions (HERs). Herein, mesoporous cobalt phosphide nanotubes (CoP-NTs) with a three-dimensional network structure have been obtained through a facile and efficient electrospinning technique combined with thermal stabilization and phosphorization treatments. The thermal stabilization process has been demonstrated to play a key role in the morphological tailoring of Co 3 O 4 nanotubes (Co 3 O 4 -NTs). As a result, the CoP-NTs show one-dimensional hollow tubular architecture instead of forming a worm-like tubular CoP structure (W-CoP-NTs) or severely aggregated CoP powder (CoP-NPs) which originate from the Co 3 O 4 nanotubes without thermal stabilization treatment and Co 3 O 4 nanoparticles, respectively. Satisfyingly, under an optimized phosphorization degree, the CoP-NT electrode exhibits a low onset overpotential of 53 mV with a low Tafel slope of 50 mV dec -1 during the HER process. Furthermore, the CoP-NT electrode is capable of driving a large cathodic current density of 10 mA cm -2 at an overpotential of 152 mV, which is much lower than those of its contrast samples, i.e. CoP-NPs (211 mV) and W-CoP-NTs (230 mV). Therefore, this work provides a feasible and general strategy for constructing three-dimensionally organized mesoporous non-noble metal phosphide nanotubes as promising alternative high-performance electrocatalysts for the commercial platinum ones.

Binary cobalt ferrite nanomesh arrays as the advanced binder-free electrode for applications in oxygen evolution reaction and supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Li; Zhang, Huijuan; Mu, Yanping; Bai, Yuanjuan; Wang, Yu

2016-09-01

The porous CoFe2O4nanomesh arrays are successfully synthesized on nickel foam substrate through a high temperature and pressure hydrothermal method, following by the thermal post-treatment in air. The CoFe2O4 nanomesh arrays own numerous pores and large specific surface area, which is in favor of exposing more active sites. In consideration of the structural preponderances and versatility of the materials, the CoFe2O4 nanomesh arrays have been researched as the binder-free electrode materials for electrocatalysis and supercapacitors. When the CoFe2O4nanomesh arrays on nickel foam (CoFe2O4 NM-As/Ni) directly act as the free-binder catalyst toward catalyzing the oxygen evolution reaction (OER) of electrochemical water splitting, CoFe2O4 NM-As/Ni exhibits an admirable OER property with a low onset potential of 1.47 V(corresponding to the onset overpotential of 240 mV), a minimal overpotential (η10 = 253 mV), a small Tafel slope (44 mV dec-1), large anodic currents and long-term durability for 35 h in alkaline media. In addition, as an electrode of supercapacitors, CoFe2O4 NM-As/Ni obtains a desired specific capacitance (1426 F/g at the current density of 1 A/g), remarkable rate capability (1024 F/g at the current density of 20 A/g) and eminent capacitance retention (92.6% after 3000 cycles). The above results demonstrate the CoFe2O4 NM-As/Ni possesses great potential application in electrocatalysis and supercapacitors.

Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications

PubMed Central

Hu, Qichao; Caputo, Antonio; Sadoway, Donald R.

2013-01-01

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (<80 °C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 °C. These cooling systems tend to increase battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed. PMID:23963203

Solid-state graft copolymer electrolytes for lithium battery applications.

PubMed

Hu, Qichao; Caputo, Antonio; Sadoway, Donald R

2013-08-12

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (< 80 °C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 °C. These cooling systems tend to increase battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed.

Amorphous MoS{sub x} on CdS nanorods for highly efficient photocatalytic hydrogen evolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Xiaofang; Tang, Chaowan; Zheng, Qun

Loading cocatalyst on semiconductors was crucially necessary for improving the photocatalytic hydrogen evolution. Amorphous MoS{sub x} as a novel and noble metal-free cocatalyst was loaded on CdS nanorods by a simple photodeposition method. Efficient hydrogen evolution with amount of 15 mmol h{sup −1} g{sup −1} was observed over the MoS{sub x} modified CdS nanorods, which was about 6 times higher than that by using Pt as cocatalyst. Meanwhile, with MoS{sub x} cocatalyst, the efficiency of CdS nanorods was superior to that of CdS nanoparticles and bulk CdS. No deactivation could be observed in the efficiency of MoS{sub x} modified CdSmore » nanorods under irradiation for successive 10 h. Further experimental results indicated that the efficient electrons transfer, low overpotential of hydrogen evolution and active S atoms over the MoS{sub x} modified CdS nanorods were responsible for the higher efficiency. Our results provided guidance for synthesizing noble metal-free materials as cocatalyst for photocatalytic hydrogen evolution. - Graphical abstract: Photodeposition of amorphous MoS{sub x} on CdS nanorods for highly efficient photocatalytic hydrogen evolution. - Highlights: • Amorphous MoSx cocatalyst was loaded on CdS NRs by a simple photodeposition. • MoS{sub x}/CdS NRs exhibited 6 times higher hydrogen evolution efficiency than Pt/CdS NRs. • The hydrogen evolution of MoS{sub x}/CdS NRs linearly increased with prolonging time. • Lower overpotential and efficient electron transfer were observed over MoS{sub x}/CdS NRs.« less

Surface spintronics enhanced photo-catalytic hydrogen evolution: Mechanisms, strategies, challenges and future

NASA Astrophysics Data System (ADS)

Zhang, Wenyan; Gao, Wei; Zhang, Xuqiang; Li, Zhen; Lu, Gongxuan

2018-03-01

Hydrogen is a green energy carrier with high enthalpy and zero environmental pollution emission characteristics. Photocatalytic hydrogen evolution (HER) is a sustainable and promising way to generate hydrogen. Despite of great achievements in photocatalytic HER research, its efficiency is still limited due to undesirable electron transfer loss, high HER over-potential and low stability of some photocatalysts, which lead to their unsatisfied performance in HER and anti-photocorrosion properties. In recent years, many spintronics works have shown their enhancing effects on photo-catalytic HER. For example, it was reported that spin polarized photo-electrons could result in higher photocurrents and HER turn-over frequency (up to 200%) in photocatalytic system. Two strategies have been developed for electron spin polarizing, which resort to heavy atom effect and magnetic induction respectively. Both theoretical and experimental studies show that controlling spin state of OHrad radicals in photocatalytic reaction can not only decrease OER over-potential (even to 0 eV) of water splitting, but improve stability and charge lifetime of photocatalysts. A convenient strategy have been developed for aligning spin state of OHrad by utilizing chiral molecules to spin filter photo-electrons. By chiral-induced spin filtering, electron polarization can approach to 74%, which is significantly larger than some traditional transition metal devices. Those achievements demonstrate bright future of spintronics in enhancing photocatalytic HER, nevertheless, there is little work systematically reviewing and analysis this topic. This review focuses on recent achievements of spintronics in photocatalytic HER study, and systematically summarizes the related mechanisms and important strategies proposed. Besides, the challenges and developing trends of spintronics enhanced photo-catalytic HER research are discussed, expecting to comprehend and explore such interdisciplinary research in photocatalytic HER.

Numerical insights into the early stages of nanoscale electrodeposition: nanocluster surface diffusion and aggregative growth.

PubMed

Mamme, Mesfin Haile; Köhn, Christoph; Deconinck, Johan; Ustarroz, Jon

2018-04-19

Fundamental understanding of the early stages of electrodeposition at the nanoscale is key to address the challenges in a wide range of applications. Despite having been studied for decades, a comprehensive understanding of the whole process is still out of reach. In this work, we introduce a novel modelling approach that couples a finite element method (FEM) with a random walk algorithm, to study the early stages of nanocluster formation, aggregation and growth, during electrochemical deposition. This approach takes into account not only electrochemical kinetics and transport of active species, but also the surface diffusion and aggregation of adatoms and small nanoclusters. The simulation results reveal that the relative surface mobility of the nanoclusters compared to that of the adatoms plays a crucial role in the early growth stages. The number of clusters, their size and their size dispersion are influenced more significantly by nanocluster mobility than by the applied overpotential itself. Increasing the overpotential results in shorter induction times and leads to aggregation prevalence at shorter times. A higher mobility results in longer induction times, a delayed transition from nucleation to aggregation prevalence, and as a consequence, a larger surface coverage of smaller clusters with a smaller size dispersion. As a consequence, it is shown that a classical first-order nucleation kinetics equation cannot describe the evolution of the number of clusters with time, N(t), in potentiostatic electrodeposition. Instead, a more accurate representation of N(t) is provided. We show that an evaluation of N(t), which neglects the effect of nanocluster mobility and aggregation, can induce errors of several orders of magnitude in the determination of nucleation rate constants. These findings are extremely important towards evaluating the elementary electrodeposition processes, considering not only adatoms, but also nanoclusters as building blocks.

Electrochemically formed 3D hierarchical thin films of cobalt-manganese (Co-Mn) hexacyanoferrate hybrids for electrochemical applications

NASA Astrophysics Data System (ADS)

Alam Venugopal, Narendra Kumar; Joseph, James

2016-02-01

Here we report the feasibility of forming 3D nanostructured hexacyanoferates of Cobalt and Manganese (Co-MnHCF) on GC surface by a facile electrochemical method. This 3D architecture on glassy carbon electrode characterised systematically by voltammetry and other physical characterisation techniques like Field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and Fourier transform Infrared spectroscopy (FTIR) etc,. Electrochemical Quartz crystal microbalance (EQCM) studies helped out to calculate the total mass change during Co-MnHCF formation. Electrochemical studies reveal that the formal redox potentials of both Co and MnHCF films remained close to that of newly formed Co-MnHCF hybrid films. These 3D modified films were successfully applied for two different electrochemical applications i) For pseudocapacitor studies in KNO3 medium ii) Investigated the electrocatalytic behaviour of redox film towards water oxidation reaction in alkaline medium. Electrochemical performances of newly formed Co-MnHCF are compared with their individual transition metal (Co, Mn) hexacyanoferrates. The resulting material shows a specific capacitance of 350 F g-1 through its fast reversible redox reaction of electrochemically formed Co-MnHCF modified film. Interestingly we showed the overpotential of 450 mV (from its thermodynamic voltage 1.2 V) to attain its optimum current density of 10 mA cm-2 for O2 evolution in alkaline medium.

Nanoimprint methods for the fabrication of macroscopic plasmonically active metal nanostructures

NASA Astrophysics Data System (ADS)

Nagel, Robin D.; Filser, Simon; Zhang, Tianyue; Manzi, Aurora; Schönleber, Konrad; Lindsly, James; Zimmermann, Josef; Maier, Thomas L.; Scarpa, Giuseppe; Krischer, Katharina; Lugli, Paolo

2017-02-01

In this article, we present a refined nanostructuring method, lift-off nanoimprint lithography (LO-NIL), which allows the deposition of high-quality metal nanostructures due to a bilayer resist process and compare it to nano-transfer printing (nTP), a purely additive metal printing technique. LO-NIL and nTP are used as accurate methods for the fabrication of ordered plasmonic metal nanostructure arrays on semiconducting substrates over large areas using the example of gold nanodisks on silicon. The possibility of feature size adjustment in LO-NIL during the fabrication process is especially useful for tuning plasmonic resonance peaks between the visible and the mid-infrared range as well as fine-tuning of these resonances. In UV-VIS-NIR spectroscopic measurements, a significant blueshift in the plasmonic resonance was found for nTP samples compared to the ones fabricated with the lift-off technique. It was concluded that this shift originates from a metal/substrate interface roughness resulting in a change in the dielectric properties of this layer. This finding was verified with finite difference time-domain simulations where a similar trend was found for a model with an assumed thin air gap in this interface. In cyclic voltammetry measurements under illumination, a reduced overpotential by almost 400 mV for CO2 reduction and hydrogen evolution was found for LO-NIL samples.

Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries

DOE PAGES

Fan, Frank Y.; Pan, Menghsuan Sam; Lau, Kah Chun; ...

2016-11-25

Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange currentmore » density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li 2S 8 and Li 2S 4).« less

Modification of molybdenum disulfide in methanol solvent for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Niyitanga, Theophile; Jeong, Hae Kyung

2018-05-01

Molybdenum disulfide is a promising catalyst to replace the expensive platinum as an electrocatalyst but needs to be modified to present excellent electrocatalytic properties. Herein, we successfully modify molybdenum disulfide in methanol solvent for hydrogen evolution reaction by using a simple hydrothermal method. Overpotential reduced to -0.6 V from -1.5 V, and energy band gap decreased from 1.73 eV to 1.58 eV after the modification. The modified molybdenum disulfide also demonstrated lower resistance (42 Ω) at high frequency (1000 kHz) compared with that (240 Ω) of the precursor, showing that conductivity of the modified molybdenum disulfide has improved.

Porous dendritic copper: an electrocatalyst for highly selective CO2 reduction to formate in water/ionic liquid electrolyte.

PubMed

Huan, Tran Ngoc; Simon, Philippe; Rousse, Gwenaëlle; Génois, Isabelle; Artero, Vincent; Fontecave, Marc

2017-01-01

Copper is currently extensively studied because it provides promising electrodes for carbon dioxide electroreduction. The original combination, reported here, of a nanostructured porous dendritic Cu-based material, characterized by electron microcopy (SEM, TEM) and X-ray diffraction methods, and a water/ionic liquid mixture as the solvent, contributing to CO 2 solubilization and activation, results in a remarkably efficient (large current densities at low overpotentials), stable and selective (large faradic yields) electrocatalytic system for the conversion of CO 2 into formic acid, a product with a variety of uses. These results provide new directions for the further improvement of Cu electrodes.

Electrochemical CO 2 Reduction on Oxide-Derived Cu Surface with Various Oxide Thicknesses

DOE PAGES

Liang, Zhixiu; Fu, Jie; Vukmirovic, Miomir B.; ...

2018-03-26

Here, cuprous oxide on copper foil electrodes prepared via electrochemical deposition and thermal annealing are investigated towards CO 2 electrochemical reduction at low overpotential. The thickness of the electrochemical deposited Cu 2O was controlled by varying the constant-current deposition time. The surface morphology and roughness were examined with SEM and CV respectively. The electrode fabricated by cuprous oxide deposited for 20 min demonstrated the best faradic efficiency (7.02%) and specific activity (0.123 mA/cm 2) towards format/formic acid formation at -0.5 V vs. RHE in CO 2 saturated 0.5 M K 2CO 3 among studied samples.

Communication — Modeling polymer-electrolyte fuel-cell agglomerates with double-trap kinetics

DOE PAGES

Pant, Lalit M.; Weber, Adam Z.

2017-04-14

A new semi-analytical agglomerate model is presented for polymer-electrolyte fuel-cell cathodes. The model uses double-trap kinetics for the oxygen-reduction reaction, which can capture the observed potential-dependent coverage and Tafel-slope changes. An iterative semi-analytical approach is used to obtain reaction rate constants from the double-trap kinetics, oxygen concentration at the agglomerate surface, and overall agglomerate reaction rate. The analytical method can predict reaction rates within 2% of the numerically simulated values for a wide range of oxygen concentrations, overpotentials, and agglomerate sizes, while saving simulation time compared to a fully numerical approach.

Electrochemical CO 2 Reduction on Oxide-Derived Cu Surface with Various Oxide Thicknesses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Zhixiu; Fu, Jie; Vukmirovic, Miomir B.

Here, cuprous oxide on copper foil electrodes prepared via electrochemical deposition and thermal annealing are investigated towards CO 2 electrochemical reduction at low overpotential. The thickness of the electrochemical deposited Cu 2O was controlled by varying the constant-current deposition time. The surface morphology and roughness were examined with SEM and CV respectively. The electrode fabricated by cuprous oxide deposited for 20 min demonstrated the best faradic efficiency (7.02%) and specific activity (0.123 mA/cm 2) towards format/formic acid formation at -0.5 V vs. RHE in CO 2 saturated 0.5 M K 2CO 3 among studied samples.

Modeling the voltage loss mechanisms in lithium-sulfur cells: the importance of electrolyte resistance and precipitation kinetics.

PubMed

Zhang, Teng; Marinescu, Monica; O'Neill, Laura; Wild, Mark; Offer, Gregory

2015-09-21

Understanding of the complex electrochemical, transport, and phase-change phenomena in Li-S cells requires experimental characterization in tandem with mechanistic modeling. However, existing Li-S models currently contradict some key features of experimental findings, particularly the evolution of cell resistance during discharge. We demonstrate that, by introducing a concentration-dependent electrolyte conductivity, the correct trends in voltage drop due to electrolyte resistance and activation overpotentials are retrieved. In addition, we reveal the existence of an often overlooked potential drop mechanism in the low voltage-plateau which originates from the limited rate of Li2S precipitation.

Active and Durable Hydrogen Evolution Reaction Catalyst Derived from Pd-Doped Metal-Organic Frameworks.

PubMed

Chen, Jitang; Xia, Guoliang; Jiang, Peng; Yang, Yang; Li, Ren; Shi, Ruohong; Su, Jianwei; Chen, Qianwang

2016-06-01

The water electrolysis is of critical importance for sustainable hydrogen production. In this work, a highly efficient and stable PdCo alloy catalyst (PdCo@CN) was synthesized by direct annealing of Pd-doped metal-organic frameworks (MOFs) under N2 atmosphere. In 0.5 M H2SO4 solution, PdCo@CN displays remarkable electrocatalytic performance with overpotential of 80 mV, a Tafel slope of 31 mV dec(-1), and excellent stability of 10 000 cycles. Our studies reveal that noble metal doped MOFs are ideal precursors for preparing highly active alloy electrocatalysts with low content of noble metal.

Solution synthesis of metal silicide nanoparticles.

PubMed

McEnaney, Joshua M; Schaak, Raymond E

2015-02-02

Transition-metal silicides are part of an important family of intermetallic compounds, but the high-temperature reactions that are generally required to synthesize them preclude the formation of colloidal nanoparticles. Here, we show that palladium, copper, and nickel nanoparticles react with monophenylsilane in trioctylamine and squalane at 375 °C to form colloidal Pd(2)Si, Cu(3)Si, and Ni(2)Si nanoparticles, respectively. These metal silicide nanoparticles were screened as electrocatalysts for the hydrogen evolution reaction, and Pd(2)Si and Ni(2)Si were identified as active catalysts that require overpotentials of -192 and -243 mV, respectively, to produce cathodic current densities of -10 mA cm(-2).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tylka, M. M.; Willit, J. L.; Williamson, M. A.

This work examines the nucleation and growth behavior of uranium and plutonium from molten LiCl-KCl eutectic on inert electrodes using electrochemical techniques. Current-time transients obtained from chronoamperometric experiments were compared with theoretical models to characterize the type of nucleation (progressive or instantaneous) for deposition of U and Pu, and co-deposition of U-Pu, from molten LiCl-KCl at inert electrodes. It was established that the nucleation mode of actinides present as chlorides in molten chloride salts changes from progressive to instantaneous with an increasing concentration of the trivalent actinide ions in the salt. The effect of the material of the working electrodemore » was investigated, and it was found that changing the material from tungsten to silver improves resolvability of the nucleation peaks and allows more accurate analysis of the experimental measurements. Using the nucleation data, diffusion coefficients were obtained for U 3+ and Pu 3+, and were found to be in very good agreement with the values obtained from other studies. Furthermore, the density of nuclei produced during instantaneous nucleation, the rate of nucleation for progressive nucleation, and the radius of the deposited nuclei were evaluated and examined at different overpotentials.« less

Surface properties and graphitization of polyacrylonitrile based fiber electrodes affecting the negative half-cell reaction in vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Langner, J.; Bruns, M.; Dixon, D.; Nefedov, A.; Wöll, Ch.; Scheiba, F.; Ehrenberg, H.; Roth, C.; Melke, J.

2016-07-01

Carbon felt electrodes for vanadium redox flow batteries are obtained by the graphitization of polyacrylonitrile based felts at different temperatures. Subsequently, the surface of the felts is modified via thermal oxidation at various temperatures. A single-cell experiment shows that the voltage efficiency is increased by this treatment. Electrode potentials measured with reference electrode setup show that this voltage efficiency increase is caused mainly by a reduction of the overpotential of the negative half-cell reaction. Consequently, this reaction is investigated further by cyclic voltammetry and the electrode activity is correlated with structural and surface chemical properties of the carbon fibers. By Raman, X-ray photoelectron and near edge X-ray absorption fine structure spectroscopy the role of edge sites and oxygen containing functional groups (OCFs) for the electrochemical activity are elucidated. A significant activity increase is observed in correlation with these two characteristics. The amount of OCFs is correlated with structural defects (e.g. edge sites) of the carbon fibers and therefore decreases with an increasing graphitization degree. Thus, for the same thermal oxidation temperature carbon fibers graphitized at a lower temperature show higher activities than those graphitized at a higher temperature.

A dynamic plug flow reactor model for a vanadium redox flow battery cell

NASA Astrophysics Data System (ADS)

Li, Yifeng; Skyllas-Kazacos, Maria; Bao, Jie

2016-04-01

A dynamic plug flow reactor model for a single cell VRB system is developed based on material balance, and the Nernst equation is employed to calculate cell voltage with consideration of activation and concentration overpotentials. Simulation studies were conducted under various conditions to investigate the effects of several key operation variables including electrolyte flow rate, upper SOC limit and input current magnitude on the cell charging performance. The results show that all three variables have a great impact on performance, particularly on the possibility of gassing during charging at high SOCs or inadequate flow rates. Simulations were also carried out to study the effects of electrolyte imbalance during long term charging and discharging cycling. The results show the minimum electrolyte flow rate needed for operation within a particular SOC range in order to avoid gassing side reactions during charging. The model also allows scheduling of partial electrolyte remixing operations to restore capacity and also avoid possible gassing side reactions during charging. Simulation results also suggest the proper placement for cell voltage monitoring and highlight potential problems associated with setting the upper charging cut-off limit based on the inlet SOC calculated from the open-circuit cell voltage measurement.

Low-Temperature Synthesis of Hierarchical Amorphous Basic Nickel Carbonate Particles for Water Oxidation Catalysis.

PubMed

Yang, Yisu; Liang, Fengli; Li, Mengran; Rufford, Thomas E; Zhou, Wei; Zhu, Zhonghua

2015-07-08

Amorphous nickel carbonate particles are catalysts for the oxygen evolution reaction (OER), which plays a critical role in the electrochemical splitting of water. The amorphous nickel carbonate particles can be prepared at a temperature as low as 60 °C by an evaporation-induced precipitation (EIP) method. The products feature hierarchical pore structures. The mass-normalized activity of the catalysts, measured at an overpotential of 0.35 V, was 55.1 A g(-1) , with a Tafel slope of only 60 mV dec(-1) . This catalytic activity is superior to the performance of crystalline NiOx particles and β-Ni(OH)2 particles, and compares favorably to state-of-the-art RuO2 catalysts. The activity of the amorphous nickel carbonate is remarkably stable during a 10 000 s chronoamperometry test. Further optimization of synthesis parameters reveals that the amorphous structure can be tuned by adjusting the H2 O/Ni ratio in the precursor mixture. These results suggest the potential application of easily prepared hierarchical basic nickel carbonate particles as cheap and robust OER catalysts with high activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water oxidation by a nickel-glycine catalyst.

PubMed

Wang, Dong; Ghirlanda, Giovanna; Allen, James P

2014-07-23

The utilization of solar energy requires an efficient means for its storage as chemical energy. In bioinspired artificial photosynthesis, light energy can be used to drive water oxidation, but catalysts that produce molecular oxygen from water are needed to avoid excessive driving potentials. In this paper, we demonstrate the utility of a novel complex utilizing earth-abundant Ni in combination with glycine as an efficient catalyst with a modest overpotential of 0.475 ± 0.005 V at a current density of 1 mA/cm(2) at pH 11. Catalysis requires the presence of the amine moiety with the glycine most likely coordinating the Ni in a 4:1 molar ratio. The production of molecular oxygen at a high potential is verified by measurement of the change in oxygen concentration, yielding a Faradaic efficiency of 60 ± 5%. The catalytic species is most likely a heterogeneous Ni-hydroxide formed by electrochemical oxidation. This Ni species can achieve a current density of 4 mA/cm(2) that persists for at least 10 h. Based upon the observed pH dependence of the current amplitude and oxidation/reduction peaks, the catalytic mechanism is an electron-proton coupled process.

Uniquely confining Cu2S nanoparticles in graphitized carbon fibers for enhanced oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Zhao, Xiaoqian; Liu, Li; Zhang, Yan; Zhang, Huijuan; Wang, Yu

2017-08-01

Up to now, the literature on Cu2S with specific morphology applied to oxygen evolution reaction (OER) in the electrocatalytic field has been limited. In this work, unique peapod-like Cu2S/C exhibiting superb electrocatalytic performance toward OER is successfully synthesized, by employing Cu(OH)2 nanorods as the template and nontoxic glucose as the carbon source and then annealing with sublimed sulfur. It can be seen that this work explores a new application area for Cu2S. More precisely, the novel morphology contributes to increasing the electrochemical active surface area effectively and promoting contact between the Cu2S nanoparticles and the electrolyte. During electrochemical measurements, the peapod-like Cu2S/C shows enhanced electrocatalytic activity with a low overpotential of 401 mV at the current density of 10 mA cm-2 and a Tafel slope of 52 mV dec-1. More importantly, our material is able to maintain stability for at least 8 h at constant potential and the current loss is negligible after 2000 cycles. Obviously, these striking properties fully demonstrate that the peapod-like Cu2S/C as an efficient catalyst shows great promise for OER.

Electrochemical Nucleation and Growth of Uranium and Plutonium from Molten Salts

DOE PAGES

Tylka, M. M.; Willit, J. L.; Williamson, M. A.

2017-07-18

This work examines the nucleation and growth behavior of uranium and plutonium from molten LiCl-KCl eutectic on inert electrodes using electrochemical techniques. Current-time transients obtained from chronoamperometric experiments were compared with theoretical models to characterize the type of nucleation (progressive or instantaneous) for deposition of U and Pu, and co-deposition of U-Pu, from molten LiCl-KCl at inert electrodes. It was established that the nucleation mode of actinides present as chlorides in molten chloride salts changes from progressive to instantaneous with an increasing concentration of the trivalent actinide ions in the salt. The effect of the material of the working electrodemore » was investigated, and it was found that changing the material from tungsten to silver improves resolvability of the nucleation peaks and allows more accurate analysis of the experimental measurements. Using the nucleation data, diffusion coefficients were obtained for U 3+ and Pu 3+, and were found to be in very good agreement with the values obtained from other studies. Furthermore, the density of nuclei produced during instantaneous nucleation, the rate of nucleation for progressive nucleation, and the radius of the deposited nuclei were evaluated and examined at different overpotentials.« less

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

NASA Technical Reports Server (NTRS)

Huang, C. J.; Yeager, E.; Ogrady, W. E.

1975-01-01

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis.

PubMed

McKendry, Ian G; Thenuwara, Akila C; Shumlas, Samantha L; Peng, Haowei; Aulin, Yaroslav V; Chinnam, Parameswara Rao; Borguet, Eric; Strongin, Daniel R; Zdilla, Michael J

2018-01-16

The effect on the electrocatalytic oxygen evolution reaction (OER) of cobalt incorporation into the metal oxide sheets of the layered manganese oxide birnessite was investigated. Birnessite and cobalt-doped birnessite were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and conductivity measurements. A cobalt:manganese ratio of 1:2 resulted in the most active catalyst for the OER. In particular, the overpotential (η) for the OER was 420 mV, significantly lower than the η = 780 mV associated with birnessite in the absence of Co. Furthermore, the Tafel slope for Co/birnessite was 81 mV/dec, in comparison to a Tafel slope of greater than 200 mV/dec for birnessite. For chemical water oxidation catalysis, an 8-fold turnover number (TON) was achieved (h = 70 mmol of O 2 /mol of metal). Density functional theory (DFT) calculations predict that cobalt modification of birnessite resulted in a raising of the valence band edge and occupation of that edge by holes with enhanced mobility during catalysis. Inclusion of extra cobalt beyond the ideal 1:2 ratio was detrimental to catalysis due to disruption of the layered structure of the birnessite phase.

Review-Physicochemical hydrodynamics of gas bubbles in two phase electrochemical systems.

