Influence of Adsorbed Hydroxyl and Carbon Monoxide on Potential-Induced Reconstruction of Au(100) as Examined by Scanning Tunneling Microscopy

DTIC Science & Technology

1994-02-01

years have witnessed substantial advances in our knowledge of metal reconstruction in electrochemical systems, primarily for low-index gold surfaces in...index gold surfaces, reconstruction can be formed or removed by applying electrode potentials corresponding to negative or positive electronic charge...potential and gold oxidation regions, for Au(100) in 0.1 M KOH, obtained in a conventional electrochemical cell (solid trace). The voltammetric

Attachment chemistry of aromatic compounds on a Silicon(100) surface

NASA Astrophysics Data System (ADS)

Henriksson, Anders; Nishiori, Daiki; Maeda, Hiroaki; Miyachi, Mariko; Yamanoi, Yoshinori; Nishihara, Hiroshi

2018-03-01

A mild method was developed for the chemical attachment of aromatic compounds directly onto a hydrogen-terminated Si(100) (H-Si(100)) surface. In the presence of palladium catalyst and base, 4-iodophenylferrocene and a π-conjugated iron complex were attached to H-Si(100) electrodes and hydrogen-terminated silicon nanowires (H-SiNWs), both of which have predominant dihydride species on their surfaces. The reactions were conducted in 1,4-dioxane at