PubMed

Taqieddin, Amir; Nazari, Roya; Rajic, Ljiljana; Alshawabkeh, Akram

2017-01-01

Electrochemical systems suffer from poor management of evolving gas bubbles. Improved understanding of bubbles behavior helps to reduce overpotential, save energy and enhance the mass transfer during chemical reactions. This work investigates and reviews the gas bubbles hydrodynamics, behavior, and management in electrochemical cells. Although the rate of bubble growth over the electrode surface is well understood, there is no reliable prediction of bubbles break-off diameter from the electrode surface because of the complexity of bubbles motion near the electrode surface. Particle Image Velocimetry (PIV) and Laser Doppler Anemometry (LDA) are the most common experimental techniques to measure bubble dynamics. Although the PIV is faster than LDA, both techniques are considered expensive and time-consuming. This encourages adapting Computational Fluid Dynamics (CFD) methods as an alternative to study bubbles behavior. However, further development of CFD methods is required to include coalescence and break-up of bubbles for better understanding and accuracy. The disadvantages of CFD methods can be overcome by using hybrid methods. The behavior of bubbles in electrochemical systems is still a complex challenging topic which requires a better understanding of the gas bubbles hydrodynamics and their interactions with the electrode surface and bulk liquid, as well as between the bubbles itself.

The application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes

NASA Technical Reports Server (NTRS)

Macdonald, D. D.; Pound, B. G.; Lenhart, S. J.

1989-01-01

Electrochemical impedance spectra of rolled and bonded and sintered porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes for rolled and bonded electrodes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (non-porous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low. Transmission line modeling results suggest that porous rolled and bonded nickel electrodes undergo restructuring during charge/discharge cycling prior to failure.

Solid oxide reversible cells (SORCs) using LaGaO3-based oxide electrolyte and oxide fuel electrode

NASA Astrophysics Data System (ADS)

Ishihara, Tatsumi

2017-09-01

Activity of La0.8Sr0.2FeO3 (LSF) to the fuel electrode reaction in Solid Oxide Reversible Cells (SORCs) was investigated by using La0.9Sr0.1Ga0.8Mg0.2O3 (LSGM) and Ba0.6La0.4CoO3 (BLC) as electrolyte and air electrode, respectively. In electrolysis mode (SOEC), LSF electrode exhibited small overpotential under the atmosphere without H2 co-feeding; the current densities reached -1.42, -0.92, -0.36 A/cm2 at 1.4 V at 900, 800, 700 °C, respectively and H2 formation rate is well agreed with that estimated by Faraday's law. On the other hand, in the SOEC-SOFC reversible mode with the gas composition of 20% steam /20%H2/60%Ar, the maximum power densities of 0.42, 0.28, 0.11 W/cm2 were achieved at 900, 800 and 700 °C, respectively. In addition, the cyclic reversible operation was also investigated at 800 °C, and it was found that the cell showed high stability over 30 cycles. DC polarization measurement suggests that the exchange current density of LSF is 14 mA/cm2 at 700 °C, which is almost the same with that of Ni-YSZ reported. XRD measurement and SEM observation after the reversible measurement suggest that LSF is highly stable under SOEC-SOFC cyclic operation condition. Therefore, LSF is promising as the fuel electrode for SORCs, although the conductivity is not sufficiently high as electrode.

Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

NASA Astrophysics Data System (ADS)

Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

2018-05-01

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

An ultrafine platinum-cobalt alloy decorated cobalt nanowire array with superb activity toward alkaline hydrogen evolution.

PubMed

Wang, Ziqiang; Ren, Xiang; Luo, Yonglan; Wang, Liang; Cui, Guanwei; Xie, Fengyu; Wang, Hongjing; Xie, Ying; Sun, Xuping

2018-06-22

It is highly desired to design and develop highly efficient electrocatalysts for alkaline hydrogen evolution reactions. Herein, we report the development of ultrafine PtCo alloy nanoparticle decorated one-dimensional Co nanowires grown on Ti mesh (PtCo-Co/TiM). Owing to its favorable composition and structure, the PtCo-Co/TiM can deliver an ultrahigh current density of 46.5 mA cm-2 at an overpotential of 70 mV in 1.0 M KOH, superior to recently reported Pt-based electrocatalysts. This catalyst also provides excellent long-term electrochemical durability with its catalytic activity being maintained for at least 50 h.

Graphite oxide and molybdenum disulfide composite for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Niyitanga, Theophile; Jeong, Hae Kyung

2017-10-01

Graphite oxide and molybdenum disulfide (GO-MoS2) composite is prepared through a wet process by using hydrolysis of ammonium tetrathiomolybdate, and it exhibits excellent catalytic activity of the hydrogen evolution reaction (HER) with a low overpotential of -0.47 V, which is almost two and three times lower than those of precursor MoS2 and GO. The high performance of HER of the composite attributes to the reduced GO supporting MoS2, providing a conducting network for fast electron transport from MoS2 to electrodes. The composite also shows high stability after 500 cycles, demonstrating a synergistic effect of MoS2 and GO for efficient HER.

Increased sensitivity of anodic stripping voltammetry at the hanging mercury drop electrode by ultracathodic deposition.

PubMed

Rodrigues, José A; Rodrigues, Carlos M; Almeida, Paulo J; Valente, Inês M; Gonçalves, Luís M; Compton, Richard G; Barros, Aquiles A

2011-09-09

An improved approach to the anodic stripping voltammetric (ASV) determination of heavy metals, using the hanging mercury drop electrode (HMDE), is reported. It was discovered that using very cathodic accumulation potentials, at which the solvent reduction occurs (overpotential deposition), the voltammetric signals of zinc(II), cadmium(II), lead(II) and copper(II) increase. When compared with the classical methodology a 5 to 10-fold signal increase is obtained. This effect is likely due to both mercury drop oscillation at such cathodic potentials and added local convection at the mercury drop surface caused by the evolution of hydrogen bubbles. Copyright © 2011 Elsevier B.V. All rights reserved.

A molecular catalyst for water oxidation that binds to metal oxide surfaces

PubMed Central

Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich; Crabtree, Robert H.; Brudvig, Gary W.; Schmuttenmaer, Charles A.

2015-01-01

Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On conductive electrode surfaces, this heterogenized molecular catalyst oxidizes water with low overpotential, high turnover frequency and minimal degradation. Spectroscopic and electrochemical studies show that it does not decompose into iridium oxide, thus preserving its molecular identity, and that it is capable of sustaining high activity towards water oxidation with stability comparable to state-of-the-art bulk metal oxide catalysts. PMID:25757425

Fuel cells with doped lanthanum gallate electrolyte

NASA Astrophysics Data System (ADS)

Feng, Man; Goodenough, John B.; Huang, Keqin; Milliken, Christopher

Single cells with doped lanthanum gallate electrolyte material were constructed and tested from 600 to 800°C. Both ceria and the electrolyte material were mixed with NiO powder respectively to form composite anodes. Doped lanthanum cobaltite was used exclusively as the cathode material. While high power density from the solid oxide fuel cells at 800°C was achieved. our results clearly indicate that anode overpotential is the dominant factor in the power loss of the cells. Better anode materials and anode processing methods need to be found to fully utilize the high ionic conductivity of the doped lanthanum galiate and achieve higher power density at 800°C from solid oxide fuel cells.

Role of solvents on the oxygen reduction and evolution of rechargeable Li-O2 battery

NASA Astrophysics Data System (ADS)

Christy, Maria; Arul, Anupriya; Zahoor, Awan; Moon, Kwang Uk; Oh, Mi Young; Stephan, A. Manuel; Nahm, Kee Suk

2017-02-01

The choice of electrolyte solvent is expected to play a key role in influencing the lithium-oxygen battery performance. The electrochemical performances of three electrolytes composed of lithium bis (trifluoromethane sulfonyl) imide (LiTFSI) salt and different solvents namely, ethylene carbonate/propylene carbonate (EC/PC), tetra ethylene glycol dimethyl ether (TEGDME) and dimethyl sulfoxide (DMSO) are investigated by assembling lithium oxygen cells. The electrolyte composition significantly varied the specific capacity of the battery. The choice of electrolyte also influences the overpotential, cycle life, and rechargeability of the battery. Electrochemical impedance spectra, cyclic voltammetry, and chronoamperometry were utilized to determine the reversible reactions associated with the air cathode.

Determination of optimal parameters for dual-layer cathode of polymer electrolyte fuel cell using computational intelligence-aided design.

PubMed

Chen, Yi; Huang, Weina; Peng, Bei

2014-01-01

Because of the demands for sustainable and renewable energy, fuel cells have become increasingly popular, particularly the polymer electrolyte fuel cell (PEFC). Among the various components, the cathode plays a key role in the operation of a PEFC. In this study, a quantitative dual-layer cathode model was proposed for determining the optimal parameters that minimize the over-potential difference η and improve the efficiency using a newly developed bat swarm algorithm with a variable population embedded in the computational intelligence-aided design. The simulation results were in agreement with previously reported results, suggesting that the proposed technique has potential applications for automating and optimizing the design of PEFCs.

A nickel phosphine complex as a fast and efficient hydrogen production catalyst.

PubMed

Gan, Lu; Groy, Thomas L; Tarakeshwar, Pilarisetty; Mazinani, Shobeir K S; Shearer, Jason; Mujica, Vladimiro; Jones, Anne K

2015-01-28

Here we report the electrocatalytic reduction of protons to hydrogen by a novel S2P2 coordinated nickel complex, [Ni(bdt)(dppf)] (bdt = 1,2-benzenedithiolate, dppf = 1,1'-bis(diphenylphosphino)ferrocene). The catalysis is fast and efficient with a turnover frequency of 1240 s(-1) and an overpotential of only 265 mV for half activity at low acid concentrations. Furthermore, catalysis is possible using a weak acid, and the complex is stable for at least 4 h in acidic solution. Calculations of the system carried out at the density functional level of theory (DFT) are consistent with a mechanism for catalysis in which both protonations take place at the nickel center.

The influence of poly(ethylene oxide) and illumination on the copper electrodeposition process onto n-Si(100).

PubMed

Muñoz, Eduardo C; Schrebler, Ricardo S; Cury, Paula K; Suarez, Claudio A; Córdova, Ricardo A; Gómez, Carlos H; Marotti, Ricardo E; Dalchiele, Enrique A

2006-10-26

In this study, we examined the influence of illumination and the presence of poly(ethylene oxide) (PEO) as an additive for the copper electrodeposition process onto n-Si(100). The study was carried out by means of cyclic voltammetry (CV) and the potential steps method, from which the corresponding nucleation and growth mechanism (NGM) were determined. Likewise, a morphologic analysis of the deposits obtained at different potential values by means of atomic force microscopy (AFM) was carried out. In a first stage, Mott-Schottky measurements so as to characterize the energetics of the semiconductor/electrolyte interface were made. Also, parallel capacity measurements were carried out in order to determine the surface state density of the substrate. It was found that when PEO concentration is increased, the number of these surface states decreases. The CV results indicated that the presence of PEO inhibits the photoelectrochemical reaction of oxide formation on the surface of the semiconductor. This allows a decrease in the overpotential associated with the electrodeposition process. The analysis of the j/t transients shows that the NGM corresponds to progressive three-dimensional (3D) diffusional controlled (PN3D(Diff)), which was confirmed by the AFM technique. Neither illumination nor the presence of PEO changes the mechanisms. Their influence is in that they diminish the size of the nuclei and the speed with which these are formed, which produces a more homogeneous electrodeposit.

Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO2-to-CO Electrochemical Conversion.

PubMed

Azcarate, Iban; Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel

2016-12-28

The starting point of this study of through-space substituent effects on the catalysis of the electrochemical CO 2 -to-CO conversion by iron(0) tetraphenylporphyrins is the linear free energy correlation between through-structure electronic effects and the iron(I/0) standard potential that we established separately. The introduction of four positively charged trimethylanilinium groups at the para positions of the tetraphenylporphyrin (TPP) phenyls results in an important positive deviation from the correlation and a parallel improvement of the catalytic Tafel plot. The assignment of this catalysis boosting effect to the Coulombic interaction of these positive charges with the negative charge borne by the initial Fe 0 -CO 2 adduct is confirmed by the negative deviation observed when the four positive charges are replaced by four negative charges borne by sulfonate groups also installed in the para positions of the TPP phenyls. The climax of this strategy of catalysis boosting by means of Coulombic stabilization of the initial Fe 0 -CO 2 adduct is reached when four positively charged trimethylanilinium groups are introduced at the ortho positions of the TPP phenyls. The addition of a large concentration of a weak acid-phenol-helps by cleaving one of the C-O bonds of CO 2 . The efficiency of the resulting catalyst is unprecedented, as can be judged by the catalytic Tafel plot benchmarking with all presently available catalysts of the electrochemical CO 2 -to-CO conversion. The maximal turnover frequency (TOF) is as high as 10 6 s -1 and is reached at an overpotential of only 220 mV; the extrapolated TOF at zero overpotential is larger than 300 s -1 . This catalyst leads to a highly selective formation of CO (practically 100%) in spite of the presence of a high concentration of phenol, which could have favored H 2 evolution. It is also very stable, showing no significant alteration after more than 80 h of electrolysis.

Effect of Concentration on the Electrochemistry and Speciation of the Magnesium Aluminum Chloride Complex Electrolyte Solution.

PubMed

See, Kimberly A; Liu, Yao-Min; Ha, Yeyoung; Barile, Christopher J; Gewirth, Andrew A

2017-10-18

Magnesium batteries offer an opportunity to use naturally abundant Mg and achieve large volumetric capacities reaching over four times that of conventional Li-based intercalation anodes. High volumetric capacity is enabled by the use of a Mg metal anode in which charge is stored via electrodeposition and stripping processes, however, electrolytes that support efficient Mg electrodeposition and stripping are few and are often prepared from highly reactive compounds. One interesting electrolyte solution that supports Mg deposition and stripping without the use of highly reactive reagents is the magnesium aluminum chloride complex (MACC) electrolyte. The MACC exhibits high Coulombic efficiencies and low deposition overpotentials following an electrolytic conditioning protocol that stabilizes species necessary for such behavior. Here, we discuss the effect of the MgCl 2 and AlCl 3 concentrations on the deposition overpotential, current density, and the conditioning process. Higher concentrations of MACC exhibit enhanced Mg electrodeposition current density and much faster conditioning. An increase in the salt concentrations causes a shift in the complex equilibria involving both cations. The conditioning process is strongly dependent on the concentration suggesting that the electrolyte is activated through a change in speciation of electrolyte complexes and is not simply due to the annihilation of electrolyte impurities. Additionally, the presence of the [Mg 2 (μ-Cl) 3 ·6THF] + in the electrolyte solution is again confirmed through careful analysis of experimental Raman spectra coupled with simulation and direct observation of the complex in sonic spray ionization mass spectrometry. Importantly, we suggest that the ∼210 cm -1 mode commonly observed in the Raman spectra of many Mg electrolytes is indicative of the C 3v symmetric [Mg 2 (μ-Cl) 3 ·6THF] + . The 210 cm -1 mode is present in many electrolytes containing MgCl 2 , so its assignment is of broad interest to the Mg electrolyte community.

Electrodeposition of copper on a Pt(111) electrode in sulfuric acid containing poly(ethylene glycol) and chloride ions as probed by in situ STM.

PubMed

Fu, YunLin; Pao, Te; Chen, Sih-Zih; Yau, ShuehLin; Dow, Wei-Ping; Lee, Yuh-Lang

2012-07-03

This study employed real-time in situ STM imaging to examine the adsorption of PEG molecules on Pt(111) modified by a monolayer of copper adatoms and the subsequent bulk Cu deposition in 1 M H(2)SO(4) + 1 mM CuSO(4)+ 1 mM KCl + 88 μM PEG. At the end of Cu underpotential deposition (~0.35 V vs Ag/AgCl), a highly ordered Pt(111)-(√3 × √7)-Cu + HSO(4)(-) structure was observed in 1 M H(2)SO(4) + 1 mM CuSO(4). This adlattice restructured upon the introduction of poly(ethylene glycol) (PEG, molecular weight 200) and chloride anions. At the onset potential for bulk Cu deposition (~0 V), a Pt(111)-(√3 × √3)R30°-Cu + Cl(-) structure was imaged with a tunneling current of 0.5 nA and a bias voltage of 100 mV. Lowering the tunneling current to 0.2 nA yielded a (4 × 4) structure, presumably because of adsorbed PEG200 molecules. The subsequent nucleation and deposition processes of Cu in solution containing PEG and Cl(-) were examined, revealing the nucleation of 2- to 3-nm-wide CuCl clusters on an atomically smooth Pt(111) surface at overpotentials of less than 50 mV. With larger overpotential (η > 150 mV), Cu deposition seemed to bypass the production of CuCl species, leading to layered Cu deposition, starting preferentially at step defects, followed by lateral growth to cover the entire Pt electrode surface. These processes were observed with both PEG200 and 4000, although the former tended to produce more CuCl nanoclusters. Raising [H(2)SO(4)] to 1 M substantiates the suppressing effect of PEG on Cu deposition. This STM study provided atomic- or molecular-level insight into the effect of PEG additives on the deposition of Cu.

Pristine multi-walled carbon nanotubes/SDS modified carbon paste electrode as an amperometric sensor for epinephrine.

PubMed

Thomas, Tony; Mascarenhas, Ronald J; D' Souza, Ozma J; Detriche, Simon; Mekhalif, Zineb; Martis, Praveen

2014-07-01

An amperometric sensor for the determination of epinephrine (EP) was fabricated by modifying the carbon paste electrode (CPE) with pristine multi-walled carbon nanotubes (pMWCNTs) using bulk modification followed by drop casting of sodium dodecyl sulfate (SDS) onto the surface for its optimal potential application. The modified electrode showed an excellent electrocatalytic activity towards EP by decreasing the overpotential and greatly enhancing the current sensitivity. FE-SEM images confirmed the dispersion of pMWCNTs in the CPE matrix. EDX analysis ensured the surface coverage of SDS. A comparative study of pMWCNTs with those of oxidized MWCNTs (MWCNTsOX) modified electrodes reveals that the former is the best base material for the construction of the sensor with advantages of lower oxidation overpotential and the least background current. The performance of the modified electrode was impressive in terms of the least charge transfer resistance (Rct), highest values for diffusion coefficient (DEP) and standard heterogeneous electron transfer rate constant (k°). Analytical characterization of the modified electrode exhibited two linear dynamic ranges from 1.0×10(-7) to 1.0×10(-6)M and 1.0×10(-6) to 1.0×10(-4)M with a detection limit of (4.5±0.18)×10(-8)M. A 100-fold excess of serotonin, acetaminophen, folic acid, uric acid, tryptophan, tyrosine and cysteine, 10-fold excess of ascorbic acid and twofold excess of dopamine do not interfere in the quantification of EP at this electrode. The analytical applications of the modified electrode were demonstrated by determining EP in spiked blood serum and adrenaline tartrate injection. The modified electrode involves a simple fabrication procedure, minimum usage of the modifier, quick response, excellent stability, reproducibility and anti-fouling effects. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrodeposition of Isolated Platinum Atoms and Clusters on Bismuth-Characterization and Electrocatalysis.

PubMed

Zhou, Min; Dick, Jeffrey E; Bard, Allen J

2017-12-06

We describe a method for the electrodeposition of an isolated single Pt atom or small cluster, up to 9 atoms, on a bismuth ultramicroelectrode (UME). This deposition was immediately followed by electrochemical characterization via the hydrogen evolution reaction (HER) that occurs readily on the electrodeposited Pt but not on Bi. The observed voltammetric current plateau, even for a single atom, which behaves as an electrode, allows the estimation of deposit size. Pt was plated from solutions of femtomolar PtCl 6 2- , which allowed precise control of the arrival of ions and thus the plating rate on the Bi UME, to one ion every few seconds. This allowed the atom-by-atom fabrication of isolated platinum deposits, ranging from single atoms to 9-atom clusters. The limiting currents in voltammetry gave the size and number of atoms of the clusters. Given the stochasticity of the plating process, we show that the number of atoms plated over a given time (10 and 20 s) follows a Poisson distribution. Taking the potential at a certain current density as a measure of the relative rate of the HER, we found that the potential shifted positively as the size increased, with single atoms showing the largest overpotentials compared to bulk Pt.

A hybrid DNA-templated gold nanocluster for enhanced enzymatic reduction of oxygen

DOE PAGES

Chakraborty, Saumen; Babanova, Sofia; Rocha, Reginaldo C.; ...

2015-08-19

We report the synthesis and characterization of a new DNA-templated gold nanocluster (AuNC) of ~1 nm in diameter and possessing ~7 Au atoms. When integrated with bilirubin oxidase (BOD) and single walled carbon nanotubes (SWNTs), the AuNC acts as an enhancer of electron transfer (ET) and lowers the overpotential of electrocatalytic oxygen reduction reaction (ORR) by ~15 mV as compared to the enzyme alone. In addition, the presence of AuNC causes significant enhancements in the electrocatalytic current densities at the electrode. Control experiments show that such enhancement of ORR by the AuNC is specific to nanoclusters and not to plasmonicmore » gold particles. Rotating ring disk electrode (RRDE) measurements confirm 4e– reduction of O 2 to H 2O with minimal production of H 2O 2, suggesting that the presence of AuNC does not perturb the mechanism of ORR catalyzed by the enzyme. This unique role of the AuNC as enhancer of ET at the enzyme-electrode interface makes it a potential candidate for the development of cathodes in enzymatic fuel cells, which often suffer from poor electronic communication between the electrode surface and the enzyme active site. In conclusion, the AuNC displays phosphorescence with large Stokes shift and microsecond lifetime.« less

Hierarchical cobalt poly-phosphide hollow spheres as highly active and stable electrocatalysts for hydrogen evolution over a wide pH range

NASA Astrophysics Data System (ADS)

Wu, Tianli; Pi, Mingyu; Wang, Xiaodeng; Guo, Weimeng; Zhang, Dingke; Chen, Shijian

2018-01-01

Exploring highly-efficient and low-cost non-noble metal electrocatalyst toward the hydrogen evolution reaction (HER) is highly desired for renewable energy system but remains challenging. In this work, three dimensional hierarchical porous cobalt poly-phosphide hollow spheres (CoP3 HSs) were prepared by topotactic phosphidation of the cobalt-based precursor via vacuum encapsulation technique. As a porous HER cathode, the CoP3 HSs delivers remarkable electrocatalytic performance over the wide pH range. It needs overpotentials of -69 mV and -118 mV with a small Tafel slope of 51 mV dec-1 to obtain current densities of 10 mA cm-2 and 50 mA cm-2, respectively, and maintains its electrocatalytic performance over 30 h in acidic solution. In addition, CoP3 also exhibit superior electrocatalytic performance and stability under neutral and alkaline conditions for the HER. Both experimental measurements and density functional theory (DFT) calculations are performed to explore the mechanism behind the excellent HER performance. The results of our study make the porous CoP3 HSs as a promising electrocatalyst for practical applications toward energy conversion system and present a new way for designing and fabricating HER electrodes through high degree of phosphorization and nano-porous architecture.

Innovative Strategy on Hydrogen Evolution Reaction Utilizing Activated Liquid Water

NASA Astrophysics Data System (ADS)

Hwang, Bing-Joe; Chen, Hsiao-Chien; Mai, Fu-Der; Tsai, Hui-Yen; Yang, Chih-Ping; Rick, John; Liu, Yu-Chuan

2015-11-01

Splitting water for hydrogen production using light, or electrical energy, is the most developed ‘green technique’. For increasing efficiency in hydrogen production, currently, the most exciting and thriving strategies are focused on efficient and inexpensive catalysts. Here, we report an innovative idea for efficient hydrogen evolution reaction (HER) utilizing plasmon-activated liquid water with reduced hydrogen-bonded structure by hot electron transfer. This strategy is effective for all HERs in acidic, basic and neutral systems, photocatalytic system with a g-C3N4 (graphite carbon nitride) electrode, as well as in an inert system with an ITO (indium tin oxide) electrode. Compared to deionized water, the efficiency of HER increases by 48% based on activated water ex situ on a Pt electrode. Increase in energy efficiency from activated water is 18% at a specific current yield of -20 mA in situ on a nanoscale-granulated Au electrode. Moreover, the onset potential of -0.023 V vs RHE was very close to the thermodynamic potential of the HER (0 V). The measured current density at the corresponding overpotential for HER in an acidic system was higher than any data previously reported in the literature. This approach establishes a new vista in clean green energy production.

Challenge for lowering concentration polarization in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shimada, Hiroyuki; Suzuki, Toshio; Yamaguchi, Toshiaki; Sumi, Hirofumi; Hamamoto, Koichi; Fujishiro, Yoshinobu

2016-01-01

In the scope of electrochemical phenomena, concentration polarization at electrodes is theoretically inevitable, and lowering the concentration overpotential to improve the performance of electrochemical cells has been a continuing challenge. Electrodes with highly controlled microstructure, i.e., high porosity and uniform large pores are therefore essential to achieve high performance electrochemical cells. In this study, state-of-the-art technology for controlling the microstructure of electrodes has been developed for realizing high performance support electrodes of solid oxide fuel cells (SOFCs). The key is controlling the porosity and pore size distribution to improve gas diffusion, while maintaining the integrity of the electrolyte and the structural strength of actual sized electrode supports needed for the target application. Planar anode-supported SOFCs developed in this study realize 5 μm thick dense electrolyte (yttria-stabilized zirconia: YSZ) and the anode substrate (Ni-YSZ) of 53.6 vol.% porosity with a large median pore diameter of 0.911 μm. Electrochemical measurements reveal that the performance of the anode-supported SOFCs improves with increasing anode porosity. This Ni-YSZ anode minimizes the concentration polarization, resulting in a maximum power density of 3.09 W cm-2 at 800 °C using humidified hydrogen fuel without any electrode functional layers.

Review—Physicochemical hydrodynamics of gas bubbles in two phase electrochemical systems

PubMed Central

Taqieddin, Amir; Nazari, Roya; Rajic, Ljiljana; Alshawabkeh, Akram

2018-01-01

Electrochemical systems suffer from poor management of evolving gas bubbles. Improved understanding of bubbles behavior helps to reduce overpotential, save energy and enhance the mass transfer during chemical reactions. This work investigates and reviews the gas bubbles hydrodynamics, behavior, and management in electrochemical cells. Although the rate of bubble growth over the electrode surface is well understood, there is no reliable prediction of bubbles break-off diameter from the electrode surface because of the complexity of bubbles motion near the electrode surface. Particle Image Velocimetry (PIV) and Laser Doppler Anemometry (LDA) are the most common experimental techniques to measure bubble dynamics. Although the PIV is faster than LDA, both techniques are considered expensive and time-consuming. This encourages adapting Computational Fluid Dynamics (CFD) methods as an alternative to study bubbles behavior. However, further development of CFD methods is required to include coalescence and break-up of bubbles for better understanding and accuracy. The disadvantages of CFD methods can be overcome by using hybrid methods. The behavior of bubbles in electrochemical systems is still a complex challenging topic which requires a better understanding of the gas bubbles hydrodynamics and their interactions with the electrode surface and bulk liquid, as well as between the bubbles itself. PMID:29731515

Effects of Al(III) and Nano-Al13 Species on Malate Dehydrogenase Activity

PubMed Central

Yang, Xiaodi; Cai, Ling; Peng, Yu; Li, Huihui; Chen, Rong Fu; Shen, Ren Fang

2011-01-01

The effects of different aluminum species on malate dehydrogenase (MDH) activity were investigated by monitoring amperometric i-t curves for the oxidation of NADH at low overpotential using a functionalized multi-wall nanotube (MWNT) modified glass carbon electrode (GCE). The results showed that Al(III) and Al13 can activate the enzymatic activity of MDH, and the activation reaches maximum levels as the Al(III) and Al13 concentration increase. Our study also found that the effects of Al(III) and Al13 on the activity of MDH depended on the pH value and aluminum speciation. Electrochemical and circular dichroism spectra methods were applied to study the effects of nano-sized aluminum compounds on biomolecules. PMID:22163924

Simple Cadmium Sulfide Compound with Stable 95 % Selectivity for Carbon Dioxide Electroreduction in Aqueous Medium.

PubMed

Li, Yu Hang; Cheng, Ling; Liu, Peng Fei; Zhang, Le; Zu, Meng Yang; Wang, Chong Wu; Jin, Yan Huan; Cao, Xiao Ming; Yang, Hua Gui; Li, Chunzhong

2018-05-09

A simple cadmium sulfide nanomaterial is found to be an efficient and stable electrocatalyst for CO 2 reduction in aqueous medium for more than 40 h with a steady CO faradaic efficiency of approximately 95 %. Moreover, it can realize a current density of -10 mA cm -2 at an overpotential of -0.55 V on a porous substrate with similar selectivity. Theoretical and experimental results confirm that the high selectivity for CO 2 reduction is due to its (0 0 0 2) face with sulfur vacancies that prefers CO 2 molecule reduction in aqueous medium. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Al(III) and nano-Al13 species on malate dehydrogenase activity.

PubMed

Yang, Xiaodi; Cai, Ling; Peng, Yu; Li, Huihui; Chen, Rong Fu; Shen, Ren Fang

2011-01-01

The effects of different aluminum species on malate dehydrogenase (MDH) activity were investigated by monitoring amperometric i-t curves for the oxidation of NADH at low overpotential using a functionalized multi-wall nanotube (MWNT) modified glass carbon electrode (GCE). The results showed that Al(III) and Al(13) can activate the enzymatic activity of MDH, and the activation reaches maximum levels as the Al(III) and Al(13) concentration increase. Our study also found that the effects of Al(III) and Al(13) on the activity of MDH depended on the pH value and aluminum speciation. Electrochemical and circular dichroism spectra methods were applied to study the effects of nano-sized aluminum compounds on biomolecules.

Bi-axial grown amorphous MoSx bridged with oxygen on r-GO as a superior stable and efficient nonprecious catalyst for hydrogen evolution

PubMed Central

Lee, Cheol-Ho; Yun, Jin-Mun; Lee, Sungho; Jo, Seong Mu; Eom, KwangSup; Lee, Doh C.; Joh, Han-Ik; Fuller, Thomas F.

2017-01-01

Amorphous molybdenum sulfide (MoSx) is covalently anchored to reduced graphene oxide (r-GO) via a simple one-pot reaction, thereby inducing the reduction of GO and simultaneous doping of heteroatoms on the GO. The oxygen atoms form a bridged between MoSx and GO and play a crucial role in the fine dispersion of the MoSx particles, control of planar MoSx growth, and increase of exposed active sulfur sites. This bridging leads to highly efficient (−157 mV overpotential and 41 mV/decade Tafel slope) and stable (95% versus initial activity after 1000 cycles) electrocatalyst for hydrogen evolution. PMID:28106126

Nitrogen-doped mesoporous carbon-armored cobalt nanoparticles as efficient hydrogen evolving electrocatalysts.

PubMed

Tang, Duihai; Li, Kuo; Zhang, Wenting; Qiao, Zhen-An; Zhu, Junjiang; Zhao, Zhen

2018-03-15

A series of Co nanoparticles embedded, N-doped mesoporous carbons have been synthesized through chelate-assisted co-assembly strategy followed by thermal treatment. The preparation is based on an assembly process, with evaporation of an ethanol-water solution containing melamine formaldehyde resin (MF resin) as carbon source, nitrogen source, and chelating agent. Moreover, F127 and Co(NO 3 ) 2 are used as template and metallic precursor, respectively. The Co nanoparticles embedded, N-doped mesoporous carbon annealed at 800 °C (denoted as MFCo800) shows high electrocatalytic activity for hydrogen evolution reaction (HER) with high current density and low overpotential, which has the ability to operate in both acidic and alkaline electrolytes. Copyright © 2017. Published by Elsevier Inc.

Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asadi, M.; Kim, K.; Liu, C.

2016-07-28

Conversion of carbon dioxide (CO2) into fuels is an attractive solution to many energy and environmental challenges. However, the chemical inertness of CO2 renders many electrochemical and photochemical conversion processes inefficient. We report a transition metal dichalcogenide nanoarchitecture for catalytic electrochemical CO2 conversion to carbon monoxide (CO) in an ionic liquid. We found that tungsten diselenide nanoflakes show a current density of 18.95 milliamperes per square centimeter, CO faradaic efficiency of 24%, and CO formation turnover frequency of 0.28 per second at a low overpotential of 54 millivolts. We also applied this catalyst in a light-harvesting artificial leaf platform thatmore » concurrently oxidized water in the absence of any external potential.« less

Enhanced activity of CaFeMg layered double hydroxides-supported gold nanodendrites for the electrochemical evolution of oxygen and hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

Havakeshian, Elaheh; Salavati, Hossein; Taei, Masoumeh; Hasheminasab, Fatemeh; Seddighi, Mohadeseh

2018-02-01

In this study, Au was electrodeposited on a support of CaFeMg layered double hydroxide and then, its catalytic activity was investigated for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Field emission scanning electron microscopy images showed that a uniform porous film of aggregated nano-particles of the LDH has been decorated with Au nanodendrite-like structures (AuNDs@LDH). The results obtained from polarization curves, Tafel plots and electrochemical impedance spectroscopy showed that the AuNDs@LDH exhibits lower overpotential, higher current density, faster kinetics and enhanced stability for both of the OER and HER, in comparison with the single AuNPs and LDH catalysts.

Ni-C-N Nanosheets as Catalyst for Hydrogen Evolution Reaction.

PubMed

Yin, Jie; Fan, Qiaohui; Li, Yuxuan; Cheng, Fangyi; Zhou, Panpan; Xi, Pinxian; Sun, Shouheng

2016-11-09

We report a facile nitrogenation/exfoliation process to prepare hybrid Ni-C-N nanosheets. These nanosheets are <2 nm thin, chemically stable, and metallically conductive. They serve as a robust catalyst for the hydrogen evolution reaction in 0.5 M H 2 SO 4 , or 1.0 M KOH or 1.0 M PBS (pH = 7). For example, they catalyze the hydrogen evolution reaction in 0.5 M H 2 SO 4 at an onset potential of 34.7 mV, an overpotential of 60.9 mV (at j = 10 mA cm -2 ) and with remarkable long-term stability (∼10% current drop after 70 h testing period). They are promising as a non-Pt catalyst for practical hydrogen evolution reaction.

Bioelectrochemical oxidation of water.

PubMed

Pita, Marcos; Mate, Diana M; Gonzalez-Perez, David; Shleev, Sergey; Fernandez, Victor M; Alcalde, Miguel; De Lacey, Antonio L

2014-04-23

The electrolysis of water provides a link between electrical energy and hydrogen, a high energy density fuel and a versatile energy carrier, but the process is very expensive. Indeed, the main challenge is to reduce energy consumption for large-scale applications using efficient renewable catalysts that can be produced at low cost. Here we present for the first time that laccase can catalyze electrooxidation of H2O to molecular oxygen. Native and laboratory-evolved laccases immobilized onto electrodes serve as bioelectrocatalytic systems with low overpotential and a high O2 evolution ratio against H2O2 production during H2O electrolysis. Our results open new research ground on H2O splitting, as they overcome serious practical limitations associated with artificial electrocatalysts currently used for O2 evolution.

Size and Electronic Modulation of Iridium Nanoparticles on Nitrogen Functionalized Carbon toward Advanced Electrocatalysts for Alkaline Water Splitting.

PubMed

Wang, Hua; Ming, Mei; Hu, Min; Xu, Caili; Wang, Yi; Zhang, Yun; Gao, Daojiang; Bi, Jian; Fan, Guangyin; Hu, Jin-Song

2018-06-14

Developing efficient catalytic materials for electrochemical water splitting is important. Herein, uniformly dispersed and size-controllable iridium (Ir) nanoparticles (NPs) were prepared using a nitrogen-functionalized carbon (Ir/CN) as the support. We found that nitrogen function can simultaneously modulate the size of Ir NPs to substantially enhance the catalytically active sites and adjust the electronic structure of Ir, thereby promoting electrocatalytic activity for water splitting. Consequently, the as-synthesized Ir/CN shows excellent electrocatalytic performance with overpotentials of 12 and 265 mV for hydrogen and oxygen evolution reactions in basic medium, respectively. These findings may pave a way for designing and synthesizing other similar materials as efficient catalysts for electrochemical water splitting.

Electrochemical oxidation of sulfites by DWCNTs, MWCNTs, higher fullerenes and manganese

NASA Astrophysics Data System (ADS)

Uzun, Dzhamal; Pchelarov, George; Dimitrov, Ognian; Vassilev, Sasho; Obretenov, Willi; Petrov, Konstantin

2018-03-01

Different electrocatalysts were tested for oxidation of sulfites to sulfates, namely, manganese thin films deposited on fullerenes and carbon nanotubes. The results presented clearly show that electrodes containing HFs (higher fullerenes), DWCNTs (double-wall carbon nanotubes) and manganese acetate are effective catalysts in S/O2 fuel cells. HFs and DWCNTs have high catalytic activity and can be employed as standalone catalysts. Manganese was deposited on DWCNTs, HFs and fullerenes C60/C70 by a thermal process. The electrocatalysts were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrochemical testing was carried out by plotting the E/V polarization curve. The polarization curves of the electrodes composed of pristine DWCNTs showed the lowest overpotentials.

Determination of Optimal Parameters for Dual-Layer Cathode of Polymer Electrolyte Fuel Cell Using Computational Intelligence-Aided Design

PubMed Central

Chen, Yi; Huang, Weina; Peng, Bei

2014-01-01

Because of the demands for sustainable and renewable energy, fuel cells have become increasingly popular, particularly the polymer electrolyte fuel cell (PEFC). Among the various components, the cathode plays a key role in the operation of a PEFC. In this study, a quantitative dual-layer cathode model was proposed for determining the optimal parameters that minimize the over-potential difference and improve the efficiency using a newly developed bat swarm algorithm with a variable population embedded in the computational intelligence-aided design. The simulation results were in agreement with previously reported results, suggesting that the proposed technique has potential applications for automating and optimizing the design of PEFCs. PMID:25490761

Decomposition mechanism of an artemisinin-type compound via hemin-electrocatalysis.

PubMed

Chen, H Y; Chen, Y; Zhu, S M; Bian, N S; Shan, F; Li, Y

1999-01-01

The interaction between a typical derivative of artemisinin and hemin was investigated by electrochemical and spectroelectrochemical methods. This derivative can be reduced via hemin-catalysis at the glassy carbon electrode, the cathodic overpotential is decreased by ca. 650 mV. A HPLC method for separating the products of the catalytic reaction was established. They were identified either in H(2)O-CH(3)CN solution or in tetrahydrofuran, respectively. The structures of these products show that the hemin-catalyzed decomposition of an artemisinin-type compound on the glassy carbon or reticulated vitreous carbon electrode can be achieved by both electrochemical reduction and rearrangement. The conclusion that the reaction of artemisinin with hemin is a critical step in the antimalarial mechanism of artemisinin can be drawn.

Study of the zinc-silver oxide battery system

NASA Technical Reports Server (NTRS)

Nanis, L.

1973-01-01

Theoretical and experimental models for the evaluation of current distribution in flooded, porous electrodes are discussed. An approximation for the local current distribution function was derived for conditions of a linear overpotential, a uniform concentration, and a very conductive matrix. By considering the porous electrode to be an analog of chemical catalyst structures, a dimensionless performance parameter was derived from the approximated current distribution function. In this manner the electrode behavior was characterized in terms of an electrochemical Thiele parameter and an effectiveness factor. It was shown that the electrochemical engineering approach makes possible the organizations of theoretical descriptions and of practical experience in the form of dimensionless parameters, such as the electrochemical Thiele parameters, and hence provides useful information for the design of new electrochemical systems.

Ultraefficient homogeneous catalyst for the CO2-to-CO electrochemical conversion.

PubMed

Costentin, Cyrille; Passard, Guillaume; Robert, Marc; Savéant, Jean-Michel

2014-10-21

A very efficient electrogenerated Fe(0) porphyrin catalyst was obtained by substituting in tetraphenylporphyrin two of the opposite phenyl rings by ortho-, ortho'-phenol groups while the other two are perfluorinated. It proves to be an excellent catalyst of the CO2-to-CO conversion as to selectivity (the CO faradaic yield is nearly quantitative), overpotential, and turnover frequency. Benchmarking with other catalysts, through catalytic Tafel plots, shows that it is the most efficient, to the best of our knowledge, homogeneous molecular catalyst of the CO2-to-CO conversion at present. Comparison with another Fe(0) tetraphenylporphyrin bearing eight ortho-, ortho'-phenol functionalities launches a general strategy where changes in substituents will be designed so as to optimize the operational combination of all catalyst elements of merit.

Superior performance of borocarbonitrides, BxCyNz , as stable, low-cost metal-free electrocatalysts for the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Chakraborty, Himanshu; Chhetri, Manjeet; Maitra, Somak; Waghmare, Umesh; Rao, C. N. R.

We report superior hydrogen evolution activity of metal-free borocarbonitride (BCN) catalysts. The highly positive onset potential (-56 mV vs. RHE) and the current density of 10 mAcm2 at an overpotential of 70 mV exhibited by a carbon-rich BCN with the composition BC7N2 demonstrates the extraordinary electrocatalytic activity at par with Pt. Theoretical studies throw light on the cause of high activity of this composition. The high activity and good stability of BCN's surpass the characteristics of other metal-free catalysts reported in recent literature. an Energy Frontier Research Centre funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0012575.

Highly-active oxygen evolution electrocatalyzed by an Fe-doped NiCr2O4 nanoparticle film.

PubMed

Zhao, Jinxiu; Li, Xianghong; Cui, Guanwei; Sun, Xuping

2018-05-11

Alkaline water splitting offers a simple method for the mass production of hydrogen but suffers from the sluggish kinetics of the anodic oxygen evolution reaction (OER). Here, we report on the development of an Fe-doped NiCr2O4 nanoparticle film on Ni foam (Fe-NiCr2O4/NF) as a non-noble-metal OER electrocatalyst with superior catalytic activity at alkaline pH. Such Fe-NiCr2O4/NF demands overpotentials as low as 228 and 318 mV to drive current densities of 20 and 500 mA cm-2, respectively, in 1.0 M KOH. Notably, it also shows strong long-term electrochemical durability with its activity being retained for at least 60 h.

Free-standing ternary NiWP film for efficient water oxidation reaction

NASA Astrophysics Data System (ADS)

Yang, Yunpeng; Zhou, Kuo; Ma, Lili; Liang, Yanqin; Yang, Xianjin; Cui, Zhenduo; Zhu, Shengli; Li, Zhaoyang

2018-03-01

High-efficient catalysts for oxygen evolution reaction (OER) is of great concern in improving energy efficiency for water splitting. Here we report a high-performance OER electrocatalyst of nickel-tungsten-phosphorus (NiWP) film prepared by template method. This free-standing ternary electrocatalyst exhibits a remarkable electrocatalytic activity of OER in alkaline medium due to the synergetic effect among these elements and the good electrical conductivity. The reported NiWP composite catalyst has an overpotential of as low as 0.4 V (vs. RHE) at 30 mA cm-2, better than that of the commercial RuO2 catalyst. Moreover, a small charge transfer resistance of 4.06 Ω and a Tafel slope of 68 mV dec-1 demonstrate the outstanding catalytic activity.

Direct selenylation of mixed Ni/Fe metal-organic frameworks to NiFe-Se/C nanorods for overall water splitting

NASA Astrophysics Data System (ADS)

Xu, Bo; Yang, He; Yuan, Lincheng; Sun, Yiqiang; Chen, Zhiming; Li, Cuncheng

2017-10-01

Development of low-cost, highly active bifunctional catalyst for efficient overall water splitting based on earth-abundant metals is still a great challenging task. In this work, we report a NiFe-Se/C composite nanorod as efficient non-precious-metal electrochemical catalyst derived from direct selenylation of a mixed Ni/Fe metal-organic framework. The as-obtained catalyst requires low overpotential to drive 10 mA cm-2 for HER (160 mV) and OER (240 mV) in 1.0 M KOH, respectively, and its catalytic activity is maintained for at least 20 h. Moreover, water electrolysis using this catalyst achieves high water splitting current density of 10 mA cm-2 at cell voltage of 1.68 V.

Modelling the aqueous and nonaqueous interfaces for CO2 electro-reduction over Sn catalysts

NASA Astrophysics Data System (ADS)

Sheng, Tian; Sun, Shi-Gang

2018-01-01

In CO2 electroreduction, Sn catalysts with a high overpotential for hydrogen evolution reaction and a high selectivity towards formic acid formation are very attractive. Many efforts have been made for improving the catalytic performance and for understanding the mechanisms. In electrochemistry, the role of solvents for surface reactions was deserved to be investigated, in particular for some nonaqueous solvents. Here, we have modeled the aqueous (water) and nonaqueous (acetonitrile and dichloromethane) for investigation of CO2 electroreduction on Sn surface, by constrained ab initio molecular dynamics simulations and thermodynamic integrations, including a number of explicit solvent molecules in computational models. It was found that CO2 reduction is initiated from formate formation and solvents, in particular, water can effectively facilitate the reaction.

Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

DOE PAGES

Zheng, Dong; Zhang, Xuran; Qu, Deyu; ...

2015-04-21

Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O 2/O 2 •- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O 2 reduction reaction is from mass diffusion. Li 2O 2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O 2 2- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings revealmore » an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.« less

Rhodium Nanoparticle-mesoporous Silicon Nanowire Nanohybrids for Hydrogen Peroxide Detection with High Selectivity

PubMed Central

Song, Zhiqian; Chang, Hucheng; Zhu, Weiqin; Xu, Chenlong; Feng, Xinjian

2015-01-01

Developing nanostructured electrocatalysts, with low overpotential, high selectivity and activity has fundamental and technical importance in many fields. We report here rhodium nanoparticle and mesoporous silicon nanowire (RhNP@mSiNW) hybrids for hydrogen peroxide (H2O2) detection with high electrocatalytic activity and selectivity. By employing electrodes that loaded with RhNP@mSiNW nanohybrids, interference caused from both many electroactive substances and dissolved oxygen were eliminated by electrochemical assaying at an optimal potential of +75 mV. Furthermore, the electrodes exhibited a high detection sensitivity of 0.53 μA/mM and fast response (< 5 s). This high-performance nanohybrid electrocatalyst has great potential for future practical application in various oxidase-base biosensors. PMID:25588953

A local proton source enhances CO2 electroreduction to CO by a molecular Fe catalyst.

PubMed

Costentin, Cyrille; Drouet, Samuel; Robert, Marc; Savéant, Jean-Michel

2012-10-05

Electrochemical conversion of carbon dioxide (CO(2)) to carbon monoxide (CO) is a potentially useful step in the desirable transformation of the greenhouse gas to fuels and commodity chemicals. We have found that modification of iron tetraphenylporphyrin through the introduction of phenolic groups in all ortho and ortho' positions of the phenyl groups considerably speeds up catalysis of this reaction by the electrogenerated iron(0) complex. The catalyst, which uses one of the most earth-abundant metals, manifests a CO faradaic yield above 90% through 50 million turnovers over 4 hours of electrolysis at low overpotential (0.465 volt), with no observed degradation. The basis for the enhanced activity appears to be the high local concentration of protons associated with the phenolic hydroxyl substituents.

Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid.

PubMed

Asadi, Mohammad; Kim, Kibum; Liu, Cong; Addepalli, Aditya Venkata; Abbasi, Pedram; Yasaei, Poya; Phillips, Patrick; Behranginia, Amirhossein; Cerrato, José M; Haasch, Richard; Zapol, Peter; Kumar, Bijandra; Klie, Robert F; Abiade, Jeremiah; Curtiss, Larry A; Salehi-Khojin, Amin

2016-07-29

Conversion of carbon dioxide (CO2) into fuels is an attractive solution to many energy and environmental challenges. However, the chemical inertness of CO2 renders many electrochemical and photochemical conversion processes inefficient. We report a transition metal dichalcogenide nanoarchitecture for catalytic electrochemical CO2 conversion to carbon monoxide (CO) in an ionic liquid. We found that tungsten diselenide nanoflakes show a current density of 18.95 milliamperes per square centimeter, CO faradaic efficiency of 24%, and CO formation turnover frequency of 0.28 per second at a low overpotential of 54 millivolts. We also applied this catalyst in a light-harvesting artificial leaf platform that concurrently oxidized water in the absence of any external potential. Copyright © 2016, American Association for the Advancement of Science.

Direct Electrochemistry of Bilirubin Oxidase from Magnaporthe orizae on Covalently-Functionalized MWCNT for the Design of High-Performance Oxygen-Reducing Biocathodes.

PubMed

Gentil, Solène; Carrière, Marie; Cosnier, Serge; Gounel, Sébastien; Mano, Nicolas; Le Goff, Alan

2018-06-12

Herein, the direct electrochemistry of bilirubin oxidase from Magnaporthe orizae (MoBOD) was studied on CNTs functionalized by electrografting several types of diazonium salts. The functionalization induces favorable or unfavorable orientation of MoBOD, the latter being compared to the well-known BOD from Myrothecium verrucaria (MvBOD). On the same nanostructured electrodes, MoBOD can surpass MvBOD in terms of both current densities and minimal overpotentials. Added to the fact that MoBOD is also highly active at the gas-diffusion electrode (GDE), these findings make MoBOD one of the MCOs with the highest catalytic activity towards the oxygen reduction reaction (ORR). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of hydrogen production and electrical power generation for energy capture in closed-loop ammonium bicarbonate reverse electrodialysis systems.

PubMed

Hatzell, Marta C; Ivanov, Ivan; Cusick, Roland D; Zhu, Xiuping; Logan, Bruce E

2014-01-28

Currently, there is an enormous amount of energy available from salinity gradients, which could be used for clean hydrogen production. Through the use of a favorable oxygen reduction reaction (ORR) cathode, the projected electrical energy generated by a single pass ammonium bicarbonate reverse electrodialysis (RED) system approached 78 W h m(-3). However, if RED is operated with the less favorable (higher overpotential) hydrogen evolution electrode and hydrogen gas is harvested, the energy recovered increases by as much ~1.5× to 118 W h m(-3). Indirect hydrogen production through coupling an RED stack with an external electrolysis system was only projected to achieve 35 W h m(-3) or ~1/3 of that produced through direct hydrogen generation.

Electrocatalysts for carbon dioxide conversion

DOEpatents

Masel, Richard I; Salehi-Khojin, Amin

2015-04-21

Electrocatalysts for carbon dioxide conversion include at least one catalytically active element with a particle size above 0.6 nm. The electrocatalysts can also include a Helper Catalyst. The catalysts can be used to increase the rate, modify the selectivity or lower the overpotential of electrochemical conversion of CO.sub.2. Chemical processes and devices using the catalysts also include processes to produce CO, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, (COOH).sub.2, or (COO.sup.-).sub.2, and a specific device, namely, a CO.sub.2 sensor.

A graphene-based electrochemical sensor for sensitive detection of paracetamol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Xinhuang; Wang, Jun; Wu, Hong

2010-05-15

An electrochemical sensor based on the electrocatalytic activity of functionalized graphene for sensitive detection of paracetamol is presented. The electrochemical behaviors of paracetamol on graphene-modified glassy carbon electrodes (GCEs) were investigated by cyclic voltammetry and square-wave voltammetry. The results showed that the graphene-modified electrode exhibited excellent electrocatalytic activity to paracetamol. A quasi-reversible redox process of paracetamol at the modified electrode was obtained, and the over-potential of paracetamol decreased significantly compared with that at the bare GCE. Such electrocatalytic behavior of graphene is attributed to its unique physical and chemical properties, e.g., subtle electronic characteristics, attractive π–π interaction, and strong adsorptivemore » capability. The sensor shows great promise for simple, sensitive, and quantitative detection of paracetamol.« less

Long-term stability of nanostructured thin film electrodes at operating potentials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahluwalia, Rajesh K.; Peng, J. -K.; Wang, X.

Long-term stability of nanostructured thin film (NSTF) catalysts at operating potentials has been investigated. Compared to high surface area Pt/C catalysts, NSTF electrodes show 20–50x smaller F – emission rates (FER) because of their high specific activity for oxygen reduction reaction (ORR), but are susceptible to poisoning by the products of membrane degradation because of their low electrochemically active surface area (ECSA). The observed voltage degradation rates at potentials corresponding to 1–1.5 A/cm 2 current density are much higher than the allowable 13–14 μV/h. Although F – is not itself responsible for performance decay, cumulative fluoride release (CFR) is amore » good marker for catalyst surface contamination. The observed performance decay is not only due to loss of active Pt sites but also adsorbed impurities impeding ORR kinetics. There is a strong correlation between measured CFR and observed decrease in specific ORR activity and limiting current density and increase in mass transfer overpotentials. Furthermore, the correlations indicate that the target of <10% lifetime performance degradation can be achieved by restricting CFR in NSTF electrodes to 0.7 μg/cm 2, as may be possible with more stable membranes, higher surface area NSTF catalysts, and cell operation at lower temperatures and higher relative humidities.« less

Cyclopentadienyl ruthenium-nickel catalysts for biomimetic hydrogen evolution: electrocatalytic properties and mechanistic DFT studies.

PubMed

Canaguier, Sigolène; Vaccaro, Loredana; Artero, Vincent; Ostermann, Rainer; Pécaut, Jacques; Field, Martin J; Fontecave, Marc

2009-09-21

The new dinuclear nickel-ruthenium complexes [Ni(xbsms)RuCp(L)][PF(6)] (H(2)xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene; Cp(-) = cyclopentadienyl; L = DMSO, CO, PPh(3), and PCy(3)) are reported and are bioinspired mimics of NiFe hydrogenases. These compounds were characterized by X-ray diffraction techniques and display novel structural motifs. Interestingly, [Ni(xbsms)RuCpCO][PF(6)] is stereochemically nonrigid in solution and an isomerization mechanism was derived with the help of density functional theory (DFT) calculations. Because of an increased electron density on the metal centers [Eur. J. Inorg. Chem. 2007, 18, 2613-2626] with respect to the previously described [Ni(xbsms)Ru(CO)(2)Cl(2)] and [Ni(xbsms)Ru(p-cymene)Cl](+) complexes, [Ni(xbsms)RuCp(dmso)][PF(6)] catalyzes hydrogen evolution from Et(3)NH(+) in DMF with an overpotential reduced by 180 mV and thus represents the most efficient NiFe hydrogenase functional mimic. DFT calculations were carried out with several methods to investigate the catalytic cycle and, coupled with electrochemical measurements, allowed a mechanism to be proposed. A terminal or bridging hydride derivative was identified as the active intermediate, with the structure of the bridging form similar to that of the Ni-C active state of NiFe hydrogenases.

Effect of sacrificial agents on the dispersion of metal cocatalysts for photocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Cao, Shaowen; Shen, Baojia; Huang, Qian; Chen, Zhe

2018-06-01

Surface photodeposition of noble metal cocatalyst has been regarded as an effective approach to facilitate the separation of charge carriers and reduce the over-potential of water reduction, thus to enhance the photocatalytic H2-production activities of semiconductor photocatalyst. Herein, the influences of sacrificial agents used in the photodeposition process on the dispersion of noble metal nanoparticles are investigated, via a series of technique of photocatalytic hydrogen evolution test, microstructure analysis and photoelectrochemical measurement. As a result, the sacrificial agents are found to show large impact on the loading amount, particle size and distribution of different metals on the surface of g-C3N4. The real loading amount of Pt and Au is higher in methanol solution than that in triethanolamine solution. Better distribution and smaller size of Pt nanoparticles are achieved in the presence of methanol; while better distribution and smaller size of Au nanoparticles are achieved in the presence of triethanolamine. As a result, quite different charge transfer ability is achieved for the synthesized Pt and Au decorated g-C3N4, which subsequently leads to disparate photocatalytic activities of the same g-C3N4 photocatalyst under various conditions. The finding in this work indicates that the valid deposition content, particle size and distribution of metal cocatalysts should be carefully taken into account when comparing the photocatalytic activities among various samples.

Influence of the interfacial peptide organization on the catalysis of hydrogen evolution.

PubMed

Doneux, Th; Dorcák, V; Palecek, E

2010-01-19

The hydrogen evolution reaction is catalyzed by peptides and proteins adsorbed on electrode materials with high overpotentials for this reaction, such as mercury. The catalytic response characteristics are known to be very sensitive to the composition and structure of the investigated biomolecule, opening the way to the implementation of a label-free, reagentless electroanalytical method in protein analysis. Herein, it is shown using the model peptide Cys-Ala-Ala-Ala-Ala-Ala that the interfacial organization significantly influences the catalytic behavior. This peptide forms at the electrode two distinct films, depending on the concentration and accumulation time. The low-coverage film, composed of flat-lying molecules (area per molecule of approximately 250-290 A(2)), yields a well-defined catalytic peak at potentials around -1.75 V. The high-coverage film, made of upright-oriented peptides (area per molecule of approximately 43 A(2)), is catalytically more active and the peak is observed at potentials less negative by approximately 0.4 V. The higher activity, evidenced by constant-current chronopotentiometry and cyclic voltammetry, is attributed to an increase in the acid dissociation constant of the amino acid residues as a result of the low permittivity of the interfacial region, as inferred from impedance measurements. An analogy is made to the known differences in acidic-basic behaviors of solvent-exposed and hydrophobic domains of proteins.

Toward an Aqueous Solar Battery: Direct Electrochemical Storage of Solar Energy in Carbon Nitrides.

PubMed

Podjaski, Filip; Kröger, Julia; Lotsch, Bettina V

2018-03-01

Graphitic carbon nitrides have emerged as an earth-abundant family of polymeric materials for solar energy conversion. Herein, a 2D cyanamide-functionalized polyheptazine imide (NCN-PHI) is reported, which for the first time enables the synergistic coupling of two key functions of energy conversion within one single material: light harvesting and electrical energy storage. Photo-electrochemical measurements in aqueous electrolytes reveal the underlying mechanism of this "solar battery" material: the charge storage in NCN-PHI is based on the photoreduction of the carbon nitride backbone and charge compensation is realized by adsorption of alkali metal ions within the NCN-PHI layers and at the solution interface. The photoreduced carbon nitride can thus be described as a battery anode operating as a pseudocapacitor, which can store light-induced charge in the form of long-lived, "trapped" electrons for hours. Importantly, the potential window of this process is not limited by the water reduction reaction due to the high intrinsic overpotential of carbon nitrides for hydrogen evolution, potentially enabling new applications for aqueous batteries. Thus, the feasibility of light-induced electrical energy storage and release on demand by a one-component light-charged battery anode is demonstrated, which provides a sustainable solution to overcome the intermittency of solar radiation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and characterization of anodic films on AZ31B Mg alloy formed in the silicate electrolytes with ethylene glycol oligomers as additives

NASA Astrophysics Data System (ADS)

Zhu, Feng; Wang, Jinwei; Li, Shanghua; Zhang, Jin

2012-09-01

Oxide coatings are prepared on AZ31B Mg alloy in an environment-friendly electrolyte with additives by plasma electrolytic anodization, and the effect of ethylene glycol oligmers on the performances of the anodized film is investigated. Under a constant current density of 10 mA cm-2, the reaction overpotential of the silicate electrolytes with additives are found higher than that of the original electrolyte as measured by potential-time test. The EIS and DC polarization results reveal that the addition of PEG increases the impedance of the film and reduces its corrosion current density (Icorr) at least by one order of magnitude. The surface morphologies are more and more compact and homogeneous with the increase in EG numbers, while a rougher surface appeared again if the PEG4000 is used as observed by SEM. As detected by XRD, the anodic films are found mainly consist of MgO, MgSiO3 and Mg2SiO4, and their relative amounts are related to the lengths of EGs, resulting in the differences in morphology and anticorrosion variations. Furthermore, the improvement in abrasive resistance of the anodic film formed in the electrolyte with PEG1000 may be attributed to its much more compact surface and the incorporation of ductile PEG chains among those oxides.

Long-term stability of nanostructured thin film electrodes at operating potentials

DOE PAGES

Ahluwalia, Rajesh K.; Peng, J. -K.; Wang, X.; ...

2017-02-09

Long-term stability of nanostructured thin film (NSTF) catalysts at operating potentials has been investigated. Compared to high surface area Pt/C catalysts, NSTF electrodes show 20–50x smaller F – emission rates (FER) because of their high specific activity for oxygen reduction reaction (ORR), but are susceptible to poisoning by the products of membrane degradation because of their low electrochemically active surface area (ECSA). The observed voltage degradation rates at potentials corresponding to 1–1.5 A/cm 2 current density are much higher than the allowable 13–14 μV/h. Although F – is not itself responsible for performance decay, cumulative fluoride release (CFR) is amore » good marker for catalyst surface contamination. The observed performance decay is not only due to loss of active Pt sites but also adsorbed impurities impeding ORR kinetics. There is a strong correlation between measured CFR and observed decrease in specific ORR activity and limiting current density and increase in mass transfer overpotentials. Furthermore, the correlations indicate that the target of <10% lifetime performance degradation can be achieved by restricting CFR in NSTF electrodes to 0.7 μg/cm 2, as may be possible with more stable membranes, higher surface area NSTF catalysts, and cell operation at lower temperatures and higher relative humidities.« less

Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

PubMed

Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

2017-06-28

Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

Analysis of total polyphenols in wines by FIA with highly stable amperometric detection using carbon nanotube-modified electrodes.

PubMed

Arribas, Alberto Sánchez; Martínez-Fernández, Marta; Moreno, Mónica; Bermejo, Esperanza; Zapardiel, Antonio; Chicharro, Manuel

2013-02-15

The use of glassy carbon electrodes (GCEs) modified with multi-walled carbon nanotube (CNT) films for the continuous monitoring of polyphenols in flow systems has been examined. The performance of these modified electrodes was evaluated and compared to bare GCE by cyclic voltammetry experiments and by flow injection analysis (FIA) with amperometric detection monitoring the response of gallic, caffeic, ferulic and p-coumaric acids in 0.050 M acetate buffer pH 4.5 containing 100 mM NaCl. The GCE modified with CNT dispersions in polyethyleneimine (PEI) provided lower overpotentials, higher sensitivity and much higher signal stability under a dynamic regime than bare GCEs. These properties allowed the estimation of the total polyphenol content in red and white wines with a remarkable long-term stability in the measurements despite the presence of potential fouling substances in the wine matrix. In addition, the versatility of the electrochemical methodology allowed the selective estimation of the easily oxidisable polyphenol fraction as well as the total polyphenol content just by tuning the detection potential at +0.30 or 0.70 V, respectively. The significance of the electrochemical results was demonstrated through correlation studies with the results obtained with conventional spectrophotometric assays for polyphenols (Folin-Ciocalteu, absorbance at 280 nm index and colour intensity index). Copyright © 2012 Elsevier Ltd. All rights reserved.

Picking a Fight with Water, and Water Lost ... an Electron

NASA Astrophysics Data System (ADS)

Herr, Jonathan D.

The global need for energy is increasing, as is the importance of producing energy by green and renewable methodologies. This document outlines a research program dedicated to investigating a possible source for this form of energy generation and storage: solar fuels. The photon-induced splitting of water into molecular hydrogen and oxygen is currently hindered by large overpotentials from the oxidation half-reaction of water-splitting. This study concentrated on fundamental models of water-spitting chemistry, using a physical and computational chemistry analysis. The oxidation was first explored via ab initio electronic structure calculations of bare cationic water clusters, comprised of 2 to 21 molecules, in order to determine key electronic interactions that facilitate oxidation. Deeper understanding of these interactions could serve as guides for the development of viable water oxidation catalysts (WOC) designed to reduce overpotentials. The cationic water cluster study was followed by an investigation into hydrated copper (I) clusters, which acted as precursor models for real WOCs. Analyzing how the copper ion perturbed the properties of water clusters led to important electronic considerations for the development of WOCs, such as copper-water interactions that go beyond simple electrostatics. The importance of diagnostic thermodynamic properties, as well as anharmonic characteristics being persistent throughout oxidized water clusters, necessitated the use of quantum and classical molecular dynamics (MD) routines. Therefore, two new methods for accelerating computationally demanding classical and quantum MD methods were developed to increase their accessibility. The first method utilized a new form of electronic extrapolation - a linear prediction routine incorporating a Burg minimization - to decrease the iterations required for solving the electronic equations throughout the dynamics. The second method utilized a multiple-timestepping description of the potential energy term in the path integral molecular dynamics (PIMD) formalism. This method led to reductions of computational time by allowing the use of less computationally laborious methods for portions of the simulation and resulted in negligible increase of error. The determination of the fundamental driving forces within water oxidation and the development of acceleration techniques for important electronic structure methods will help drive progress into fully solar-initiated water oxidation.

Turning on the protonation-first pathway for electrocatalytic CO 2 reduction by manganese bipyridyl tricarbonyl complexes

DOE PAGES

Ngo, Ken T.; McKinnon, Meaghan; Mahanti, Bani; ...

2017-01-24

Electrocatalytic reduction of CO 2 to CO is reported for the complex, { fac-Mn I([(MeO) 2Ph] 2bpy)(CO) 3(CH 3CN)}(OTf), containing four pendant methoxy groups, where [(MeO) 2Ph] 2bpy = 6,6'-bis(2,6-dimethoxyphenyl)-2,2'-bipyridine. In addition to a steric influence similar to that previously established for the 6,6'-dimesityl-2,2'-bipyridine ligand in [ fac-MnI(mes 2bpy)(CO) 3(CH 3CN)](OTf), which prevents Mn 0–Mn 0 dimerization, the [(MeO) 2Ph] 2bpy ligand introduces an additional electronic influence combined with a weak allosteric hydrogen-bonding interaction that significantly lowers the activation barrier for C–OH bond cleavage from the metallocarboxylic acid intermediate. This provides access to the thus far elusive protonation-first pathway, minimizingmore » the required overpotential for electrocatalytic CO 2 to CO conversion by Mn(I) polypyridyl catalysts, while concurrently maintaining a respectable turnover frequency. Comprehensive electrochemical and computational studies here confirm the positive influence of the [(MeO) 2Ph] 2bpy ligand framework on electrocatalytic CO 2 reduction and its dependence upon the concentration and p K a of the external Bronsted acid proton source (water, methanol, trifluoroethanol, and phenol) that is required for this class of manganese catalyst. Linear sweep voltammetry studies show that both phenol and trifluoroethanol as proton sources exhibit the largest protonation-first catalytic currents in combination with { fac-Mn I([(MeO) 2Ph] 2bpy)(CO) 3(CH 3CN)}(OTf), saving up to 0.55 V in overpotential with respect to the thermodynamically demanding reduction-first pathway, while bulk electrolysis studies confirm a high product selectivity for CO formation. As a result, to gain further insight into catalyst activation, time-resolved infrared (TRIR) spectroscopy combined with pulse-radiolysis (PR-TRIR), infrared spectroelectrochemistry, and density functional theory calculations were used to establish the v(CO) stretching frequencies and energetics of key redox intermediates relevant to catalyst activation.« less

Facile synthesis of mesoporous spinel NiCo2O4 nanostructures as highly efficient electrocatalysts for urea electro-oxidation

NASA Astrophysics Data System (ADS)

Ding, Rui; Qi, Li; Jia, Mingjun; Wang, Hongyu

2014-01-01

Mesoporous spinel nickel cobaltite (NiCo2O4) nanostructures were synthesized via a facile chemical deposition method coupled with a simple post-annealing process. The physicochemical properties were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and nitrogen sorption measurements. The electrocatalytic performances were investigated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) tests. The obtained NiCo2O4 materials exhibit typical agglomerate mesoporous nanostructures with a large surface area (190.1 m2 g-1) and high mesopore volume (0.943 cm3 g-1). Remarkably, the NiCo2O4 shows much higher catalytic activity, lower overpotential, better stability and greater tolerance towards urea electro-oxidation compared to those of cobalt oxide (Co3O4) synthesized by the same procedure. The NiCo2O4 electrode delivers a current density of 136 mA cm-2 mg-1 at 0.7 V (vs. Hg/HgO) in 1 M KOH and 0.33 M urea electrolytes accompanied with a desirable stability. The impressive electrocatalytic activity is largely ascribed to the high intrinsic electronic conductivity, superior mesoporous nanostructures and rich surface Ni active species of the NiCo2O4 materials, which can largely boost the interfacial electroactive sites and charge transfer rates for urea electro-oxidation, indicating promising applications in future wastewater remediation, hydrogen production and fuel cells.Mesoporous spinel nickel cobaltite (NiCo2O4) nanostructures were synthesized via a facile chemical deposition method coupled with a simple post-annealing process. The physicochemical properties were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and nitrogen sorption measurements. The electrocatalytic performances were investigated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) tests. The obtained NiCo2O4 materials exhibit typical agglomerate mesoporous nanostructures with a large surface area (190.1 m2 g-1) and high mesopore volume (0.943 cm3 g-1). Remarkably, the NiCo2O4 shows much higher catalytic activity, lower overpotential, better stability and greater tolerance towards urea electro-oxidation compared to those of cobalt oxide (Co3O4) synthesized by the same procedure. The NiCo2O4 electrode delivers a current density of 136 mA cm-2 mg-1 at 0.7 V (vs. Hg/HgO) in 1 M KOH and 0.33 M urea electrolytes accompanied with a desirable stability. The impressive electrocatalytic activity is largely ascribed to the high intrinsic electronic conductivity, superior mesoporous nanostructures and rich surface Ni active species of the NiCo2O4 materials, which can largely boost the interfacial electroactive sites and charge transfer rates for urea electro-oxidation, indicating promising applications in future wastewater remediation, hydrogen production and fuel cells. Electronic supplementary information (ESI) available: XRD patterns of NO and CO; XRD patterns and XPS profiles of CO; SEM images of CO; BET plots of CO; XPS quantitative analysis of NCO; a comparison of N2 sorption data between NCO and CO; the fitted values of impedimetric parameters of NCO and CO electrodes. See DOI: 10.1039/c3nr05359h

A Single-Use Paper-Shaped Microbial Fuel Cell for Rapid Aqueous Biosensing.

PubMed

Zuo, Kuichang; Liu, Han; Zhang, Qiaoying; Liang, Peng; Huang, Xia; Vecitis, Chad D

2015-06-22

The traditional chamber-based microbial fuel cell (MFC) often has the disadvantages of high ohmic resistance, large volume requirements, and delayed start-up. In this study, paper-shaped MFCs utilizing a porous carbon anode, a solid Ag2 O-coated carbon cathode, and a micrometer-thin porous polyvinylidene fluoride (PVDF) separator are investigated to address the classical MFC issues. The Ag2 O-coated cathode has a low overpotential of 0.06 V at a reducing current of 1 mA compared to a Pt-air cathode. Rapid inoculation by filtration results in an instantaneous power density of 92 mW m(-2) with an internal resistance of 162 Ω. Integrated current over the first 30 min of operation has a linear relation with microbial concentration. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Free-standing, flexible β-Ni(OH)2/electrochemically-exfoliated graphene film electrode for efficient oxygen evolution

NASA Astrophysics Data System (ADS)

Wang, Lanlan; Zhang, Jian; Jiang, Weitao; Zhao, Hong; Liu, Hongzhong

2018-03-01

The oxidation of water into molecular oxygen (oxygen evolution reaction, OER) is a pivotal reaction in many energy conversion devices. The high cost of IrO2, however, seriously hinder its large-scale applications in water oxidation. Here, we have at first reported a free-standing and flexible film electrode consisting of 2D β-Ni(OH)2/electrochemically-exfoliated graphene hybrid nanosheets (NiG-2), which is synthesized by a solvothermal reaction and an assembly process. The as-obtained NiG-2 film electrode exhibited an excellent electrocatalytic OER activity with an extremely low OER onset overpotential of ∼250 mV in a 1 M KOH aqueous solution, which is lower than these of the commercial Ir/C (370 mV at 10 mA cm-2) catalyst.

Amine-Modulated/Engineered Interfaces of NiMo Electrocatalysts for Improved Hydrogen Evolution Reaction in Alkaline Solutions.

PubMed

Gao, Wei; Gou, Wangyan; Zhou, Xuemei; Ho, Johnny C; Ma, Yuanyuan; Qu, Yongquan

2018-01-17

The interface between electrolytes and electrocatalysts would largely determine their corresponding activity and stability. Herein, modulating the surface characteristics of NiMo nanoparticles by various adsorbed amines gives the tunability on their interfacial properties and subsequently improves their catalytic performance for hydrogen evolution reaction (HER) in alkaline solutions. Diamines can significantly improve their HER activity by decreasing the charge-transfer resistance and modulating the electronic structures of interfacial active sites. Importantly, among various amines, ethylenediamine facilitates the HER activity of NiMo with a remarkable decrease of 268 mV in the overpotential to reach 10 mA cm -2 as compared with that of the unmodified NiMo in 1.0 M KOH. This method provides a novel strategy of regulating the interfacial properties to strengthen the catalytic performance of electrocatalysts.

Molecular molybdenum persulfide and related catalysts for generating hydrogen from water

DOEpatents

Long, Jeffrey R.; Chang, Christopher J.; Karunadasa, Hemamala I.; Majda, Marcin

2016-11-22

New metal persulfido compositions of matter are described. In one embodiment the metal is molybdenum and the metal persulfido complex mimics the structure and function of the triangular active edge site fragments of MoS.sub.2, a material that is the current industry standard for petroleum hydro desulfurization, as well as a promising low-cost alternative to platinum for electrocatalytic hydrogen production. This molecular [(PY5W.sub.2)MoS.sub.2].sup.x+ containing catalyst is capable of generating hydrogen from acidic-buffered water or even seawater at very low overpotentials at a turnover frequency rate in excess of 500 moles H.sub.2 per mole catalyst per second, with a turnover number (over a 20 hour period) of at least 19,000,000 moles H.sub.2 per mole of catalyst.

High performance electrodes in vanadium redox flow batteries through oxygen-enriched thermal activation

NASA Astrophysics Data System (ADS)

Pezeshki, Alan M.; Clement, Jason T.; Veith, Gabriel M.; Zawodzinski, Thomas A.; Mench, Matthew M.

2015-10-01

The roundtrip electrochemical energy efficiency is improved from 63% to 76% at a current density of 200 mA cm-2 in an all-vanadium redox flow battery (VRFB) by utilizing modified carbon paper electrodes in the high-performance no-gap design. Heat treatment of the carbon paper electrodes in a 42% oxygen/58% nitrogen atmosphere increases the electrochemically wetted surface area from 0.24 to 51.22 m2 g-1, resulting in a 100-140 mV decrease in activation overpotential at operationally relevant current densities. An enriched oxygen environment decreases the amount of treatment time required to achieve high surface area. The increased efficiency and greater depth of discharge doubles the total usable energy stored in a fixed amount of electrolyte during operation at 200 mA cm-2.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, XF; Zhao, X; Huang, K

A high-fidelity two-dimensional axial symmetrical multi-physics model is described in this paper as an effort to simulate the cycle performance of a recently discovered solid oxide metal-air redox battery (SOMARB). The model collectively considers mass transport, charge transfer and chemical redox cycle kinetics occurring across the components of the battery, and is validated by experimental data obtained from independent research. In particular, the redox kinetics at the energy storage unit is well represented by Johnson-Mehl-Avrami-Kolmogorov (JIVIAK) and Shrinking Core models. The results explicitly show that the reduction of Fe3O4 during the charging cycle limits the overall performance. Distributions of electrodemore » potential, overpotential, Nernst potential, and H-2/H2O-concentration across various components of the battery are also systematically investigated. (C) 2015 Elsevier B.V. All rights reserved.« less

Three dimensional electrochemical simulation of solid oxide fuel cell cathode based on microstructure reconstructed by marching cubes method

NASA Astrophysics Data System (ADS)

He, An; Gong, Jiaming; Shikazono, Naoki

2018-05-01

In the present study, a model is introduced to correlate the electrochemical performance of solid oxide fuel cell (SOFC) with the 3D microstructure reconstructed by focused ion beam scanning electron microscopy (FIB-SEM) in which the solid surface is modeled by the marching cubes (MC) method. Lattice Boltzmann method (LBM) is used to solve the governing equations. In order to maintain the geometries reconstructed by the MC method, local effective diffusivities and conductivities computed based on the MC geometries are applied in each grid, and partial bounce-back scheme is applied according to the boundary predicted by the MC method. From the tortuosity factor and overpotential calculation results, it is concluded that the MC geometry drastically improves the computational accuracy by giving more precise topology information.

Water Oxidation Catalysis for NiOOH by a Metropolis Monte Carlo Algorithm.

PubMed

Hareli, Chen; Caspary Toroker, Maytal

2018-05-08

Understanding catalytic mechanisms is important for discovering better catalysts, particularly for water splitting reactions that are of great interest to the renewable energy field. One of the best performing catalysts for water oxidation is nickel oxyhydroxide (NiOOH). However, only one mechanism has been adopted so far for modeling catalysis of the active plane: β-NiOOH(01̅5). In order to understand how a second reaction mechanism affects catalysis, we perform Density Functional Theory + U (DFT+U) calculations of a second mechanism for water oxidation reaction of NiOOH. Then, we use a Metropolis Monte Carlo algorithm to calculate how many catalytic cycles are completed when two reaction mechanisms are competing. We find that within the Metropolis algorithm, the second mechanism has a higher overpotential and is therefore not active even for large applied biases.

Self-Supported Ni(P, O)x·MoOx Nanowire Array on Nickel Foam as an Efficient and Durable Electrocatalyst for Alkaline Hydrogen Evolution.

PubMed

Hua, Wei; Liu, Huanyan; Wang, Jian-Gan; Wei, Bingqing

2017-12-06

Earth-abundant and low-cost catalysts with excellent electrocatalytic hydrogen evolution reaction (HER) activity in alkaline solution play an important role in the sustainable production of hydrogen energy. In this work, a catalyst of Ni(P, O) x ·MoO x nanowire array on nickel foam has been prepared via a facile route for efficient alkaline HER. Benefiting from the collaborative advantages of Ni(P, O) x and amorphous MoO x , as well as three-dimensional porous conductive nickel scaffold, the hybrid electrocatalyst shows high catalytic activity in 1 M KOH aqueous solution, including a small overpotential of 59 mV at 10 mA cm -2 , a low Tafel slope of 54 mV dec -1 , and excellent cycling stability.

Self-Supported Ni(P, O)x·MoOx Nanowire Array on Nickel Foam as an Efficient and Durable Electrocatalyst for Alkaline Hydrogen Evolution

PubMed Central

Hua, Wei; Liu, Huanyan

2017-01-01

Earth-abundant and low-cost catalysts with excellent electrocatalytic hydrogen evolution reaction (HER) activity in alkaline solution play an important role in the sustainable production of hydrogen energy. In this work, a catalyst of Ni(P, O)x·MoOx nanowire array on nickel foam has been prepared via a facile route for efficient alkaline HER. Benefiting from the collaborative advantages of Ni(P, O)x and amorphous MoOx, as well as three-dimensional porous conductive nickel scaffold, the hybrid electrocatalyst shows high catalytic activity in 1 M KOH aqueous solution, including a small overpotential of 59 mV at 10 mA cm−2, a low Tafel slope of 54 mV dec-1, and excellent cycling stability. PMID:29210991

Bio-inspired nanocatalysts for the oxygen reduction reaction.

PubMed

Grumelli, Doris; Wurster, Benjamin; Stepanow, Sebastian; Kern, Klaus

2013-01-01

Electrochemical conversions at fuel cell electrodes are complex processes. In particular, the oxygen reduction reaction has substantial overpotential limiting the electrical power output efficiency. Effective and inexpensive catalytic interfaces are therefore essential for increased performance. Taking inspiration from enzymes, earth-abundant metal centres embedded in organic environments present remarkable catalytic active sites. Here we show that these enzyme-inspired centres can be effectively mimicked in two-dimensional metal-organic coordination networks self-assembled on electrode surfaces. Networks consisting of trimesic acid and bis-pyridyl-bispyrimidine coordinating to single iron and manganese atoms on Au(111) effectively catalyse the oxygen reduction and reveal distinctive catalytic activity in alkaline media. These results demonstrate the potential of surface-engineered metal-organic networks for electrocatalytic conversions. Specifically designed coordination complexes at surfaces inspired by enzyme cofactors represent a new class of nanocatalysts with promising applications in electrocatalysis.

MgCl 2 : The Key Ingredient to Improve Chloride Containing Electrolytes for Rechargeable Magnesium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Baofei; Huang, Jinhua; Sa, Niya

The effect of MgCl2 on a series of chloride containing magnesium electrolytes was investigated. In the presence of extra MgCl2, the electrochemical properties of Grignard reagents (RMgCl, R = Ph, Et, iPr) were significantly improved, and the advance of MgCl2 was further demonstrated in Mg-Mo6S8 rechargeable batteries with improved capacities and much smaller over-potentials. MgCl2 was then further proven to be powerful reagent to improve the performance of well-established strong Lewis acid derived magnesium electrolytes including the “all-phenyl” complex (APC) and alkoxide-based magnesium electrolytes. The results suggest that MgCl2 salt is a very important species to benefit all chloride containingmore » electrolytes for rechargeable magnesium-ion batteries.« less

Dioxygen Binding, Activation, and Reduction to H2O by Cu Enzymes.

PubMed

Solomon, Edward I

2016-07-05

Oxygen intermediates in copper enzymes exhibit unique spectroscopic features that reflect novel geometric and electronic structures that are key to reactivity. This perspective will describe: (1) the bonding origin of the unique spectroscopic features of the coupled binuclear copper enzymes and how this overcomes the spin forbiddenness of O2 binding and activates monooxygenase activity, (2) how the difference in exchange coupling in the non-coupled binuclear Cu enzymes controls the reaction mechanism, and (3) how the trinuclear Cu cluster present in the multicopper oxidases leads to a major structure/function difference in enabling the irreversible reductive cleavage of the O-O bond with little overpotential and generating a fully oxidized intermediate, different from the resting enzyme studied by crystallography, that is key in enabling fast PCET in the reductive half of the catalytic cycle.

Metal-Organic-Framework-Derived Yolk-Shell-Structured Cobalt-Based Bimetallic Oxide Polyhedron with High Activity for Electrocatalytic Oxygen Evolution.

PubMed

Yu, Zhou; Bai, Yu; Liu, Yuxuan; Zhang, Shimin; Chen, Dandan; Zhang, Naiqing; Sun, Kening

2017-09-20

The development of inexpensive, efficient, and environmentally friendly catalysts for oxygen evolution reaction (OER) is of great significant for green energy utilization. Herein, binary metal oxides (M x Co 3-x O 4 , M = Zn, Ni, and Cu) with yolk-shell polyhedron (YSP) structure were fabricated by facile pyrolysis of bimetallic zeolitic imidazolate frameworks (MCo-ZIFs). Benefiting from the synergistic effects of metal ions and the unique yolk-shell structure, M x Co 3-x O 4 YSP displays good OER catalytic activity in alkaline media. Impressively, Zn x Co 3-x O 4 YSP shows a comparable overpotential of 337 mV at 10 mA cm -2 to commercial RuO 2 and exhibits superior long-term durability. The high activity and good stability reveals its promising application.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Esswein, AJ; Surendranath, Y; Reece, SY

A high surface area electrode is functionalized with cobalt-based oxygen evolving catalysts (Co-OEC = electrodeposited from pH 7 phosphate, Pi, pH 8.5 methylphosphonate, MePi, and pH 9.2 borate electrolyte, Bi). Co-OEC prepared from MePi and operated in Pi and Bi achieves a current density of 100 mA cm(-2) for water oxidation at 442 and 363 mV overpotential, respectively. The catalyst retains activity in near-neutral pH buffered electrolyte in natural waters such as those from the Charles River (Cambridge, MA) and seawater (Woods Hole, MA). The efficacy and ease of operation of anodes functionalized with Co-OEC at appreciable current density togethermore » with its ability to operate in near neutral pH buffered natural water sources bodes well for the translation of this catalyst to a viable renewable energy storage technology.« less

Bimetallic cooperative effect on O-O bond formation: copper polypyridyl complexes as water oxidation catalyst.

PubMed

Su, Xiao-Jun; Zheng, Chu; Hu, Qin-Qin; Du, Hao-Yi; Liao, Rong-Zhen; Zhang, Ming-Tian

2018-06-13

The performance of water oxidation catalysis by a Cu-based polypyridyl complex, [CuII(TPA)(OH2)]2+ (1H; TPA = tris-(pyridylmethyl)amine), has been investigated in neutral aqueous solution by electrochemical methods. Compared with our previously reported binuclear catalyst, [(BPMAN)(CuII)2(μ-OH)]3+ (2; BPMAN = 2,7-[bis(2-pyridylmethyl)aminomethyl]-1,8-naphthyridine), mononuclear catalyst 1 has a higher overpotential and lower catalytic activity toward water oxidation under the same conditions. Experimental results revealed that the O-O bond formation occurred via a water nucleophilic attack mechanism in which formal CuIV(O) is proposed as a key intermediate for the mononuclear catalyst 1H. In contrast, for the binuclear catalyst, O-O bond formation was facilitated by bimetallic cooperation between the two CuIII centers.

A New Member of Electrocatalysts Based on Nickel Metaphosphate Nanocrystals for Efficient Water Oxidation.

PubMed

Huang, Jianwen; Sun, Yinghui; Zhang, Yadong; Zou, Guifu; Yan, Chaoyi; Cong, Shan; Lei, Tianyu; Dai, Xiao; Guo, Jun; Lu, Ruifeng; Li, Yanrong; Xiong, Jie

2018-02-01

High-performance electrocatalysts are desired for electrochemical energy conversion, especially in the field of water splitting. Here, a new member of phosphate electrocatalysts, nickel metaphosphate (Ni 2 P 4 O 12 ) nanocrystals, is reported, exhibiting low overpotential of 270 mV to generate the current density of 10 mA cm -2 and a superior catalytic durability of 100 h. It is worth noting that Ni 2 P 4 O 12 electrocatalyst has remarkable oxygen evolution performance operating in basic media. Further experimental and theoretical analyses demonstrate that N dopant boosts the catalytic performance of Ni 2 P 4 O 12 due to optimizing the surface electronic structure for better charge transfer and decreasing the adsorption energy for the oxygenic intermediates. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hollow Nanostructured Anode Materials for Li-Ion Batteries

PubMed Central

2010-01-01

Hollow nanostructured anode materials lie at the heart of research relating to Li-ion batteries, which require high capacity, high rate capability, and high safety. The higher capacity and higher rate capability for hollow nanostructured anode materials than that for the bulk counterparts can be attributed to their higher surface area, shorter path length for Li+ transport, and more freedom for volume change, which can reduce the overpotential and allow better reaction kinetics at the electrode surface. In this article, we review recent research activities on hollow nanostructured anode materials for Li-ion batteries, including carbon materials, metals, metal oxides, and their hybrid materials. The major goal of this review is to highlight some recent progresses in using these hollow nanomaterials as anode materials to develop Li-ion batteries with high capacity, high rate capability, and excellent cycling stability. PMID:21076674

Molecular molybdenum persulfide and related catalysts for generating hydrogen from water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, Jeffrey R.; Chang, Christopher J.; Karunadasa, Hemamala I.

New metal persulfido compositions of matter are described. In one embodiment the metal is molybdenum and the metal persulfido complex mimics the structure and function of the triangular active edge site fragments of MoS.sub.2, a material that is the current industry standard for petroleum hydro desulfurization, as well as a promising low-cost alternative to platinum for electrocatalytic hydrogen production. This molecular [(PY5W.sub.2)MoS.sub.2].sup.x+ containing catalyst is capable of generating hydrogen from acidic-buffered water or even seawater at very low overpotentials at a turnover frequency rate in excess of 500 moles H.sub.2 per mole catalyst per second, with a turnover number (overmore » a 20 hour period) of at least 19,000,000 moles H.sub.2 per mole of catalyst.« less

Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating.

PubMed

Liang, Zheng; Lin, Dingchang; Zhao, Jie; Lu, Zhenda; Liu, Yayuan; Liu, Chong; Lu, Yingying; Wang, Haotian; Yan, Kai; Tao, Xinyong; Cui, Yi

2016-03-15

Lithium metal-based battery is considered one of the best energy storage systems due to its high theoretical capacity and lowest anode potential of all. However, dendritic growth and virtually relative infinity volume change during long-term cycling often lead to severe safety hazards and catastrophic failure. Here, a stable lithium-scaffold composite electrode is developed by lithium melt infusion into a 3D porous carbon matrix with "lithiophilic" coating. Lithium is uniformly entrapped on the matrix surface and in the 3D structure. The resulting composite electrode possesses a high conductive surface area and excellent structural stability upon galvanostatic cycling. We showed stable cycling of this composite electrode with small Li plating/stripping overpotential (<90 mV) at a high current density of 3 mA/cm(2) over 80 cycles.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miao, Ran; Dutta, Biswanath; Sahoo, Sanjubala

Here, we report a facile synthetic protocol to pre-pare mesoporous FeS 2 without the aid of hard template as an electrocatalyst for the hydrogen evolution reaction (HER). The mesoporous FeS 2 materials with high surface area were successfully prepared by a sol-gel method follow-ing a sulfurization treatment in an H 2S atmosphere. A re-markable HER catalytic performance was achieved with a low overpotential of 96 mV at a current density of 10 mA·cm 2 and a Tafel slope of 78 mV per decade under alka-line conditions (pH 13). These theoretical calculations indicate that the excellent catalytic activity of mesoporous FeSmore » 2 is attributed to the exposed (210) facets. The mesoporous FeS 2 material might be a promising alternative to the Pt-based electrocatalysts for water splitting.« less

Synthesis, Characterization, and Reactivity of Functionalized Trinuclear Iron–Sulfur Clusters – A New Class of Bioinspired Hydrogenase Models

PubMed Central

Kaiser, Manuel; Knör, Günther

2015-01-01

The air- and moisture-stable iron–sulfur carbonyl clusters Fe3S2(CO)7(dppm) (1) and Fe3S2(CO)7(dppf) (2) carrying the bisphosphine ligands bis(diphenylphosphanyl)methane (dppm) and 1,1′-bis(diphenylphosphanyl)ferrocene (dppf) were prepared and fully characterized. Two alternative synthetic routes based on different thionation reactions of triiron dodecacarbonyl were tested. The molecular structures of the methylene-bridged compound 1 and the ferrocene-functionalized derivative 2 were determined by single-crystal X-ray diffraction. The catalytic reactivity of the trinuclear iron–sulfur cluster core for proton reduction in solution at low overpotential was demonstrated. These deeply colored bisphosphine-bridged sulfur-capped iron carbonyl systems are discussed as promising candidates for the development of new bioinspired model compounds of iron-based hydrogenases. PMID:26512211

Co(II)-Doped Cd-MOF as an Efficient Water Oxidation Catalyst: Doubly Interpenetrated Boron Nitride Network with the Encapsulation of Free Ligand Containing Pyridine Moieties.

PubMed

Maity, Kartik; Bhunia, Kousik; Pradhan, Debabrata; Biradha, Kumar

2017-11-01

Development of an efficient and inexpensive water oxidation electrocatalyst using the earth-abundant elements is still far to go. Herein, a novel strategy has been demonstrated for developing the OER electrocatalyst by doping Co(II) in to a three-dimensional Cd-based MOF that contains a naked pyridine moieties in the form of uncoordinated ligand. Electrochemically active CoCd-MOF was resulted through the doping of Co(II) into the inactive Cd-MOF. CoCd-MOF exhibited very high catalytic activity in water oxidation reaction. An overpotential of 353 mV is required to produce an anodic current density of 1 mA/cm 2 under alkaline conditions. Further, the CoCd-MOF exhibits remarkable recyclability over 1000 cycles.

Composite cathode materials development for intermediate temperature solid oxide fuel cell systems

NASA Astrophysics Data System (ADS)

Qin, Ya

Solid oxide fuel cell (SOFC) systems are of particular interest as electrochemical power systems that can operate on various hydrocarbon fuels with high fuel-to-electrical energy conversion efficiency. Within the SOFC stack, La0.8Sr 0.2Ga0.8Mg0.115Co0.085O3-delta (LSGMC) has been reported as an optimized composition of lanthanum gallate based electrolytes to achieve higher oxygen ionic conductivity at intermediate temperatures, i.e., 500-700°C. The electrocatalytic properties of interfaces between LSGMC electrolytes and various candidate intermediate-temperature SOFC cathodes have been investigated. Sm0.5Sr0.5CoO 3-delta (SSC), and La0.6Sr0.4Co0.2Fe 0.8O3-delta (LSCF), in both pure and composite forms with LSGMC, were investigated with regards to both oxygen reduction and evolution, A range of composite cathode compositions, having ratios of SSC (in wt.%) with LSGMC (wt.%) spanning the compositions 9:1, 8:2, 7:3, 6:4 and 5:5, were investigated to determine the optimal cathode-electrolyte interface performance at intermediate temperatures. All LSGMC electrolyte and cathode powders were synthesized using the glycine-nitrate process (GNP). Symmetrical electrochemical cells were investigated with three-electrode linear dc polarization and ac impedance spectroscopy to characterize the kinetics of the interfacial reactions in detail. Composite cathodes were found to perform better than the single phase cathodes due to significantly reduced polarization resistances. Among those composite SSC-LSGMC cathodes, the 7:3 composition has demonstrated the highest current density at the equivalent overpotential values, indicating that 7:3 is an optimal mixing ratio of the composite cathode materials to achieve the best performance. For the composite SC-LSGMC cathode/LSGMC interface, the cathodic overpotential under 1 A/cm2 current density was as low as 0.085 V at 700°C, 0.062V at 750°C and 0.051V at 800°C in air. Composite LSCF-LSGMC cathode/LSGMC interfaces were found to have about twice the exchange current density of composite SSC-LSGMC/LSGMC interfaces at 700°C. In this research effort, it has been found that: (1) the glycine-nitrate combustion process is favorable to produce perovskite-type oxide powders with good phase purity and negligible intermediate or contaminant phases; (2) The electrochemical performance for both the SSC-LSGMC and LSCF-LSGMC composite electrode materials on LSGMC confirm their potential for use in intermediate temperature SOFC applications; (3) The composite LSCF-LSGMC electrode exhibited much higher current density than the composite SSC-LSGMC electrode in the current dc polarization measurements; and (4) Primary market study results showed promising commercialization feasibility of these new materials sets, provided production is scaled up (with dramatic cost reductions).

Nuclear resonance vibrational spectroscopy reveals the FeS cluster composition and active site vibrational properties of an O 2-tolerant NAD +-reducing [NiFe] hydrogenase

DOE PAGES

Lauterbach, Lars; Wang, Hongxin; Horch, Marius; ...

2014-10-30

Hydrogenases are complex metalloenzymes that catalyze the reversible splitting of molecular hydrogen into protons and electrons essentially without overpotential. The NAD+-reducing soluble hydrogenase (SH) from Ralstonia eutropha is capable of H 2 conversion even in the presence of usually toxic dioxygen. The molecular details of the underlying reactions are largely unknown, mainly because of limited knowledge of the structure and function of the various metal cofactors present in the enzyme. Here, all iron-containing cofactors of the SH were investigated by 57Fe specific nuclear resonance vibrational spectroscopy (NRVS). Our data provide experimental evidence for one [2Fe2S] center and four [4Fe4S] clusters,more » which is consistent with the amino acid sequence composition. Only the [2Fe2S] cluster and one of the four [4Fe4S] clusters were reduced upon incubation of the SH with NADH. This finding explains the discrepancy between the large number of FeS clusters and the small amount of FeS cluster-related signals as detected by electron paramagnetic resonance spectroscopic analysis of several NAD+-reducing hydrogenases. For the first time, Fe–CO and Fe–CN modes derived from the [NiFe] active site could be distinguished by NRVS through selective 13C labeling of the CO ligand. This strategy also revealed the molecular coordinates that dominate the individual Fe–CO modes. The present approach explores the complex vibrational signature of the Fe–S clusters and the hydrogenase active site, thereby showing that NRVS represents a powerful tool for the elucidation of complex biocatalysts containing multiple cofactors.« less

Nuclear resonance vibrational spectroscopy reveals the FeS cluster composition and active site vibrational properties of an O2-tolerant NAD+-reducing [NiFe] hydrogenase.

PubMed

Lauterbach, Lars; Wang, Hongxin; Horch, Marius; Gee, Leland B; Yoda, Yoshitaka; Tanaka, Yoshihito; Zebger, Ingo; Lenz, Oliver; Cramer, Stephen P

Hydrogenases are complex metalloenzymes that catalyze the reversible splitting of molecular hydrogen into protons and electrons essentially without overpotential. The NAD + -reducing soluble hydrogenase (SH) from Ralstonia eutropha is capable of H 2 conversion even in the presence of usually toxic dioxygen. The molecular details of the underlying reactions are largely unknown, mainly because of limited knowledge of the structure and function the various metal cofactors present in the enzyme. Here all iron-containing cofactors of the SH were investigated by 57 Fe specific nuclear resonance vibrational spectroscopy (NRVS). Our data provide experimental evidence for one [2Fe2S] center and four [4Fe4S] clusters, which is consistent with amino acid sequence composition. Only the [2Fe2S] cluster and one of the four [4Fe4S] clusters were reduced upon incubation of the SH with NADH. This finding explains the discrepancy between the large number of FeS clusters and the small amount of FeS cluster-related signals as detected by electron paramagnetic resonance spectroscopic analysis of several NAD + -reducing hydrogenases. For the first time, Fe-CO and Fe-CN modes derived from the [NiFe] active site could be distinguished by NRVS through selective 13 C labeling of the CO ligand. This strategy also revealed the molecular coordinates that dominate the individual Fe-CO modes. The present approach explores the complex vibrational signature of the Fe-S clusters and the hydrogenase active site, thereby showing that NRVS represents a powerful tool for the elucidation of complex biocatalysts containing multiple cofactors.

Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates.

PubMed

Wang, Zhijiang; Wu, Lina; Sun, Kun; Chen, Ting; Jiang, Zhaohua; Cheng, Tao; Goddard, William A

2018-05-23

We have explored functionalizing metal catalysts with surface ligands as an approach to facilitate electrochemical carbon dioxide reduction reaction (CO 2 RR). To provide a molecular level understanding of the mechanism by which this enhancement occurs, we combine in situ spectroscopy analysis with an interpretation based on quantum mechanics (QM) calculations. We find that a surface ligand can play a critical role in stabilizing the chemisorbed CO 2 , which facilitates CO 2 activation and leads to a 0.3 V decrease in the overpotential for carbon monoxide (CO) formation. Moreover, the presence of the surface ligand leads to nearly exclusive CO production. At -0.6 V (versus reversible hydrogen electrode, RHE), CO is the only significant product with a faradic efficiency of 93% and a current density of 1.9 mA cm -2 . This improvement corresponds to 53-fold enhancement in turnover frequency compared with the Ag nanoparticles (NPs) without surface ligands.

Tunable Molecular-Scale Materials for Catalyzing the Low-Overpotential Electrochemical Conversion of CO2.

PubMed

Rosen, Brian A; Hod, Idan

2018-04-25

Electrochemical CO 2 reduction provides a clean and viable alternative for mitigating the environmental aspects of global greenhouse gas emissions. To date, the simultaneous goals of CO 2 reduction at high selectivity and activity have yet to be achieved. Here, the importance of engineering both sides of the electrode-electrolyte interface as a rational strategy for achieving this milestone is highlighted. An emphasis is placed on researchers contributing to the design of solid electrodes based on metal-organic frameworks (MOFs) and electrolytes based on room-temperature ionic liquids (RTILs). Future research geared toward optimizing the electrode-electrolyte interface for efficient and selective CO 2 reduction can be achieved by understanding the structure of newly designed RTILs at the electrified interface, as well as structure-activity relationships in highly tunable MOF platforms. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances.

PubMed

Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

2018-05-25

This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co 9 S 8 aerogel with a high surface area (274.2 m 2 g -1 ) and large pore volume (0.87 cm 3 g -1 ) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co 9 S 8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g -1 at 1 A g -1 ), good rate capability (74.3% capacitance retention from 1 to 20 A g -1 ) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

Ruthenium-cobalt nanoalloys encapsulated in nitrogen-doped graphene as active electrocatalysts for producing hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

Su, Jianwei; Yang, Yang; Xia, Guoliang; Chen, Jitang; Jiang, Peng; Chen, Qianwang

2017-04-01

The scalable production of hydrogen could conveniently be realized by alkaline water electrolysis. Currently, the major challenge confronting hydrogen evolution reaction (HER) is lacking inexpensive alternatives to platinum-based electrocatalysts. Here we report a high-efficient and stable electrocatalyst composed of ruthenium and cobalt bimetallic nanoalloy encapsulated in nitrogen-doped graphene layers. The catalysts display remarkable performance with low overpotentials of only 28 and 218 mV at 10 and 100 mA cm-2, respectively, and excellent stability of 10,000 cycles. Ruthenium is the cheapest platinum-group metal and its amount in the catalyst is only 3.58 wt.%, showing the catalyst high activity at a very competitive price. Density functional theory calculations reveal that the introduction of ruthenium atoms into cobalt core can improve the efficiency of electron transfer from alloy core to graphene shell, beneficial for enhancing carbon-hydrogen bond, thereby lowing ΔGH* of HER.

In-situ confined formation of NiFe layered double hydroxide quantum dots in expanded graphite for active electrocatalytic oxygen evolution

NASA Astrophysics Data System (ADS)

Guo, Jinxue; Li, Xiaoyan; Sun, Yanfang; Liu, Qingyun; Quan, Zhenlan; Zhang, Xiao

2018-06-01

Development of noble-metal-free catalysts towards highly efficient electrochemical oxygen evolution reaction (OER) is critical but challenging in the renewable energy area. Herein, we firstly embed NiFe LDHs quantum dots (QDs) into expanded graphite (NiFe LDHs/EG) via in-situ confined formation process. The interlayer spacing of EG layers acts as nanoreactors for spatially confined formation of NiFe LDHs QDs. The QDs supply huge catalytic sites for OER. The in-situ decoration endows the strong affinity between QDs with EG, thus inducing fast charge transfer. Based on the aforementioned benefits, the designed catalyst exhibits outstanding OER properties, in terms of small overpotential (220 mV required to generate 10 mA cm-2), low Tafel slope, and good durable stability, making it a promising candidate for inexpensive OER catalyst.

Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances

NASA Astrophysics Data System (ADS)

Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

2018-05-01

This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co9S8 aerogel with a high surface area (274.2 m2 g‑1) and large pore volume (0.87 cm3 g‑1) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co9S8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g‑1 at 1 A g‑1), good rate capability (74.3% capacitance retention from 1 to 20 A g‑1) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

Parameter estimation and characterization of a single-chamber microbial fuel cell for dairy wastewater treatment.

PubMed

Sedaqatvand, Ramin; Nasr Esfahany, Mohsen; Behzad, Tayebeh; Mohseni, Madjid; Mardanpour, Mohammad Mahdi

2013-10-01

In this study, for the first time, the conduction-based model is extended, and then combined with Genetic Algorithm to estimate the design parameters of a MFC treating dairy wastewater. The optimized parameters are, then, validated. The estimated half-saturation potential of -0.13 V (vs. SHE) is in good agreement while the biofilm conductivity of 8.76×10(-4) mS cm(-1) is three orders of magnitude lower than that previously-reported for pure-culture biofilm. Simulations show that the ohmic and concentration overpotentials contribute almost equally in dropping cell voltage in which the concentration film and biofilm conductivity comprise the main resistances, respectively. Thus, polarization analysis and determining the controlling steps will be possible through that developed extension. This study introduces a reliable method to estimate the design parameters of a particular MFC and to characterize it. Copyright © 2013 Elsevier Ltd. All rights reserved.

An amorphous FeMoS4 nanorod array toward efficient hydrogen evolution electrocatalysis under neutral conditions.

PubMed

Ren, Xiang; Wang, Weiyi; Ge, Ruixiang; Hao, Shuai; Qu, Fengli; Du, Gu; Asiri, Abdullah M; Wei, Qin; Chen, Liang; Sun, Xuping

2017-08-08

It is highly attractive to develop efficient hydrogen-evolving electrocatalysts under neutral conditions. In this communication, we report an amorphous FeMoS 4 nanorod array on carbon cloth (FeMoS 4 NRA/CC) prepared by hydrothermal treatment of an FeOOH nanorod array on carbon cloth (FeOOH NRA/CC) in (NH 4 ) 2 MoS 4 solution. As a 3D electrode for hydrogen evolution electrocatalysis, this FeMoS 4 NRA/CC demonstrates superior catalytic activity and strong long-term electrochemical durability in 1.0 M phosphate buffered saline (pH: 7). It needs an overpotential of 204 mV to drive a geometrical current density of 10 mA cm -2 , which is 450 mV less than that for FeOOH NRA/CC. Density functional theory calculations suggest that FeMoS 4 has a more favourable hydrogen adsorption free energy than FeOOH.

A review of high-temperature polymer electrolyte membrane fuel-cell (HT-PEMFC)-based auxiliary power units for diesel-powered road vehicles

NASA Astrophysics Data System (ADS)

Liu, Yongfeng; Lehnert, Werner; Janßen, Holger; Samsun, Remzi Can; Stolten, Detlef

2016-04-01

This paper presents an extensive review of research on the development of auxiliary power units with enhanced reformate tolerance for high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Developments in diesel reforming for fuel cells as auxiliary power units (APUs), single fuel cells and stacks and systems are outlined in detail and key findings are presented. Summaries of HT-PEMFC APU applications and start-up times for HT-PEMFC systems are then given. A summary of cooling HT-PEMFC stacks using a classic schematic diagram of a 24-cell HT-PEMFC stack, with a cooling plate for every third cell, is also presented as part of a stack analysis. Finally, a summary of CO tolerances for fuel cells is given, along with the effects of different CO volume fractions on polarization curves, the fraction of CO coverage, hydrogen coverage, anode overpotential and cell potential.

Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating

PubMed Central

Liang, Zheng; Lin, Dingchang; Zhao, Jie; Lu, Zhenda; Liu, Yayuan; Liu, Chong; Lu, Yingying; Wang, Haotian; Yan, Kai; Tao, Xinyong; Cui, Yi

2016-01-01

Lithium metal-based battery is considered one of the best energy storage systems due to its high theoretical capacity and lowest anode potential of all. However, dendritic growth and virtually relative infinity volume change during long-term cycling often lead to severe safety hazards and catastrophic failure. Here, a stable lithium–scaffold composite electrode is developed by lithium melt infusion into a 3D porous carbon matrix with “lithiophilic” coating. Lithium is uniformly entrapped on the matrix surface and in the 3D structure. The resulting composite electrode possesses a high conductive surface area and excellent structural stability upon galvanostatic cycling. We showed stable cycling of this composite electrode with small Li plating/stripping overpotential (<90 mV) at a high current density of 3 mA/cm2 over 80 cycles. PMID:26929378

Semiconductor-Based Photoelectrochemical Conversion of Carbon Dioxide: Stepping Towards Artificial Photosynthesis.

PubMed

Pang, Hong; Masuda, Takuya; Ye, Jinhua

2018-01-18

The photoelectrochemical (PEC) carbon dioxide reduction process stands out as a promising avenue for the conversion of solar energy into chemical feedstocks, among various methods available for carbon dioxide mitigation. Semiconductors derived from cheap and abundant elements are interesting candidates for catalysis. Whether employed as intrinsic semiconductors or hybridized with metallic cocatalysts, biocatalysts, and metal molecular complexes, semiconductor photocathodes exhibit good performance and low overpotential during carbon dioxide reduction. Apart from focusing on carbon dioxide reduction materials and chemistry, PEC cells towards standalone devices that use photohybrid electrodes or solar cells have also been a hot topic in recent research. An overview of the state-of-the-art progress in PEC carbon dioxide reduction is presented and a deep understanding of the catalysts of carbon dioxide reduction is also given. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Underpotential deposition-mediated layer-by-layer growth of thin films

DOEpatents

Wang, Jia Xu; Adzic, Radoslav R.

2015-05-19

A method of depositing contiguous, conformal submonolayer-to-multilayer thin films with atomic-level control is described. The process involves the use of underpotential deposition of a first element to mediate the growth of a second material by overpotential deposition. Deposition occurs between a potential positive to the bulk deposition potential for the mediating element where a full monolayer of mediating element forms, and a potential which is less than, or only slightly greater than, the bulk deposition potential of the material to be deposited. By cycling the applied voltage between the bulk deposition potential for the mediating element and the material to be deposited, repeated desorption/adsorption of the mediating element during each potential cycle can be used to precisely control film growth on a layer-by-layer basis. This process is especially suitable for the formation of a catalytically active layer on core-shell particles for use in energy conversion devices such as fuel cells.

Co9 S8 /Co as a High-Performance Anode for Sodium-Ion Batteries with an Ether-Based Electrolyte.

PubMed

Zhao, Yingying; Pang, Qiang; Wei, Yingjin; Wei, Luyao; Ju, Yanming; Zou, Bo; Gao, Yu; Chen, Gang

2017-12-08

Co 9 S 8 has been regarded as a desirable anode material for sodium-ion batteries because of its high theoretical capacity. In this study, a Co 9 S 8 anode material containing 5.5 wt % Co (Co 9 S 8 /Co) was prepared by a solid-state reaction. The electrochemical properties of the material were studied in carbonate and ether-based electrolytes (EBE). The results showed that the material had a longer cycle life and better rate capability in EBE. This excellent electrochemical performance was attributed to a low apparent activation energy and a low overpotential for Na deposition in EBE, which improved the electrode kinetic properties. Furthermore, EBE suppressed side reactions of the electrode and electrolyte, which avoided the formation of a solid electrolyte interphase film. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transition Metal Nitrides for Electrocatalytic Energy Conversion: Opportunities and Challenges.

PubMed

Xie, Junfeng; Xie, Yi

2016-03-07

Electrocatalytic energy conversion has been considered as one of the most efficient and promising pathways for realizing energy storage and energy utilization in modern society. To improve electrocatalytic reactions, specific catalysts are needed to lower the overpotential. In the search for efficient alternatives to noble metal catalysts, transition metal nitrides have attracted considerable interest due to their high catalytic activity and unique electronic structure. Over the past few decades, numerous nitride-based catalysts have been explored with respect to their ability to drive various electrocatalytic reactions, such as the hydrogen evolution reaction and the oxygen evolution reaction to achieve water splitting and the oxygen reduction reaction coupled with the methanol oxidation reaction to construct fuel cells or rechargeable Li-O2 batteries. This Minireview provides a brief overview of recent progress on electrocatalysts based on transition metal nitrides, and outlines the current challenges and future opportunities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Proton enhanced dynamic battery chemistry for aprotic lithium-oxygen batteries.

PubMed

Zhu, Yun Guang; Liu, Qi; Rong, Yangchun; Chen, Haomin; Yang, Jing; Jia, Chuankun; Yu, Li-Juan; Karton, Amir; Ren, Yang; Xu, Xiaoxiong; Adams, Stefan; Wang, Qing

2017-02-06

Water contamination is generally considered to be detrimental to the performance of aprotic lithium-air batteries, whereas this view is challenged by recent contrasting observations. This has provoked a range of discussions on the role of water and its impact on batteries. In this work, a distinct battery chemistry that prevails in water-contaminated aprotic lithium-oxygen batteries is revealed. Both lithium ions and protons are found to be involved in the oxygen reduction and evolution reactions, and lithium hydroperoxide and lithium hydroxide are identified as predominant discharge products. The crystallographic and spectroscopic characteristics of lithium hydroperoxide monohydrate are scrutinized both experimentally and theoretically. Intriguingly, the reaction of lithium hydroperoxide with triiodide exhibits a faster kinetics, which enables a considerably lower overpotential during the charging process. The battery chemistry unveiled in this mechanistic study could provide important insights into the understanding of nominally aprotic lithium-oxygen batteries and help to tackle the critical issues confronted.

Fabricating Ir/C Nanofiber Networks as Free-Standing Air Cathodes for Rechargeable Li-CO2 Batteries.

PubMed

Wang, Chengyi; Zhang, Qinming; Zhang, Xin; Wang, Xin-Gai; Xie, Zhaojun; Zhou, Zhen

2018-06-07

Li-CO 2 batteries are promising energy storage systems by utilizing CO 2 at the same time, though there are still some critical barriers before its practical applications such as high charging overpotential and poor cycling stability. In this work, iridium/carbon nanofibers (Ir/CNFs) are prepared via electrospinning and subsequent heat treatment, and are used as cathode catalysts for rechargeable Li-CO 2 batteries. Benefitting from the unique porous network structure and the high activity of ultrasmall Ir nanoparticles, Ir/CNFs exhibit excellent CO 2 reduction and evolution activities. The Li-CO 2 batteries present extremely large discharge capacity, high coulombic efficiency, and long cycling life. Moreover, free-standing Ir/CNF films are used directly as air cathodes to assemble Li-CO 2 batteries, which show high energy density and ultralong operation time, demonstrating great potential for practical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

PubMed

Gan, Patrick; Foord, John S; Compton, Richard G

2015-10-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur.

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering

PubMed Central

Shinagawa, Tatsuya

2017-01-01

Abstract Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine‐tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions. PMID:27984671

Polyoxometalate-Graphene Nanocomposite Modified Electrode for Electrocatalytic Detection of Ascorbic Acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Weiying; Du, Dan; Gunaratne, Don

Phosphomolybdate functionalized graphene nanocomposite (PMo 12-GS) has been successfully formed on a glassy carbon electrode (GCE) for the detection of ascorbic acid (AA). The obtained PMo 12-GS modified GCE, was characterized by cyclic voltammetry, electrochemical impedance spectroscopy, scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy and compared with GCE, GS modified GCE, and PMo 12 modified GCE. It shows an increased current and a decrease in over-potential of ~210 mV. The amperometric signals are linearly proportional to the AA concentration in a wide concentration range from 1×10 -6 M to 8×10 -3 M, with a detection limit ofmore » 0.5×10 -6 M. Finally, the PMo 12-GS modified electrode was employed for the determination of the AA level in vitamin C tablets, with recoveries between 96.3 and 100.8 %.« less

Stress Corrosion Cracking Study of Aluminum Alloys Using Electrochemical Noise Analysis

NASA Astrophysics Data System (ADS)

Rathod, R. C.; Sapate, S. G.; Raman, R.; Rathod, W. S.

2013-12-01

Stress corrosion cracking studies of aluminum alloys AA2219, AA8090, and AA5456 in heat-treated and non heat-treated condition were carried out using electrochemical noise technique with various applied stresses. Electrochemical noise time series data (corrosion potential vs. time) was obtained for the stressed tensile specimens in 3.5% NaCl aqueous solution at room temperature (27 °C). The values of drop in corrosion potential, total corrosion potential, mean corrosion potential, and hydrogen overpotential were evaluated from corrosion potential versus time series data. The electrochemical noise time series data was further analyzed with rescaled range ( R/ S) analysis proposed by Hurst to obtain the Hurst exponent. According to the results, higher values of the Hurst exponents with increased applied stresses showed more susceptibility to stress corrosion cracking as confirmed in case of alloy AA 2219 and AA8090.

On the cobalt and cobalt oxide electrodeposition from a glyceline deep eutectic solvent.

PubMed

Sakita, Alan M P; Della Noce, Rodrigo; Fugivara, Cecílio S; Benedetti, Assis V

2016-09-14

The electrodeposition of cobalt and cobalt oxides from a glyceline deep eutectic solvent is reported. Cyclic voltammetry, chronoamperometry, scanning electron microscopy, and Raman spectroscopy are employed to study the Co deposition processes. Surface analysis reveals that metallic cobalt is deposited at potentials less negative than the current peak potential whereas cobalt oxides are detected and electrochemically observed when the deposition is done at more negative potentials. i-t transients are analyzed by applying the Scharifker and Hills (SH) theoretical model. It is concluded that cobalt deposition occurs via a progressive nucleation and growth mechanism for concentrations higher than 0.05 mol L -1 cobalt ions. For concentrations ≤0.025 mol L -1 cobalt ions and low overpotentials, the mechanism changes to instantaneous nucleation. The i m -t m relationships of the SH model are used to determine the values of the kinetic parameters and the cobalt ion diffusion coefficient.

Potentiostatic controlled nucleation and growth modes of electrodeposited cobalt thin films on n-Si(1 1 1)

NASA Astrophysics Data System (ADS)

Mechehoud, Fayçal; Khelil, Abdelbacet; Eddine Hakiki, Nour; Bubendorff, Jean-Luc

2016-08-01

The nucleation and growth of Co electrodeposits on n-Si(1 1 1) substrate have been investigated as a function of the applied potential in a large potential range using electrochemical techniques (voltammetry and chrono-amperometry) and surface imaging by atomic force microscopy (AFM). The surface preparation of the sample is crucial and we achieve a controlled n-Si(1 1 1) surface with mono-atomic steps and flat terraces. Using Scharifker-Hills models for fitting the current-time transients, we show that a transition from an instantaneous nucleation process to a progressive one occurs when the overpotential increases. A good agreement between the nucleation and growth parameters extracted from the models and the AFM data's is observed. The growth is of the Volmer-Weber type with a roughness and a spatial extension in the substrate plane of the deposited islands that increase with thickness.

Electrodeposition of platinum and silver into chemically modified microporous silicon electrodes

PubMed Central

2012-01-01

Electrodeposition of platinum and silver into hydrophobic and hydrophilic microporous silicon layers was investigated using chemically modified microporous silicon electrodes. Hydrophobic microporous silicon enhanced the electrodeposition of platinum in the porous layer. Meanwhile, hydrophilic one showed that platinum was hardly deposited within the porous layer, and a film of platinum on the top of the porous layer was observed. On the other hand, the electrodeposition of silver showed similar deposition behavior between these two chemically modified electrodes. It was also found that the electrodeposition of silver started at the pore opening and grew toward the pore bottom, while a uniform deposition from the pore bottom was observed in platinum electrodeposition. These electrodeposition behaviors are explained on the basis of the both effects, the difference in overpotential for metal deposition on silicon and on the deposited metal, and displacement deposition rate of metal. PMID:22720690

Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes.

PubMed

Pérez-Gallent, Elena; Figueiredo, Marta C; Calle-Vallejo, Federico; Koper, Marc T M

2017-03-20

Carbon dioxide and carbon monoxide can be electrochemically reduced to useful products such as ethylene and ethanol on copper electrocatalysts. The process is yet to be optimized and the exact mechanism and the corresponding reaction intermediates are under debate or unknown. In particular, it has been hypothesized that the C-C bond formation proceeds via CO dimerization and further hydrogenation. Although computational support for this hypothesis exists, direct experimental evidence has been elusive. In this work, we detect a hydrogenated dimer intermediate (OCCOH) using Fourier transform infrared spectroscopy at low overpotentials in LiOH solutions. Density functional theory calculations support our assignment of the observed vibrational bands. The formation of this intermediate is structure sensitive, as it is observed only during CO reduction on Cu(100) and not on Cu(111), in agreement with previous experimental and computational observations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study.

PubMed

Gomez-Mingot, Maria; Porcher, Jean-Philippe; Todorova, Tanya K; Fogeron, Thibault; Mellot-Draznieks, Caroline; Li, Yun; Fontecave, Marc

2015-10-29

Bis(dithiolene)tungsten complexes, W(VI)O2 (L = dithiolene)2 and W(IV)O (L = dithiolene)2, which mimic the active site of formate dehydrogenases, have been characterized by cyclic voltammetry and controlled potential electrolysis in acetonitrile. They are shown to be able to catalyze the electroreduction of protons into hydrogen in acidic organic media, with good Faradaic yields (75-95%) and good activity (rate constants of 100 s(-1)), with relatively high overpotentials (700 mV). They also catalyze proton reduction into hydrogen upon visible light irradiation, in combination with [Ru(bipyridine)3](2+) as a photosensitizer and ascorbic acid as a sacrificial electron donor. On the basis of detailed DFT calculations, a reaction mechanism is proposed in which the starting W(VI)O2 (L = dithiolene)2 complex acts as a precatalyst and hydrogen is further formed from a key reduced W-hydroxo-hydride intermediate.

Metal oxide composite enabled nanotextured Si photoanode for efficient solar driven water oxidation.

PubMed

Sun, Ke; Pang, Xiaolu; Shen, Shaohua; Qian, Xueqiang; Cheung, Justin S; Wang, Deli

2013-05-08

We present a study of a transition metal oxide composite modified n-Si photoanode for efficient and stable water oxidation. This sputter-coated composite functions as a protective coating to prevent Si from photodecomposition, a Schottky heterojunction, a hole conducting layer for efficient charge separation and transportation, and an electrocatalyst to reduce the reaction overpotential. The formation of mixed-valence oxides composed of Ni and Ru effectively modifies the optical, electrical, and catalytic properties of the coating material, as well as the interfaces with Si. The successful application of this oxide composite on nanotextured Si demonstrates improved conversion efficiency due to enhanced catalytic activity, minimized reflection, and increased surface reaction sites. Although the coated nanotextured Si shows a noticeable degradation from 500 cycles of operation, the oxide composite provides a simple method to enable unstable photoanode materials for solar fuel conversion.

Surface-modified Mg{sub 2}Ni-type negative electrode materials for Ni-MH battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, N.; Luan, B.; Bradhurst, D.

1997-12-01

In order to further improve the electrode performance of Mg{sub 1.9}Y{sub 0.1}Ni{sub 0.9}Al{sub 0.1} alloy at ambient temperature, its surface was modified by an ultrasound pretreatment in the alkaline solution and microencapsulation with Ni-P coating. The effects of various surface modifications on the microstructure and electrochemical performance of the alloy electrodes were investigated and compared in this paper. It was found that the modification with ultrasound pretreatment significantly improved the electrocatalytic activity of the negative electrode and then reduced the overpotential of charging/discharging, resulting in a remarkable increase of electrode capacity and high-rate discharge capability but having little influence onmore » the cycle life. However, the electrode fabricated from the microencapsulated alloy powder showed a higher discharge capacity, better high-rate discharge capability and longer cycle life as well.« less

Nickel-cobalt bimetallic anode catalysts for direct urea fuel cell

PubMed Central

Xu, Wei; Zhang, Huimin; Li, Gang; Wu, Zucheng

2014-01-01

Nickel is an ideal non-noble metal anode catalyst for direct urea fuel cell (DUFC) due to its high activity. However, there exists a large overpotential toward urea electrooxidation. Herein, NiCo/C bimetallic nanoparticles were prepared with various Co contents (0, 10, 20, 30 and 40 wt%) to improve the activity. The best Co ratio was 10% in the aspect of cell performance, with a maximum power density of 1.57 mW cm−2 when 0.33 M urea was used as fuel, O2 as oxidant at 60°C. The effects of temperature and urea concentration on DUFC performance were investigated. Besides, direct urine fuel cell reaches a maximum power density of 0.19 mW cm−2 with an open circuit voltage of 0.38 V at 60°C. PMID:25168632

Pulse electrodeposition of CoFe thin films covered with layered double hydroxides as a fast route to prepare enhanced catalysts for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Sakita, Alan M. P.; Noce, Rodrigo Della; Vallés, Elisa; Benedetti, Assis V.

2018-03-01

A novel, ultra-fast, and one-step method for obtaining an effective catalyst for oxygen evolution reaction is proposed. The procedure consists in direct electrodeposition, in a free-nitrate bath, of CoFe alloy films covered with layered double hydroxides (LDH), by potentiostatic mode, in continuous or pulsed regime. The catalyst is directly formed on glassy carbon substrates. The best-prepared catalyst material reveals a mixed morphology with granular and dendritic CoFe alloy covered with a sponge of CoFe-LDH containing a Cl interlayer. An overpotential of η10 mA = 286 mV, with a Tafel slope of 48 mV dec-1, is obtained for the OER which displays the enhanced properties of the catalyst. These improved results demonstrate the competitiveness and efficacy of our proposal for the production of OER catalysts.

Cathodic electrochemical activation of Co3O4 nanoarrays: a smart strategy to significantly boost the hydrogen evolution activity.

PubMed

Yang, Li; Zhou, Huang; Qin, Xin; Guo, Xiaodong; Cui, Guanwei; Asiri, Abdullah M; Sun, Xuping

2018-02-22

Co(hydro)oxides show unsatisfactory catalytic activity for the hydrogen evolution reaction (HER) in alkaline media, and it is thus highly desirable but still remains a challenge to design and develop Co(hydro)oxide derived materials as superb hydrogen-evolving catalysts using a facile, rapid and less energy-intensive method. Here, we propose a cathodic electrochemical activation strategy toward greatly boosted HER activity of a Co 3 O 4 nanoarray via room-temperature cathodic polarization in sodium hypophosphite solution. After activation, the overpotential significantly decreases from 260 to 73 mV to drive a geometrical catalytic current density of 10 mA cm -2 in 1.0 M KOH. Notably, this activated electrode also shows strong long-term electrochemical durability with the retention of its catalytic activity at 100 mA cm -2 for at least 40 h.

Confined Molybdenum Phosphide in P-Doped Porous Carbon as Efficient Electrocatalysts for Hydrogen Evolution.

PubMed

Li, Ji-Sen; Zhang, Shuai; Sha, Jing-Quan; Wang, Hao; Liu, Ming-Zhu; Kong, Ling-Xin; Liu, Guo-Dong

2018-05-09

Highly efficient electrocatalysts for hydrogen evolution reactions (HER) are crucial for electrochemical water splitting, where high-cost and low-abundance Pt-based materials are the benchmark catalysts for HER. Herein, we report the fabrication of MoP nanoparticles confined in P-doped porous carbon (MoP@PC) via a metal-organic framework-assisted route for the first time. Remarkably, due to the synergistic effects of MoP nanocrystals, P dopant, and porous carbon, the resulting MoP@PC composite exhibits superior HER catalytic activity with an onset overpotential of 97 mV, a Tafel slope of 59.3 mV dec -1 , and good long-term durability, which compares to those of most reported MoP-based HER catalysts. Most importantly, the work opens a new route in the development of high-performance nonprecious HER electrocatalysts derived from MOFs.

Modeling and Simulations in Photoelectrochemical Water Oxidation: From Single Level to Multiscale Modeling.

PubMed

Zhang, Xueqing; Bieberle-Hütter, Anja

2016-06-08

This review summarizes recent developments, challenges, and strategies in the field of modeling and simulations of photoelectrochemical (PEC) water oxidation. We focus on water splitting by metal-oxide semiconductors and discuss topics such as theoretical calculations of light absorption, band gap/band edge, charge transport, and electrochemical reactions at the electrode-electrolyte interface. In particular, we review the mechanisms of the oxygen evolution reaction, strategies to lower overpotential, and computational methods applied to PEC systems with particular focus on multiscale modeling. The current challenges in modeling PEC interfaces and their processes are summarized. At the end, we propose a new multiscale modeling approach to simulate the PEC interface under conditions most similar to those of experiments. This approach will contribute to identifying the limitations at PEC interfaces. Its generic nature allows its application to a number of electrochemical systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A multiscale physical model for the transient analysis of PEM water electrolyzer anodes.

PubMed

Oliveira, Luiz Fernando L; Laref, Slimane; Mayousse, Eric; Jallut, Christian; Franco, Alejandro A

2012-08-07

Polymer electrolyte membrane water electrolyzers (PEMWEs) are electrochemical devices that can be used for the production of hydrogen. In a PEMWE the anode is the most complex electrode to study due to the high overpotential of the oxygen evolution reaction (OER), not widely understood. A physical bottom-up multi-scale transient model describing the operation of a PEMWE anode is proposed here. This model includes a detailed description of the elementary OER kinetics in the anode, a description of the non-equilibrium behavior of the nanoscale catalyst-electrolyte interface, and a microstructural-resolved description of the transport of charges and O(2) at the micro and mesoscales along the whole anode. The impact of different catalyst materials on the performance of the PEMWE anode, and a study of sensitivity to the operation conditions are evaluated from numerical simulations and the results are discussed in comparison with experimental data.

Protic ionic liquid modified electrocatalyst enables robust anode under cell reversal condition

NASA Astrophysics Data System (ADS)

Zhu, Zhengyu; Yan, Xiaocong; Tang, Haolin; Cai, Haopeng; Pan, Mu; Zhang, Haining; Luo, Jiangshui

2017-05-01

Pt/C has been commercially used as anode electrocatalyst for fuel cells but generally exhibits limited durability under conditions of fuel starvation and subsequent cell reversal. Herein we report an improved scaffold concept to simultaneously stabilize the catalyst against particle growth and reduce the adverse effects of cell reversal by modifying Pt/C with suitable protic ionic liquids (PILs). The modified Pt/C catalysts show enhanced cell reversal tolerance because of their high activity towards oxygen evolution reaction (OER), up to 300 mV lower overpotential compared to the unmodified Pt/C. Moreover, the PIL modified catalysts show better resistance to the loss of electrochemical surface area (ECSA) under simulated cell reversal conditions. The results indicate that modification of Pt/C catalysts with PILs is a promising strategy to enhance the stability and durability of electrocatalysts in fuel cell applications with the risk of frequent fuel starvation events, such as automotive fuel cells.

Issues associated with modelling of proton exchange membrane fuel cell by computational fluid dynamics

NASA Astrophysics Data System (ADS)

Bednarek, Tomasz; Tsotridis, Georgios

2017-03-01

The objective of the current study is to highlight possible limitations and difficulties associated with Computational Fluid Dynamics in PEM single fuel cell modelling. It is shown that an appropriate convergence methodology should be applied for steady-state solutions, due to inherent numerical instabilities. A single channel fuel cell model has been taken as numerical example. Results are evaluated for quantitative as well qualitative points of view. The contribution to the polarization curve of the different fuel cell components such as bi-polar plates, gas diffusion layers, catalyst layers and membrane was investigated via their effects on the overpotentials. Furthermore, the potential losses corresponding to reaction kinetics, due to ohmic and mas transport limitations and the effect of the exchange current density and open circuit voltage, were also investigated. It is highlighted that the lack of reliable and robust input data is one of the issues for obtaining accurate results.

One-Dimensional RuO2/Mn2O3 Hollow Architectures as Efficient Bifunctional Catalysts for Lithium-Oxygen Batteries.

PubMed

Yoon, Ki Ro; Lee, Gil Yong; Jung, Ji-Won; Kim, Nam-Hoon; Kim, Sang Ouk; Kim, Il-Doo

2016-03-09

Rational design and massive production of bifunctional catalysts with fast oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics are critical to the realization of highly efficient lithium-oxygen (Li-O2) batteries. Here, we first exploit two types of double-walled RuO2 and Mn2O3 composite fibers, i.e., (i) phase separated RuO2/Mn2O3 fiber-in-tube (RM-FIT) and (ii) multicomposite RuO2/Mn2O3 tube-in-tube (RM-TIT), by controlling ramping rate during electrospinning process. Both RM-FIT and RM-TIT exhibited excellent bifunctional electrocatalytic activities in alkaline media. The air electrodes using RM-FIT and RM-TIT showed enhanced overpotential characteristics and stable cyclability over 100 cycles in the Li-O2 cells, demonstrating high potential as efficient OER and ORR catalysts.

Proton enhanced dynamic battery chemistry for aprotic lithium–oxygen batteries

PubMed Central

Zhu, Yun Guang; Liu, Qi; Rong, Yangchun; Chen, Haomin; Yang, Jing; Jia, Chuankun; Yu, Li-Juan; Karton, Amir; Ren, Yang; Xu, Xiaoxiong; Adams, Stefan; Wang, Qing

2017-01-01

Water contamination is generally considered to be detrimental to the performance of aprotic lithium–air batteries, whereas this view is challenged by recent contrasting observations. This has provoked a range of discussions on the role of water and its impact on batteries. In this work, a distinct battery chemistry that prevails in water-contaminated aprotic lithium–oxygen batteries is revealed. Both lithium ions and protons are found to be involved in the oxygen reduction and evolution reactions, and lithium hydroperoxide and lithium hydroxide are identified as predominant discharge products. The crystallographic and spectroscopic characteristics of lithium hydroperoxide monohydrate are scrutinized both experimentally and theoretically. Intriguingly, the reaction of lithium hydroperoxide with triiodide exhibits a faster kinetics, which enables a considerably lower overpotential during the charging process. The battery chemistry unveiled in this mechanistic study could provide important insights into the understanding of nominally aprotic lithium–oxygen batteries and help to tackle the critical issues confronted. PMID:28165008

Binder-free NiFe2O4/C nanofibers as air cathodes for Li-O2 batteries

NASA Astrophysics Data System (ADS)

Zhang, Xin; Wang, Chengyi; Chen, Ya-Nan; Wang, Xin-Gai; Xie, Zhaojun; Zhou, Zhen

2018-02-01

Rechargeable Li-O2 batteries have aroused much attention for their high energy density. However, the poor rechargeability and low efficiency hinder their practical applications. To solve these issues, free-standing carbon films combined with high-activity NiFe2O4 catalysts are prepared by electrospinning method, and directly used as air cathodes for Li-O2 batteries. The obtained films have 3D networks formed by stacking and interlacing massive nanofibers with uniformly dispersed NiFe2O4 nanoparticles on them. The Li-O2 batteries with such binder-free air cathodes show low charging overpotential even comparable to precious metal cathodes, and can sustain excellent discharge/charge cyclic stability. The unique structure and binder-free superiority greatly facilitates the Li+ and O2 diffusion, accelerates the decomposition of Li2O2, and avoid the disturbance of polymer binders.

A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

NASA Astrophysics Data System (ADS)

Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I.; Tiwary, Chandrasekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N.; Vajtai, Robert; Yu, Aaron Z.; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J. A.; Ajayan, Pulickel M.

2016-12-01

Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts.

An investigation of energy balances in palladium cathode electrolysis experiments

NASA Astrophysics Data System (ADS)

Longhurst, G. R.; Dolan, T. J.; Henriksen, G. L.

1990-09-01

A series of experiments was performed at the Idaho National Engineering Laboratory (INEL) to investigate mechanisms that may contribute to energy flows in electrolysis cells like those of Fleischmann and Pons. Ordinary water (H2O), heavy water (D2O), and a mixture of the two were used in the INEL experiments. Cathodes used include a 51-μm Pd foil and 1-mm diameter extruded wire Pd rods in straight and coiled configurations. Energy balances in these experiments revealed no significant net gain or net loss of energy. Cell overpotential curves were fit well with a Tafel equation, with parameters dependent on electrode configuration, electrolyte composition, and temperature. Water evaporation and interactions of hydrogen isotopes with the Pd cathode were evaluated and found not to be significant to energy balances. No ionizing radiation, tritium production, or other evidence of fusion reactions was observed in the INEL experiments.

Computational analysis of species transport and electrochemical characteristics of a MOLB-type SOFC

NASA Astrophysics Data System (ADS)

Hwang, J. J.; Chen, C. K.; Lai, D. Y.

A multi-physics model coupling electrochemical kinetics with fluid dynamics has been developed to simulate the transport phenomena in mono-block-layer built (MOLB) solid oxide fuel cells (SOFC). A typical MOLB module is composed of trapezoidal flow channels, corrugated positive electrode-electrolyte-negative electrode (PEN) plates, and planar inter-connecters. The control volume-based finite difference method is employed for calculation, which is based on the conservation of mass, momentum, energy, species, and electric charge. In the porous electrodes, the flow momentum is governed by a Darcy model with constant porosity and permeability. The diffusion of reactants follows the Bruggman model. The chemistry within the plates is described via surface reactions with a fixed surface-to-volume ratio, tortuosity and average pore size. Species transports as well as the local variations of electrochemical characteristics, such as overpotential and current density distributions in the electrodes of an MOLB SOFC, are discussed in detail.

Development of a Novel Electrochemical Sensor for Determination of Matrine in Sophora flavescens.

PubMed

Zhang, Junping; Wang, Yanchun; Zheng, Wei

2017-04-01

A simple and sensitive electrochemical sensor fabricated with graphene nanosheets (GNs) and a hydroxyapatite (HA) nanocomposite-modified glassy carbon electrode (GCE) was developed for the determination of matrine (MT). The as-prepared electrode (GNs/HA/GCE) was verified to outperform bare a GCE and GNs-modified electrode with increased oxidation peak currents and the decreased over-potential in the redox process of MT, indicating the great enhancement of electrocatalytic activity toward the oxidation of MT by the composite of GNs and HA. Under the optimized conditions, the oxidation peak currents were related linearly with the concentration of MT, ranging from 2 μM to 3 mM, and the detection limit (S/N = 3) was 1.2 μM. In addition, the proposed electrochemical sensor can be successfully applied in the quantitative determination of MT in Sophora flavescens extract.

Driving the Oxygen Evolution Reaction by Nonlinear Cooperativity in Bimetallic Coordination Catalysts.

PubMed

Wurster, Benjamin; Grumelli, Doris; Hötger, Diana; Gutzler, Rico; Kern, Klaus

2016-03-23

Developing efficient catalysts for electrolysis, in particular for the oxygen evolution in the anodic half cell reaction, is an important challenge in energy conversion technologies. By taking inspiration from the catalytic properties of single-atom catalysts and metallo-proteins, we exploit the potential of metal-organic networks as electrocatalysts in the oxygen evolution reaction (OER). A dramatic enhancement of the catalytic activity toward the production of oxygen by nearly 2 orders of magnitude is demonstrated for novel heterobimetallic organic catalysts compared to metallo-porphyrins. Using a supramolecular approach we deliberately place single iron and cobalt atoms in either of two different coordination environments and observe a highly nonlinear increase in the catalytic activity depending on the coordination spheres of Fe and Co. Catalysis sets in at about 300 mV overpotential with high turnover frequencies that outperform other metal-organic catalysts like the prototypical hangman porphyrins.

A molecular approach to self-supported cobalt-substituted ZnO materials as remarkably stable electrocatalysts for water oxidation.

PubMed

Pfrommer, Johannes; Lublow, Michael; Azarpira, Anahita; Göbel, Caren; Lücke, Marcel; Steigert, Alexander; Pogrzeba, Martin; Menezes, Prashanth W; Fischer, Anna; Schedel-Niedrig, Thomas; Driess, Matthias

2014-05-12

In regard to earth-abundant cobalt water oxidation catalysts, very recent findings show the reorganization of the materials to amorphous active phases under catalytic conditions. To further understand this concept, a unique cobalt-substituted crystalline zinc oxide (Co:ZnO) precatalyst has been synthesized by low-temperature solvolysis of molecular heterobimetallic Co(4-x)Zn(x) O4 (x = 1-3) precursors in benzylamine. Its electrophoretic deposition onto fluorinated tin oxide electrodes leads after oxidative conditioning to an amorphous self-supported water-oxidation electrocatalyst, which was observed by HR-TEM on FIB lamellas of the EPD layers. The Co-rich hydroxide-oxidic electrocatalyst performs at very low overpotentials (512 mV at pH 7; 330 mV at pH 12), while chronoamperometry shows a stable catalytic current over several hours. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesoporous Iron Sulfide for Highly Efficient Electrocatalytic Hydrogen Evolution

DOE PAGES

Miao, Ran; Dutta, Biswanath; Sahoo, Sanjubala; ...

2017-09-05

Here, we report a facile synthetic protocol to pre-pare mesoporous FeS 2 without the aid of hard template as an electrocatalyst for the hydrogen evolution reaction (HER). The mesoporous FeS 2 materials with high surface area were successfully prepared by a sol-gel method follow-ing a sulfurization treatment in an H 2S atmosphere. A re-markable HER catalytic performance was achieved with a low overpotential of 96 mV at a current density of 10 mA·cm 2 and a Tafel slope of 78 mV per decade under alka-line conditions (pH 13). These theoretical calculations indicate that the excellent catalytic activity of mesoporous FeSmore » 2 is attributed to the exposed (210) facets. The mesoporous FeS 2 material might be a promising alternative to the Pt-based electrocatalysts for water splitting.« less

Evaluation of homogeneous electrocatalysts by cyclic voltammetry.

PubMed

Rountree, Eric S; McCarthy, Brian D; Eisenhart, Thomas T; Dempsey, Jillian L

2014-10-06

The pursuit of solar fuels has motivated extensive research on molecular electrocatalysts capable of evolving hydrogen from protic solutions, reducing CO2, and oxidizing water. Determining accurate figures of merit for these catalysts requires the careful and appropriate application of electroanalytical techniques. This Viewpoint first briefly presents the fundamentals of cyclic voltammetry and highlights practical experimental considerations before focusing on the application of cyclic voltammetry for the characterization of electrocatalysts. Key metrics for comparing catalysts, including the overpotential (η), potential for catalysis (E(cat)), observed rate constant (k(obs)), and potential-dependent turnover frequency, are discussed. The cyclic voltammetric responses for a general electrocatalytic one-electron reduction of a substrate are presented along with methods to extract figures of merit from these data. The extension of this analysis to more complex electrocatalytic schemes, such as those responsible for H2 evolution and CO2 reduction, is then discussed.

An engineered polypeptide around nano-sized manganese-calcium oxide: copying plants for water oxidation.

PubMed

Najafpour, Mohammad Mahdi; Ghobadi, Mohadeseh Zarei; Sarvi, Bahram; Haghighi, Behzad

2015-09-14

Synthesis of new efficient catalysts inspired by Nature is a key goal in the production of clean fuel. Different compounds based on manganese oxide have been investigated in order to find their water-oxidation activity. Herein, we introduce a novel engineered polypeptide containing tyrosine around nano-sized manganese-calcium oxide, which was shown to be a highly active catalyst toward water oxidation at low overpotential (240 mV), with high turnover frequency of 1.5 × 10(-2) s(-1) at pH = 6.3 in the Mn(III)/Mn(IV) oxidation range. The compound is a novel structural and efficient functional model for the water-oxidizing complex in Photosystem II. A new proposed clever strategy used by Nature in water oxidation is also discussed. The new model of the water-oxidizing complex opens a new perspective for synthesis of efficient water-oxidation catalysts.

Theoretical Insights into a CO Dimerization Mechanism in CO2 Electroreduction.

PubMed

Montoya, Joseph H; Shi, Chuan; Chan, Karen; Nørskov, Jens K

2015-06-04

In this work, we present DFT simulations that demonstrate the ability of Cu to catalyze CO dimerization in CO2 and CO electroreduction. We describe a previously unreported CO dimer configuration that is uniquely stabilized by a charged water layer on both Cu(111) and Cu(100). Without this charged water layer at the metal surface, the formation of the CO dimer is prohibitively endergonic. Our calculations also demonstrate that dimerization should have a lower activation barrier on Cu(100) than Cu(111), which, along with a more exergonic adsorption energy and a corresponding higher coverage of *CO, is consistent with experimental observations that Cu(100) has a high activity for C-C coupling at low overpotentials. We also demonstrate that this effect is present with cations other than H(+), a finding that is consistent with the experimentally observed pH independence of C2 formation on Cu.

Influence of dissolved hydrogen on aluminum-lithium alloy fracture behavior

NASA Technical Reports Server (NTRS)

Rivet, F. C.; Swanson, R. E.

1989-01-01

The objective of this work is to study the effects of dissolved hydrogen on the mechanical properties of 2090 and 2219 alloys. Prior to mechanical testing, potentiostatic and potentiodynamic tests were performed using NaCl/HCl solutions varying in pH from 1.5 to 7.5 (3.5 pct NaCl in deionized water). After analysis of the potentiodynamic curve for each solution, several potentiostatic experiments were conducted for various times (from 10 minutes to several hours) with a cathodic overpotential of 300 mV. These experiments were performed to select charging conditions. It is shown that the fracture of L-S and T-S orientations proceeds via slipping of layers in the S-T direction. The T-S and L-S orientations fractured with substantially higher propagation energy that the L-T and T-L orientations, due in large part to the extensive delamination propagation of the fracture.

Ultrafine Co Nanoparticles Encapsulated in Carbon-Nanotubes-Grafted Graphene Sheets as Advanced Electrocatalysts for the Hydrogen Evolution Reaction.

PubMed

Chen, Ziliang; Wu, Renbing; Liu, Yang; Ha, Yuan; Guo, Yanhui; Sun, Dalin; Liu, Miao; Fang, Fang

2018-06-10

The rational design of an efficient and inexpensive electrocatalyst based on earth-abundant 3d transition metals (TMs) for the hydrogen evolution reaction still remains a significant challenge in the renewable energy area. Herein, a novel and effective approach is developed for synthesizing ultrafine Co nanoparticles encapsulated in nitrogen-doped carbon nanotubes (N-CNTs) grafted onto both sides of reduced graphene oxide (rGO) (Co@N-CNTs@rGO) by direct annealing of GO-wrapped core-shell bimetallic zeolite imidazolate frameworks. Benefiting from the uniform distribution of Co nanoparticles, the in-situ-formed highly graphitic N-CNTs@rGO, the large surface area, and the abundant porosity, the as-fabricated Co@N-CNTs@rGO composites exhibit excellent electrocatalytic hydrogen evolution reaction (HER) activity. As demonstrated in electrochemical measurements, the composites can achieve 10 mA cm -2 at low overpotential with only 108 and 87 mV in 1 m KOH and 0.5 m H 2 SO 4 , respectively, much better than most of the reported Co-based electrocatalysts over a wide pH range. More importantly, the synthetic strategy is versatile and can be extended to prepare other binary or even ternary TMs@N-CNTs@rGO (e.g., Co-Fe@N-CNTs@rGO and Co-Ni-Cu@N-CNTs@rGO). The strategy developed here may open a new avenue toward the development of nonprecious high-performance HER catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Sensitive Electrochemical Biosensor for Evaluation of Oxidative Stress Based on the Nanointerface of Graphene Nanocomposites Blended with Gold, Fe3O4, and Platinum Nanoparticles.

PubMed

Wang, Le; Zhang, Yuanyuan; Cheng, Chuansheng; Liu, Xiaoli; Jiang, Hui; Wang, Xuemei

2015-08-26

High levels of H2O2 pertain to high oxidative stress and are associated with cancer, autoimmune, and neurodegenerative disease, and other related diseases. In this study, a sensitive H2O2 biosensor for evaluation of oxidative stress was fabricated on the basis of the reduced graphene oxide (RGO) nanocomposites decorated with Au, Fe3O4, and Pt nanoparticles (RGO/AuFe3O4/Pt) modified glassy carbon electrode (GCE) and used to detect the released H2O2 from cancer cells and assess the oxidative stress elicited from H2O2 in living cells. Electrochemical behavior of RGO/AuFe3O4/Pt nanocomposites exhibits excellent catalytic activity toward the relevant reduction with high selection and sensitivity, low overpotential of 0 V, low detection limit of ∼0.1 μM, large linear range from 0.5 μM to 11.5 mM, and outstanding reproducibility. The as-prepared biosensor was applied in the measurement of efflux of H2O2 from living cells including healthy normal cells and tumor cells under the external stimulation. The results display that this new nanocomposites-based biosensor is a promising candidate of nonenzymatic H2O2 sensor which has the possibility of application in clinical diagnostics to assess oxidative stress of different kinds of living cells.

A facile method to synthesize boron-doped Ni/Fe alloy nano-chains as electrocatalyst for water oxidation

NASA Astrophysics Data System (ADS)

Yang, Yisu; Zhuang, Linzhou; Lin, Rijia; Li, Mengran; Xu, Xiaoyong; Rufford, Thomas E.; Zhu, Zhonghua

2017-05-01

We report a novel magnetic field assisted chemical reduction method for the synthesis of boron-doped Ni/Fe nano-chains as promising catalysts for the oxygen evolution reaction (OER). The boron-doped Ni/Fe nano-chains were synthesised in a one step process at room temperature using NaBH4 as a reducing agent. The addition of boron reduced the magnetic moment of the intermediate synthesis products and produced nano-chains with a high specific surface area of 73.4 m2 g-1. The boron-doped Ni/Fe nano-chains exhibited catalytic performance superior to state-of-the-art Ba0.5Sr0.5Co0.8Fe0.2O3-δ perovskite and RuO2 noble metal oxide catalysts. The mass normalized activity of the boron-doped Ni/Fe nano-chains measured at an overpotential of 0.35 V was 64.0 A g-1, with a Tafel slope of only 40 mV dec-1. The excellent performance of the boron-doped Ni/Fe nano-chains can be attributed to the uniform elemental distribution and highly amorphous structure of the B-doped nano-chains. These results provide new insights into the effect of doping transition-metal based OER catalysts with non-metallic elements. The study demonstrates a facile approach to prepare transition metal nano-chains using magnetic field assisted chemical reduction method as cheap and highly active catalysts for electrochemical water oxidation.

Microbial Challenge Testing of Single Liquid Cathode Feed Water Electrolysis Cells for the International Space Station (ISS) Oxygen Generator Assembly (OGA)

NASA Technical Reports Server (NTRS)

Roy, Robert J.; Wilson, Mark E.; Diderich, Greg S.; Steele, John W.

2011-01-01

The International Space Station (ISS) Oxygen Generator Assembly (OGA) operational performance may be adversely impacted by microbiological growth and biofilm formation over the electrolysis cell membranes. Biofilms could hinder the transport of water from the bulk fluid stream to the membranes and increase the cell concentration overpotential resulting in higher cell voltages and a shorter cell life. A microbial challenge test was performed on duplicate single liquid-cathode feed water electrolysis cells to evaluate operational performance with increasing levels of a mixture of five bacteria isolated from ISS and Space Shuttle potable water systems. Baseline performance of the single water electrolysis cells was determined for approximately one month with deionized water. Monthly performance was also determined following each inoculation of the feed tank with 100, 1000, 10,000 and 100,000 cells/ml of the mixed suspension of test bacteria. Water samples from the feed tank and recirculating water loops for each cell were periodically analyzed for enumeration and speciation of bacteria and total organic carbon. While initially a concern, this test program has demonstrated that the performance of the electrolysis cell is not adversely impacted by feed water containing the five species of bacteria tested at a concentration measured as high as 1,000,000 colony forming units (CFU)/ml. This paper presents the methodologies used in the conduct of this test program along with the performance test results at each level of bacteria concentration.

Determination of O₂ Mass Transport at the Pt | PFSA Ionomer Interface under Reduced Relative Humidity.

PubMed

Novitski, David; Holdcroft, Steven

2015-12-16

Oxygen mass transport resistance through the ionomer component in the cathode catalyst layer is considered to contribute overpotential losses in polymer electrolyte membrane fuel cells. Whereas it is known that water uptake, water transport, and proton conductivity are reduced upon reducing relative humidity, the effect on oxygen mass transport remains unknown. We report a two-electrode approach to determine mass transport coefficients for the oxygen reduction reaction in air at the Pt/perfluorosulfonic acid ionomer membrane interface between 90 and 30% RH at 70 °C using a Pt microdisk in a solid state electrochemical cell. Potential-step chronoamperometry was performed at specific mass-transport limiting potentials to allow for the elucidation of the oxygen diffusion coefficient (D(bO2)) and oxygen concentration (c(bO2)). In our efforts, novel approaches in data acquisition, as well as analysis, were examined because of the dynamic nature of the membrane under lowered hydration conditions. Linear regression analysis reveals a decrease in oxygen permeability (D(bO2c(bO2)) by a factor of 1.7 and 3.4 from 90 to 30% RH for Nafion 211 membrane and membranes cast from Nafion DE2020 ionomer solutions, respectively. Additionally, nonlinear curve fitting by way of the Shoup-Szabo equation is employed to analyze the entire current transient during potential step controlled ORR. We also report on the presence of an RH dependence of our previously reported time-dependency measurements for O2 mass transport coefficients.

Carbon Nanotube-based microelectrodes for enhanced detection of neurotransmitters

NASA Astrophysics Data System (ADS)

Jacobs, Christopher B.

Fast-scan cyclic voltammetry (FSCV) is one of the common techniques used for rapid measurement of neurotransmitters in vivo. Carbon-fiber microelectrodes (CFMEs) are typically used for neurotransmitter detection because of sub-second measurement capabilities, ability to measure changes in neurotransmitter concentration during neurotransmission, and the small size electrode diameter, which limits the amount of damage caused to tissue. Cylinder CFMEs, typically 50 -- 100 microm long, are commonly used for in vivo experiments because the electrode sensitivity is directly related to the electrode surface area. However the length of the electrode can limit the spatial resolution of neurotransmitter detection, which can restrict experiments in Drosophila and other small model systems. In addition, the electrode sensitivity toward dopamine and serotonin detection drops significantly for measurements at rates faster than 10 Hz, limiting the temporal resolution of CFMEs. While the use of FSCV at carbon-fiber microelectrodes has led to substantial strides in our understanding of neurotransmission, techniques that expand the capabilities of CFMEs are crucial to fully maximize the potential uses of FSCV. This dissertation introduces new methods to integrate carbon nanotubes (CNT) into microelectrodes and discusses the electrochemical enhancements of these CNT-microelectrodes. The electrodes are specifically designed with simple fabrication procedures so that highly specialized equipment is not necessary, and they utilize commercially available materials so that the electrodes could be easily integrated into existing systems. The electrochemical properties of CNT modified CFMEs are characterized using FSCV and the effect of CNT functionalization on these properties is explored in Chapter 2. For example, CFME modification using carboxylic acid functionalized CNTs yield about a 6-fold increase in dopamine oxidation current, but modification with octadecylamine CNTs results in a negligible change to the signal. Chapter 3 is devoted to the development and characterization of new CNT-Yarn Microelectrodes (CNTYME) which display a beneficial enhancement in sensitivity and reduction in both electron transfer kinetics and overpotential. Chapter 4 introduces the high-speed dopamine detection capabilities of CNTYMEs, almost two orders of magnitude faster than at CFMEs without any compromise in electrochemical sensitivity, and discusses how adsorption and desorption relate to this phenomenon.

Multiphysics Modelling of Sodium Sulfur Battery

NASA Astrophysics Data System (ADS)

Mason, Jerry Hunter

Due to global climate change and the desire to decrease greenhouse gas emissions, large scale energy storage has become a critical issue. Renewable energy sources such as wind and solar will not be a viable energy source unless the storage problem is solved. One of the practical and cost effective solutions for this problem is sodium sulfur batteries. These batteries are comprised of liquid electrode materials suspended in porous media and operate at relatively high temperatures (>300°C). The sodium anode and the sulfur/sodium-polysulfide cathode are separated by a solid electrolyte made of beta-alumina or NASICON material. Due to the use of porous materials in the electrodes, capillary pressure and the combination of capillary action and gravity become important. Capillary pressure has a strong dependence on the wetting phase (liquid electrode material) saturation; therefore sharp concentration gradients can occur between the inert gas and the electrode liquid, especially within the cathode. These concentration gradients can have direct impacts on the electrodynamics of the battery as they may produce areas of high electrical potential variation, which can decrease efficiency and even cause failures. Then, thermal management also becomes vital since the electrochemistry and material properties are sensitive to temperature gradients. To investigate these phenomena in detail and to attempt to improve upon battery design a multi-dimensional, multi-phase code has been developed and validated in this study. Then a porous media flow model is implemented. Transport equations for charge, mass and heat are solved in a time marching fashion using finite volume method. Material properties are calculated and updated as a function of time. The porous media model is coupled with the continuity equation and a separate diffusion equation for the liquid sodium in the melt. The total mass transport model is coupled with charge transport via Faraday's law. Results show that overpotential is significantly higher in the porous region of the cathode as was predicted by models in the literature. Overpotential is also high on the electrolyte surface and wall. Alternative electrode configurations with high resistive layers recommended by previous researchers also produce areas of high potential gradient. New electrode designs including conductivity gradients and porous media property variations are simulated and compared to previous designs and then recommendations are made for optimum cell operating conditions.

Bioinspired design of redox-active ligands for multielectron catalysis: Effects of positioning pyrazine reservoirs on cobalt for electro- and photocatalytic generation of hydrogen from water

DOE PAGES

Jurss, Jonah W.; Khnayzer, Rony S.; Panetier, Julien A.; ...

2015-06-09

Mononuclear metalloenzymes in nature can function in cooperation with precisely positioned redox-active organic cofactors in order to carry out multielectron catalysis. Inspired by the finely tuned redox management of these bioinorganic systems, we present the design, synthesis, and experimental and theoretical characterization of a homologous series of cobalt complexes bearing redox-active pyrazines. These donor moieties are locked into key positions within a pentadentate ligand scaffold in order to evaluate the effects of positioning redox non-innocent ligands on hydrogen evolution catalysis. Both metal- and ligand-centered redox features are observed in organic as well as aqueous solutions over a range of pHmore » values, and comparison with analogs bearing redox-inactive zinc(II) allows for assignments of ligand-based redox events. Varying the geometric placement of redox non-innocent pyrazine donors on isostructural pentadentate ligand platforms results in marked effects on observed cobalt-catalyzed proton reduction activity. Electrocatalytic hydrogen evolution from weak acids in acetonitrile solution, under diffusion-limited conditions, reveals that the pyrazine donor of axial isomer 1-Co behaves as an unproductive electron sink, resulting in high overpotentials for proton reduction, whereas the equatorial pyrazine isomer complex 2-Co is significantly more active for hydrogen generation at lower voltages. Addition of a second equatorial pyrazine in complex 3-Co further minimizes overpotentials required for catalysis. The equatorial derivative 2-Co is also superior to its axial 1-Co congener for electrocatalytic and visible-light photocatalytic hydrogen generation in biologically relevant, neutral pH aqueous media. Density functional theory calculations (B3LYP-D2) indicate that the first reduction of catalyst isomers 1-Co, 2-Co, and 3-Co is largely metal-centered while the second reduction occurs at pyrazine. Taken together, the data establish that proper positioning of non-innocent pyrazine ligands on a single cobalt center is indeed critical for promoting efficient hydrogen catalysis in aqueous media, akin to optimally positioned redox-active cofactors in metalloenzymes. In a broader sense, these findings highlight the significance of electronic structure considerations in the design of effective electron–hole reservoirs for multielectron transformations.« less

Methods and Strategies for the Ab Initio Design of Novel Manganese Oxide- Based Water Splitting Photocatalyst Materials

NASA Astrophysics Data System (ADS)

Kanan, Dalal K.

Photoelectrochemical cells (PECs) use sunlight to drive endoergic reactions such as carbon dioxide reduction to fuels or water-splitting for renewable hydrogen production. However, materials that combine both the efficiency and low cost needed to make solar-powered catalysis a practical reality have yet to be discovered. This thesis presents methods and new design strategies for developing novel, efficient, robust, and inexpensive photocatalysts based on transition metal oxides (TMOs). Quantum mechanics methodologies are developed and tested for their ability to predict the properties of known materials and then used to predict how altering the composition by alloying and doping with abundant elements affects optical, electronic, transport, and catalytic properties. The first material considered for photocatalysis is MnO, the bio-inspired solid state analogue of the photosystem II active site. GW theory with input from hybrid DFT and ab initio DFT+U capably predicts the photoemission/inverse photoemission (PE/IPE) band gap and dielectric properties. An ab initio value of U-J = 3.5 eV for Mn2+ was determined using unrestricted Hartree-Fock theory on cluster-size-converged electrostatically embedded clusters. The lowest-lying excitations in MnO, studied using ECW theory, are found to be single Mn d → d ligand field excitations (~2.5 eV, ~108 s lifetime), followed by double d → d excitations (~5.2 eV, ~106 s lifetime), Mn 3d-4s excitations (~6.3 eV, ~10-3 s lifetime), and higher-lying O 2p → Mn 3d ligand-to-metal charge-transfer (LMCT) excitations (~10.1 eV, ~10-4 s lifetime). The longer-lived transitions should exhibit better electron-hole pair separation and enhance photoconductivity depending on ease of carrier transport. While MnO possesses suitable band edge energies, its band gap is too large for efficient sunlight absorption. We predict alloying MnO with ZnO in varying amounts reduces the PE/IPE band gap (to 2.6 eV for the 1:1 alloy) while preserving potential redox reactivity. Optical excitation studies show alloying lowers the LMCT transition to ~8.3 eV leaving all other absorption properties relatively unchanged. We find near degeneracies among spin-allowed and spin-forbidden LMCT states that could facilitate intersystem crossing (ISC) resulting in longer lifetimes. We suggest seeking other materials that exhibit similar LMCT excitations but that are visible-light activated as a design strategy for further enhancing photon conversion efficiencies. Additionally, several dopants (Al, Ga, In, Sc, Y, Ti, Sb, Gd, F (n-type dopants) and Li (a p-type dopant)) were assessed for their ability to enhance conductivity in MnO:ZnO. We find Ga, Sc, Ti, F, and Sb dopants create deep traps whereas In forms shallower traps that merit further investigation. In contrast, Y, Al, Gd, and Li dopants should increase the carrier concentration while maintaining favorable electron and hole transport pathways. The adsorption and oxidation of water on MnO:ZnO(001) surface was studied with ab initio DFT+U calculations. The computed phase diagram for the water/MnO:ZnO(001) interface reveals the surface is quite hydrophilic with the half-dissociated 1 ML (2 ML) structure being most stable under water-poor (water-rich) conditions. For the gas phase water oxidation reaction, we compute a thermodynamic overpotential of 0.82 V without yet modeling reaction kinetics or solvation. The overpotential mainly results from the *OOH intermediate being too weakly bound to the surface because of a loss of resonance stabilization in the adsorbate. We suggest judicious doping as a way to stabilize *OOH and potentially reduce the overpotential to just 0.05 V (for 0.5 ML reaction coverage). (Abstract shortened by UMI.)

Prevention of redox shuttle using electropolymerized polypyrrole film in a lithium-oxygen battery

NASA Astrophysics Data System (ADS)

Togasaki, Norihiro; Shibamura, Ryuji; Naruse, Takuya; Momma, Toshiyuki; Osaka, Tetsuya

2018-04-01

Among the recent advancements in lithium-oxygen (Li-O2) chemistries, redox mediators (RMs) have been revealed to play a significant role in decreasing overpotential on charging and in improving cycling performance. However, an intrinsic problem is redox shuttle of RMs, which leads to degraded RM utilization and induces the accumulation of discharge products on the cathode surface; this remains a significant issue in the current battery cell configuration (Li anode/separator/cathode). To address this detrimental problem, herein we propose a novel Li-O2 cell incorporating a freestanding electropolymerized polypyrrole (PPy) film for the restriction of the redox-shuttle phenomenon of lithium iodide (Li anode/separator/PPy film/cathode). In this study, a PPy film, which is prepared through oxidative electropolymerization using an ionic liquid of 1-methyl-1-butylpyrrolidinium mixed with pyrrole and lithium bis(trifluoromethanesulfonyl)imide, is introduced between the cathode and the separator. From the charge-discharge voltage profile, it is confirmed that the PPy film suppresses the diffusion of the oxidized I3- to the Li anode, while allowing Li ion transport. Secondary scanning electron microscope measurements confirm that the chemical reactions between I3- and Li2O2 are facilitated by the presence of the PPy film because I3- remains near the cathode surface during the charging process. As a result, the cycling performance in the Li-O2 cells with PPy film exhibits a cycling life four times as long as that of the Li-O2 cells without PPy film.

Nanofluidic structures for coupled sensing and remediation of toxins

NASA Astrophysics Data System (ADS)

Shaw, K.; Contento, N. M.; Xu, Wei; Bohn, P. W.

2014-05-01

One foundational motivation for chemical sensing is that knowledge of the presence and level of a chemical agent informs decisions about treatment of the agent, for example by sequestration, separation or chemical conversion to a less harmful substance. Commonly the sensing and treatment steps are separate. However, the disjoint detection/treatment approach is neither optimal, nor required. Thus, we are investigating how nanostructured architectures can be constructed so that molecular transport (analyte/reagent delivery), chemical sensing (optical or electrochemical) and subsequent treatment can all be coupled in the same physical space during the same translocation event. Chemical sensors that are uniquely well-poised for integration into 3-D micro-/nanofluidic architectures include those based on plasmonics and impedance. Following detection, treatment can be substantially enhanced if mass transport limitations can be overcome. In this context, in situ generation of reactive species within confined geometries, such as nanopores or nanochannels, is of significant interest, because of its potential utility in overcoming mass transport limitations in chemical reactivity. Solvent electrolysis in electrochemically coupled nanochannels supporting electrokinetic flow for the generation of reactive species, can produce arbitrarily tunable quantities of reagents, such as O2 or H2, in situ in close proximity to the site of a hydrogenation catalyst, for example. Semi-quantitative estimates of the local H2 concentration are obtained by comparing the spatiotemporal fluorescence behavior and current measurements with finite element simulations accounting for electrolysis and subsequent convection and diffusion within the confined geometry. H2 saturation can easily be achieved at modest overpotentials.

Simultaneous electrochemical detection of dopamine and uric acid over ceria supported three dimensional gold nanoclusters

NASA Astrophysics Data System (ADS)

Palanisamy, Sivakumar

2014-12-01

CeO2 is well known for being an active material to support the growth of Au nanoclusters (Au NCs). In this work, three dimensional (3D) Au NCs were deposited on three different shaped CeO2 nanostructures such as nanoparticles (NPs), nanorod arrays (NRAs) and nanoflowers (NFs) modified Ti substrate for electrochemical simultaneous detection of dopamine (DA) and uric acid (UA). The electrodeposition of 3D Au NCs were carried out via cyclic voltammetric (CV) method at over-potential, while CeO2 nanostructures were deposited by galvanostatic constant current method under the optimized conditions. The morphology and elemental composition analysis of 3D Au NCs with CeO2 nanostructures were characterized by SEM, XRD, XPS and EDAX measurements. The electrocatalytic activity of 3D Au NCs on different CeO2 supports were thoroughly investigated by using voltammetric and amperometric techniques. According to the obtained results, CeO2 NPs supported 3D Au NCs (3D Au NCs@CeO2 NPs) displayed strong signal for DA as compared to that of CeO2 NRAs (3D Au NCs@CeO2 NRAs) and CeO2 NFs supported 3D Au NCs (3D Au NCs@CeO2 NFs). In addition, the 3D Au NCs@CeO2 NPs electrode resulted in more sensitive and simultaneous detection of DA in the presence of excess UA. Thus, the 3D Au NCs@CeO2 NPs electrode can practically be applied for the detection of DA using biological samples.

Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts

DOE PAGES

Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P.; ...

2015-07-30

CO electroreduction activity on oxide-derived Cu (OD-Cu) was found to correlate with metastable surface features that bind CO strongly. OD-Cu electrodes prepared by H 2 reduction of Cu 2O precursors reduce CO to acetate and ethanol with nearly 50% Faradaic efficiency at moderate overpotential. Temperature-programmed desorption of CO on OD-Cu revealed the presence of surface sites with strong CO binding that are distinct from the terraces and stepped sites found on polycrystalline Cu foil. After annealing at 350 °C, the surface-area corrected current density for CO reduction is 44-fold lower and the Faradaic efficiency is less than 5%. These changesmore » are accompanied by a reduction in the proportion of strong CO binding sites. Here, we propose that the active sites for CO reduction on OD-Cu surfaces are strong CO binding sites that are supported by grain boundaries. Uncovering these sites is a first step toward understanding the surface chemistry necessary for efficient CO electroreduction.« less

Efficient carbon dots/NiFe-layered double hydroxide/BiVO4 photoanodes for photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Lv, Xiaowei; Xiao, Xin; Cao, Minglei; Bu, Yi; Wang, Chuanqing; Wang, Mingkui; Shen, Yan

2018-05-01

Modification of semiconductor photoanodes with oxygen evolution catalyst (OEC) is an effective approach for improving photoelectrochemical (PEC) water splitting efficiency. In the configuration, how to increase the activity of OEC is crucial to further improve PEC performance. Herein, a ternary photoanode system was designed to enhance PEC efficiency of photoelectrodes through introducing carbon dots (CDs), NiFe-layered double hydroxide (NiFe-LDH) nanosheets on BiVO4 particles. Systematic research shows that NiFe-LDH serves as an OEC which accelerates oxygen evolution kinetics, while the introduction of CDs can further reduce charge transfer resistance and overpotential for oxygen evolution. Under the synergistic effect of NiFe-LDH and CDs, the photocurrent and incident photon to current conversion efficiency (IPCE) of the resulting CDs/NiFe-LDH/BiVO4 photoanode is improved significantly than those of the NiFe-LDH/BiVO4 electrode. Consequently, such a ternary heterostructure could be an alternative way to further enhance PEC water splitting performance.

Investigation on porous MnO microsphere anode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhong, Kaifu; Zhang, Bin; Luo, Shihai; Wen, Wen; Li, Hong; Huang, Xuejie; Chen, Liquan

MnO microspheres with and without carbon coating are prepared as anode materials for lithium ion batteries. The MnO microsphere material shows a reversible capacity of 800 mAh g -1 and an initial efficiency of 71%. It can deliver 600 mAh g -1 at a rate of 400 mA g -1. Results of Mn K-edge X-ray absorption near-edge structure (XANES) spectra and extended X-ray absorption fine structure (EXAFS) confirm further the conversion reaction mechanism, indicate that pristine MnO is reduced to Mn 0 after discharging to 0 V and part of reduced Mn 0 is not oxidized to Mn 2+ after charging to 3 V. This explains the origin of the initial irreversible capacity loss partially. The quasi open circuit voltage and the relationship between the current density and the overpotential are investigated. Both indicate that there is a significant voltage difference between the charging and discharging profiles even when the current density decreases to zero.

Subnanometer Molybdenum Sulfide on Carbon Nanotubes as a Highly Active and Stable Electrocatalyst for Hydrogen Evolution Reaction.

PubMed

Li, Ping; Yang, Zhi; Shen, Juanxia; Nie, Huagui; Cai, Qiran; Li, Luhua; Ge, Mengzhan; Gu, Cancan; Chen, Xi'an; Yang, Keqin; Zhang, Lijie; Chen, Ying; Huang, Shaoming

2016-02-10

Electrochemically splitting water for hydrogen evolution reaction (HER) has been viewed as a promising approach to produce renewable and clean hydrogen energy. However, searching for cheap and efficient HER electrocatalysts to replace the currently used Pt-based catalysts remains an urgent task. Herein, we develop a one-step carbon nanotube (CNT) assisted synthesis strategy with CNTs' strong adsorbability to mediate the growth of subnanometer-sized MoS(x) on CNTs. The subnanometer MoS(x)-CNT hybrids achieve a low overpotential of 106 mV at 10 mA cm(-2), a small Tafel slope of 37 mV per decade, and an unprecedentedly high turnover frequency value of 18.84 s(-1) at η = 200 mV among all reported non-Pt catalysts in acidic conditions. The superior performance of the hybrid catalysts benefits from the presence of a higher number of active sites and the abundant exposure of unsaturated S atoms rooted in the subnanometer structure, demonstrating a new class of subnanometer-scale catalysts.

A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

DOE PAGES

Liu, Wen; Hu, Enyuan; Jiang, Hong; ...

2016-02-19

Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superiormore » activity for hydrogen evolution, achieving current densities of 10 mA cm –2 and 100 mA cm –2 at overpotentials of 48 mV and 109 mV, respectively. Lastly, phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.« less

Surface Engineering of a Nickel Oxide-Nickel Hybrid Nanoarray as a Versatile Catalyst for Both Superior Water and Urea Oxidation.

PubMed

Yue, Zhihao; Zhu, Wenxin; Li, Yuanzhen; Wei, Ziyi; Hu, Na; Suo, Yourui; Wang, Jianlong

2018-04-16

Developing efficient and low-cost oxygen evolution reaction (OER) electrodes is a pressing but still challenging task for energy conversion technologies such as water electrolysis, regenerative fuel cells, and rechargeable metal-air batteries. Hence, this study reports that a nickel oxide-nickel hybrid nanoarray on nickel foam (NiO-Ni/NF) could act as a versatile anode for superior water and urea oxidation. Impressively, this anode could attain high current densities of 50 and 100 mA cm -2 at extremely low overpotentials of 292 and 323 mV for OER, respectively. Besides, this electrode also shows excellent activity for urea oxidation with the need for just 0.28 and 0.36 V (vs SCE) to attain 10 and 100 mA cm -2 in 1.0 M KOH with 0.33 M urea, respectively. The enhanced oxidation performance should be due to the synergistic effect of NiO and Ni, improved conductivity, and enlarged active surface area.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

PubMed

Zhang, Peili; Li, Lin; Nordlund, Dennis; Chen, Hong; Fan, Lizhou; Zhang, Biaobiao; Sheng, Xia; Daniel, Quentin; Sun, Licheng

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

Catalyst mixtures

DOEpatents

Masel, Richard I.; Rosen, Brian A.

2017-02-14

Catalysts that include at least one catalytically active element and one helper catalyst can be used to increase the rate or lower the overpotential of chemical reactions. The helper catalyst can simultaneously act as a director molecule, suppressing undesired reactions and thus increasing selectivity toward the desired reaction. These catalysts can be useful for a variety of chemical reactions including, in particular, the electrochemical conversion of CO.sub.2 or formic acid. The catalysts can also suppress H.sub.2 evolution, permitting electrochemical cell operation at potentials below RHE. Chemical processes and devices using the catalysts are also disclosed, including processes to produce CO, OH.sup.-, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, O.sub.2, H.sub.2, (COOH).sub.2, or (COO.sup.-).sub.2, and a specific device, namely, a CO.sub.2 sensor.

Role of strain and conductivity in oxygen electrocatalysis on LaCoO3 thin films

DOE PAGES

Stoerzinger, Kelsey; Choi, Woo Seok; Jeen, Hyoung Jeen; ...

2015-01-19

The slow kinetics of the oxygen reduction and evolution reactions (ORR, OER) hinder energy conversion and storage in alkaline fuel cells and electrolyzers employing abundant transition metal oxide catalysts. Systematic studies linking material properties to catalytic activity are lacking, in part due to the heterogeneous nature of powder-based electrodes. We demonstrate, for the first time, that epitaxial strain can tune the activity of oxygen electrocatalysis in alkaline solutions, focusing on the model chemistry of LaCoO 3, where moderate tensile strain can further induce changes in the electronic structure via spin state to increase activity. The resultant decrease in charge transfermore » resistance to the electrolyte reduces the overpotential in the ORR more notably than the OER and suggests a different dependence of the respective rate-limiting steps on electron transfer. This provides new insight into the reaction mechanism applicable to a range of perovskite chemistries, key to the rational design of highly active catalysts.« less

Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts.

PubMed

Feng, Jin-Xian; Tong, Si-Yao; Tong, Ye-Xiang; Li, Gao-Ren

2018-04-18

The search for high active, stable, and cost-efficient hydrogen evolution reaction (HER) electrocatalysts for water electrolysis has attracted great interest. The coordinated water molecules in the hydronium ions will obviously reduce the positive charge density of H + and hamper the ability of H + to receive electrons from the cathode, leading to large overpotential of HER on nonprecious metal catalysts. Here we realize Pt-like hydrogen evolution electrocatalysis on polyaniline (PANI) nanodots (NDs)-decorated CoP hybrid nanowires (HNWs) supported on carbon fibers (CFs) (PANI/CoP HNWs-CFs) as PANI can effectively capture H + from hydronium ions to form protonated amine groups that have higher positive charge density than those of hydronium ions and can be electro-reduced easily. The PANI/CoP HNWs-CFs as low-cost electrocatalysts show excellent catalytic performance toward HER in acidic solution, such as super high catalytic activity, small Tafel slope, and superior stability.

Electrochemically driven three-phase interlines into insulator compounds: electroreduction of solid SiO2 in molten CaCl2.

PubMed

Xiao, Wei; Jin, Xianbo; Deng, Yuan; Wang, Dihua; Hu, Xiaohong; Chen, George Z

2006-08-11

The electrochemical reduction of solid SiO2 (quartz) to Si is studied in molten CaCl2 at 1173 K. Experimental observations are compared and agree well with a novel penetration model in relation with electrochemistry at the dynamic conductor|insulator|electrolyte three-phase interlines. The findings show that the reduction of a cylindrical quartz pellet at certain potentials is mainly determined by the diffusion of the O(2-) ions and also the ohmic polarisation in the reduction-generated porous silicon layer. The reduction rate increases with the overpotential to a maximum after which the process is retarded, most likely due to precipitation of CaO in the reaction region (cathodic passivation). Data are reported on the reduction rate, current efficiency and energy consumption during the electroreduction of quartz under potentiostatic conditions. These theoretical and experimental findings form the basis for an in-depth discussion on the optimisation of the electroreduction method for the production of silicon.

Laser-Induced Graphene Formation on Wood.

PubMed

Ye, Ruquan; Chyan, Yieu; Zhang, Jibo; Li, Yilun; Han, Xiao; Kittrell, Carter; Tour, James M

2017-10-01

Wood as a renewable naturally occurring resource has been the focus of much research and commercial interests in applications ranging from building construction to chemicals production. Here, a facile approach is reported to transform wood into hierarchical porous graphene using CO 2 laser scribing. Studies reveal that the crosslinked lignocellulose structure inherent in wood with higher lignin content is more favorable for the generation of high-quality graphene than wood with lower lignin content. Because of its high electrical conductivity (≈10 Ω per square), graphene patterned on wood surfaces can be readily fabricated into various high-performance devices, such as hydrogen evolution and oxygen evolution electrodes for overall water splitting with high reaction rates at low overpotentials, and supercapacitors for energy storage with high capacitance. The versatility of this technique in formation of multifunctional wood hybrids can inspire both research and industrial interest in the development of wood-derived graphene materials and their nanodevices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Benchmarking nanoparticulate metal oxide electrocatalysts for the alkaline water oxidation reaction

DOE PAGES

Jung, Suho; McCrory, Charles C. L.; Ferrer, Ivonne M.; ...

2016-11-27

Nanoparticulate metal-oxide catalysts are among the most prevalent systems for alkaline water oxidation. However, comparisons of the electrochemical performance of these materials have been challenging due to the different methods of attachment, catalyst loadings, and electrochemical test conditions reported in the literature. Here in this paper, we have leveraged a conventional drop-casting method that allows for the successful adhesion of a wide range of nanoparticulate catalysts to glassy-carbon electrode surfaces. We have applied this adhesion method to prepare catalyst films from 16 crystalline metal-oxide nanoparticles with a constant loading of 0.8 mg cm -2, and evaluated the resulting nanoparticulate filmsmore » for the oxygen evolution reaction under conditions relevant to an integrated solar fuels device. In general, the activities of the adhered nanoparticulate films are similar to those of thin-film catalysts prepared by electrodeposition or sputtering, achieving 10 mA cm -2 current densities per geometric area at overpotentials of ~0.35–0.5 V.« less

Revealing the Origin of Activity in Nitrogen-Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide.

PubMed

Xu, Junyuan; Kan, Yuhe; Huang, Rui; Zhang, Bingsen; Wang, Bolun; Wu, Kuang-Hsu; Lin, Yangming; Sun, Xiaoyan; Li, Qingfeng; Centi, Gabriele; Su, Dangsheng

2016-05-23

Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2 ). The investigation explores the origin of the catalyst's activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90 % current efficiency for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO2 proceeds through an initial rate-determining transfer of one electron to CO2 , which leads to the formation of carbon dioxide radical anion (CO2 (.-) ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO2 reduction. The doped nitrogen atoms stabilize the radical anion, thereby lowering the initial reduction barrier and improving the intrinsic activity. The most efficient nitrogen chemical state for this reaction is quaternary nitrogen, followed by pyridinic and pyrrolic nitrogen. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The reaction mechanism with free energy barriers at constant potentials for the oxygen evolution reaction at the IrO 2 (110) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ping, Yuan; Nielsen, Robert J.; Goddard, William A.

How to efficiently oxidize H 2O to O 2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO 2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OERmore » at the IrO 2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. Furthermore, this allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.« less

Photoelectrochemical Performance of the Ag(III)-Based Oxygen-Evolving Catalyst.

PubMed

Sordello, Fabrizio; Ghibaudo, Manuel; Minero, Claudio

2017-07-19

We report the electrosynthesis of a water oxidation catalyst based on Ag oxides (AgCat). The deposited AgCat is composed of mixed valence crystalline Ag oxides with the presence of particle aggregates whose size is ∼1 μm. This catalyst, coupled with TiO 2 and hematite, and under photoelectrochemical conditions, substantially increases photocurrents in a wide range of applied potentials compared with bare and Co-Pi-modified photocatalysts. AgCat can sustain current densities comparable with other water oxidation catalysts. Dark bulk electrolysis demonstrated that AgCat is stable and can sustain high turnover number in operative conditions. Oxygen evolution from water occurs in mild conditions: pH = 2-13, room temperature and pressure, and moderate overpotentials (600 mV) compatible with the coupling with semiconducting oxides as sensitizers. Using hematite in sustained electrolysis O 2 production is significant, both in the dark and under irradiation, after an initial slow induction time in which modification of surface species occurs.

Operando Evidence for a Universal Oxygen Evolution Mechanism on Thermal and Electrochemical Iridium Oxides.

PubMed

Saveleva, Viktoriia A; Wang, Li; Teschner, Detre; Jones, Travis; Gago, Aldo S; Friedrich, K Andreas; Zafeiratos, Spyridon; Schlögl, Robert; Savinova, Elena R

2018-06-07

Progress in the development of proton exchange membrane (PEM) water electrolysis technology requires decreasing the anode overpotential, where the sluggish multistep oxygen evolution reaction (OER) occurs. This calls for an understanding of the nature of the active OER sites and reaction intermediates, which are still being debated. In this work, we apply synchrotron radiation-based near-ambient pressure X-ray photoelectron and absorption spectroscopies under operando conditions in order to unveil the nature of the reaction intermediates and shed light on the OER mechanism on electrocatalysts most widely used in PEM electrolyzers-electrochemical and thermal iridium oxides. Analysis of the O K-edge and Ir 4f spectra backed by density functional calculations reveals a universal oxygen anion red-ox mechanism regardless of the nature (electrochemical or thermal) of the iridium oxide. The formation of molecular oxygen is considered to occur through a chemical step from the electrophilic O I- species, which itself is formed in an electrochemical step.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harrington, Timothy D.; Babauta, Jerome T.; Davenport, Emily K.

We investigated ion transport limitations on 3D graphite felt electrodes by growing Geobacter sulfurreducens biofilms with advection to eliminate external mass transfer limitations. We characterized ion transport limitations by: (i) showing that serially increasing NaCl concentration up to 200mM increased current linearly up to a total of þ273% vs. 0mM NaCl under advective conditions; (ii) growing the biofilm with a starting concentration of 200mM NaCl, which led to a maximum current increase of 400% vs. current generation without NaCl, and (iii) showing that un-colonized surface area remained even after steadystate current was reached. After accounting for iR effects, we confirmedmore » that the excess surface area existed despite a non-zero overpotential. The fact that the biofilm was constrained from colonizing and producing further current under these conditions confirmed the biofilms under study here were ion transport-limited. Our work demonstrates that the use of high surface area electrodes may not increase current density when the system design allows ion transport limitations to become dominant.« less

Entropy production and energy dissipation in symmetric redox supercapacitors

NASA Astrophysics Data System (ADS)

Palma-Aramburu, N.; Santamaría-Holek, I.

2017-08-01

In this work we propose a theoretical model that accounts for the main features of the loading-unloading process of a symmetric redox MnO2-based supercapacitor dominated by fast electrochemical reactions at the electrodes. The model is formulated on the basis of nonequilibrium thermodynamics from which we are able to deduce generalized expressions for the electrochemical affinity, the load-voltage and the current-voltage equations that constitute generalizations of the current-overpotential and Butler-Volmer equations, and that are used to describe experimental voltagram data with good agreement. These equations allowed us to derive the behavior of the energy dissipated per cycle showing that it has a nonmonotonic behavior and that in the operation regime it follows a power-law behavior as a function of the frequency. The existence of a maximum for the energy dissipated as a function of the frequency suggests the that the corresponding optimal operation frequency should be similar in value to ωmax.

Electrodeposition of Si from an Ionic Liquid Bath at Room Temperature in the Presence of Water.

PubMed

Shah, Nisarg K; Pati, Ranjan Kumar; Ray, Abhijit; Mukhopadhyay, Indrajit

2017-02-21

The electrochemical deposition of Si has been carried out in an ionic liquid medium in the presence of water in a limited dry nitrogen environment on highly oriented pyrolytic graphite (HOPG) at room temperature. It has been found that the presence of water in ionic liquids does not affect the available effective potential window to a large extent. Silicon has been successfully deposited electrochemically in the overpotential regime in two different ionic liquids, namely, BMImTf 2 N and BMImPF 6 , in the presence of water. Although a Si thin film has been obtained from BMImTf 2 N; only distinguished Si crystals protected in ionic liquid droplets have been observed from BMImPF 6 . The most important observation of the present investigation is that the Si precursor, SiCl 4 , instead of undergoing hydrolysis, even in the presence of water, coexisted with ionic liquids, and elemental Si has been successfully electrodeposited.

In situ glass antifouling using Pt nanoparticle coating for periodic electrolysis of seawater

NASA Astrophysics Data System (ADS)

Xue, Yuxi; Zhao, Jin; Qiu, Ri; Zheng, Jiyong; Lin, Cunguo; Ma, Bojiang; Wang, Peng

2015-12-01

In situ electrochemical chlorination is a promising way to prohibit the biofouling on glass used for optical devices in seawater. To make this approach practical, a conductive glass should have low overpotential to generate Cl2, so that the electrical energy consumption, a critical issue for field application, will be low. Moreover, a long sustainability should also be taken into consideration from the application perspective. Following these criteria, we propose Pt/ITO surface to electrochemically generate Cl2, which immunizes biofouling for glass substrate. In this report, firstly, Pt nanoparticle/ITO is prepared via an electrodeposition approach. Secondly, electrocatalysis capability of Pt/ITO is elucidated, which shows the catalysis for Cl2 generation from NaCl solution and seawater has been sparked with Pt on the surface. Also, Pt/ITO is more sustainable and efficient than the bare ITO in natural seawater. Thirdly, the antifouling property is evaluated taking diatom as the target organism. Electrochemical chlorination on Pt/ITO can efficiently prevent the glass from fouling.

Influence of lead ions on the macromorphology of electrodeposited zinc

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsuda, Tetsuaki; Tobias, Charles W.

1981-09-01

The morphology of zinc as it is electrodeposited from acid solutions demonstrates a remarkable imprint of electrolyte flow conditions. The development of macromorphology of zinc deposits has been investigated under galvanostatic conditions on a rotating plantinum disk electrode by use of photomacrography, scanning electron microscopy, electron probe microanalysis and Auger microprobe analysis. Logarithmic spiral markings, which reflect the hydrodynamic flow on a rotating disk, appear in a certain region of current density well below the limiting current density. Morphological observations revealed the major influence of trace lead ions on the amplifications of surface roughness through coalescence and preferred growth ofmore » initial protrusions. Results obtained from ultra-pure electrolyte suggest preferred crystal growth towards well-mixed orientation in the concentration field caused by slight differences in crystallization overpotential. A qualitative model involving a coupling mechanism between the evolving surface roughness and instability phenomena in the boundary layer is advanced to explain the formation of spiral patterns.« less

Characterization of nanostructured surfaces generated by reconstitution of the porin MspA from Mycobacterium smegmatis.

PubMed

Wörner, Michael; Lioubashevski, Oleg; Basel, Matthew T; Niebler, Sandra; Gogritchiani, Eliso; Egner, Nicole; Heinz, Christian; Hoferer, Jürgen; Cipolloni, Michela; Janik, Katharine; Katz, Evgeny; Braun, Andre M; Willner, Itamar; Niederweis, Michael; Bossmann, Stefan H

2007-06-01

Nanostructures with long-term stability at the surface of gold electrodes are generated by reconstituting the porin MspA from Mycobacterium smegmatis into a specially designed monolayer of long-chain lipid surfactant on gold. Tailored surface coverage of gold electrodes with long-chain surfactants is achieved by electrochemically assisted deposition of organic thiosulfates (Bunte salts). The subsequent reconstitution of the octameric-pore MspA is guided by its extraordinary self-assembling properties. Importantly, electrochemical reduction of copper(II) yields copper nanoparticles within the MspA nanopores. Electrochemical impedance spectroscopy, reflection electron microscopy, and atomic force microscopy (AFM) show that: 1) the MspA pores within the self-assembled monolayer (SAM) are monodisperse and electrochemically active, 2) MspA reconstitutes in SAMs and with a 10-nm thickness, 3) AFM is a suitable method to detect pores within SAMs, and 4) the electrochemical reduction of Cu2+ to Cu0 under overpotential conditions starts within the MspA pores.

A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

DOE PAGES

Hod, Idan; Deria, Pravas; Bury, Wojciech; ...

2015-09-14

The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm −2. In conclusion,more » although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.« less

The reaction mechanism with free energy barriers at constant potentials for the oxygen evolution reaction at the IrO 2 (110) surface

DOE PAGES

Ping, Yuan; Nielsen, Robert J.; Goddard, William A.

2016-12-09

How to efficiently oxidize H 2O to O 2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO 2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OERmore » at the IrO 2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. Furthermore, this allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.« less

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis

PubMed Central

Gan, Patrick; Foord, John S; Compton, Richard G

2015-01-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur. PMID:26491640

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Co3 O4 Nanowire Arrays toward Superior Water Oxidation Electrocatalysis in Alkaline Media by Surface Amorphization.

PubMed

Zhou, Dan; He, Liangbo; Zhang, Rong; Hao, Shuai; Hou, Xiandeng; Liu, Zhiang; Du, Gu; Asiri, Abdullah M; Zheng, Chengbin; Sun, Xuping

2017-11-07

It is highly desirable to develop a simple, fast and straightforward method to boost the alkaline water oxidation of metal oxide catalysts. In this communication, we report our recent finding that the generation of amorphous Co-borate layer on Co 3 O 4 nanowire arrays supported on Ti mesh (Co 3 O 4 @Co-Bi NA/TM) leads to significantly boosted OER activity. The as-prepared Co 3 O 4 @Co-Bi NA/TM demands overpotential of 304 mV to drive a geometrical current density of 20 mA cm -2 in 1.0 M KOH, which is 109 mV less than that for Co 3 O 4 NA/TM, with its catalytic activity being preserved for at least 20 h. It suggests that the existence of amorphous Co-Bi layer promotes more CoO x (OH) y generation on Co 3 O 4 surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functional Independent Scaling Relation for ORR/OER Catalysts

DOE PAGES

Christensen, Rune; Hansen, Heine A.; Dickens, Colin F.; ...

2016-10-11

A widely used adsorption energy scaling relation between OH* and OOH* intermediates in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), has previously been determined using density functional theory and shown to dictate a minimum thermodynamic overpotential for both reactions. Here, we show that the oxygen–oxygen bond in the OOH* intermediate is, however, not well described with the previously used class of exchange-correlation functionals. By quantifying and correcting the systematic error, an improved description of gaseous peroxide species versus experimental data and a reduction in calculational uncertainty is obtained. For adsorbates, we find that the systematic error largelymore » cancels the vdW interaction missing in the original determination of the scaling relation. An improved scaling relation, which is fully independent of the applied exchange–correlation functional, is obtained and found to differ by 0.1 eV from the original. Lastly, this largely confirms that, although obtained with a method suffering from systematic errors, the previously obtained scaling relation is applicable for predictions of catalytic activity.« less

Performance of mixed-species biocathode microbial fuel cells using saline mustard tuber wastewater as self-buffered catholyte.

PubMed

Guo, Fei; Fu, Guokai; Zhang, Zhi

2015-03-01

Mixed-species biocathode microbial fuel cells (MFCs) were constructed. Mustard tuber wastewater (MTWW) was used as catholyte. Simultaneous organic matters and nitrogen removal at the cathode was observed, and majority of contaminants reduced were accomplished within acclimating period (AP). Concerning nitrogen removal, aerobic and anaerobic microenvironment could be formed within the cathodic biofilms, and both heterotrophic denitrification and bioelectrochemical denitrification were involved. Also, it was demonstrated that organic matters and ammonium could have detrimental effects on voltage output, but it could retrieve finally. Similar maximum power densities were obtained during stage1 (1.20Wm(-3)), stage2 (1.24Wm(-3)) and stage3 (1.32Wm(-3)). However, overpotential for oxygen reduction was investigated due to lower bacteria activity at cathode, which could major limitation for energy recovery. Considering similar performance of MFCs during different stages, it could be concluded that MTWW was adequately self-buffered when used as catholyte at mixed-species biocathodes. Copyright © 2015. Published by Elsevier Ltd.

A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

PubMed Central

Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I.; Tiwary, ChandraSekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N.; Vajtai, Robert; Yu, Aaron Z.; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J. A.; Ajayan, Pulickel M.

2016-01-01

Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts. PMID:27958290

CoP/WS2 nanoflake heterostructures as efficient electrocatalysts for significant improvement in hydrogen evolution activity

NASA Astrophysics Data System (ADS)

Chen, Yajie; Kang, Chuanhong; Wang, Ruihong; Ren, Zhiyu; Fu, Huiying; Xiao, Yuting; Tian, Guohui

2018-06-01

The CoP/WS2 nanoflake composites were synthesized via the sulfuration and subsequent phosphidation using the pre-prepared WO2.72 nanowires as precursors. Originally, WO2.72 nanowires were prepared and followed by sulfuration to obtain WS2 nanoflakes. The as-prepared WS2 nanoflakes were used as substrates, on which the Co3O4 nanoparticles were uniformly anchored to construct the Co3O4/WS2 nanoflakes. Finally, the Co3O4/WS2 composites were subjected to phosphidation and in-situ converted into CoP/WS2 nanoflakes. Because of the dual functionalities of both CoP and WS2, the abundant interfaces as well as their synergy, the CoP/WS2 nanoflakes exhibited much higher electrocatalytic activity, smaller overpotential (-81 mV), lower Tafel slope (62 mV decade-1), and higher stability toward hydrogen-evolution reaction than those for the single CoP and WS2.

Cycle Analysis of Two-stage Planar SOFC Power Generation by Series Connection of Low and High Temperature SOFCs

NASA Astrophysics Data System (ADS)

Ohba, Takahiro; Takezawa, Shinya; Araki, Takuto; Onda, Kazuo; Sakaki, Yoshinori

Solid Oxide Fuel Cell (SOFC) can be composed by solid components, and high power generation efficiency of a whole cycle is obtained by using high temperature exhaust heat for fuel reforming and bottoming power generation. Recently, the low temperature SOFC, which runs in the temperature range of around 600°C or above, has been developed with the high efficiency of power generation. On the other hand, multi-stage power generation system has been proposed by the United States DOE. In this study, a power generation system of two-stage SOFC by series connection of low and high temperature SOFCs has been studied. Overpotential data for low-temperature SOFC used in this study are based on recent published data, and those for high temperature SOFC arhaihe based on our previous study. The analytical results show the two-stage SOFC power generation efficiency of 50.3% and the total power generation efficiency of 56.1% under a standard operating condition.

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering.

PubMed

Shinagawa, Tatsuya; Takanabe, Kazuhiro

2017-04-10

Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine-tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Bottom–Up Electrodeposition of Large-Scale Nanotwinned Copper within 3D Through Silicon Via

PubMed Central

Sun, Fu-Long; Li, Cai-Fu; Zhu, Qing-Sheng; Zhang, Hao; Suganuma, Katsuaki

2018-01-01

This paper is the first to report a large-scale directcurrent electrodeposition of columnar nanotwinned copper within through silicon via (TSV) with a high aspect ratio (~4). With this newly developed technique, void-free nanotwinned copper array could be fabricated in low current density (30 mA/cm2) and convection conditions (300 rpm), which are the preconditions for copper deposition with a uniform deep-hole microstructure. The microstructure of a whole cross-section of deposited copper array was made up of (111) orientated columnar grains with parallel nanoscale twins that had thicknesses of about 22 nm. The hardness was also uniform along the growth direction, with 2.34 and 2.68 GPa for the top and bottom of the TSV, respectively. The gelatin additive is also first reported hereas a key factor in forming nanoscale twins by adsorbing on the cathode surface, in order to enhance the overpotential for cathodic reaction during the copper deposition process. PMID:29473865

Design Rules for Oxygen Evolution Catalysis at Porous Iron Oxide Electrodes: A 1000-Fold Current Density Increase.

PubMed

Haschke, Sandra; Pankin, Dmitrii; Petrov, Yuri; Bochmann, Sebastian; Manshina, Alina; Bachmann, Julien

2017-09-22

Nanotubular iron(III) oxide electrodes are optimized for catalytic efficiency in the water oxidation reaction at neutral pH. The nanostructured electrodes are prepared from anodic alumina templates, which are coated with Fe 2 O 3 by atomic layer deposition. Scanning helium ion microscopy, X-ray diffraction, and Raman spectroscopy are used to characterize the morphologies and phases of samples submitted to various treatments. These methods demonstrate the contrasting effects of thermal annealing and electrochemical treatment. The electrochemical performances of the corresponding electrodes under dark conditions are quantified by steady-state electrolysis and electrochemical impedance spectroscopy. A rough and amorphous Fe 2 O 3 with phosphate incorporation is critical for the optimization of the water oxidation reaction. For the ideal pore length of 17 μm, the maximum catalytic turnover is reached with an effective current density of 140 μA cm -2 at an applied overpotential of 0.49 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electroactive Film of Myoglobin Incorporated in a 3D-porous Calcium Alginate Film with Polyvinyl Alcohol, Glycerin and Gelatin.

PubMed

Zheng, Xueqin; Sun, Hong; Hou, Shifeng

2015-01-01

In this work, an electroactive porous Mb-CA's composite film was fabricated by incorporating myoglobin (Mb) in a three-dimension (3D) porous calcium alginate (CA) film with polyvinyl alcohol, glycerol, and gelatin. The porous Mb-CA's film modified electrodes exhibited a pair of well-defined, quasi-reversible cyclic voltammetric (CV) peaks at about -0.37 V vs. SCE in pH 7.0 buffers, characteristic of Mb heme Fe((III))/Fe((II)) redox couples. The electrochemical parameters, such as formal potentials (E(o')) and apparent heterogeneous electron-transfer rate constants (ks), were estimated by square-wave voltammetry with nonlinear regression analysis. The porous CA's composite film could form hydrogel in aqueous solution. The positions of the Soret absorbance band suggest that Mb in the CA's composite film kept its native states in the medium pH range. Hydrogen peroxide, oxygen, and nitrite were electrochemically catalyzed by the Mb-CA's composite film with significant lowering of the reduction overpotential.

CFD analysis of a solid oxide fuel cell with internal reforming: Coupled interactions of transport, heterogeneous catalysis and electrochemical processes

NASA Astrophysics Data System (ADS)

Janardhanan, Vinod M.; Deutschmann, Olaf

Direct internal reforming in solid oxide fuel cell (SOFC) results in increased overall efficiency of the system. Present study focus on the chemical and electrochemical process in an internally reforming anode supported SOFC button cell running on humidified CH 4 (3% H 2 O). The computational approach employs a detailed multi-step model for heterogeneous chemistry in the anode, modified Butler-Volmer formalism for the electrochemistry and Dusty Gas Model (DGM) for the porous media transport. Two-dimensional elliptic model equations are solved for a button cell configuration. The electrochemical model assumes hydrogen as the only electrochemically active species. The predicted cell performances are compared with experimental reports. The results show that model predictions are in good agreement with experimental observation except the open circuit potentials. Furthermore, the steam content in the anode feed stream is found to have remarkable effect on the resulting overpotential losses and surface coverages of various species at the three-phase boundary.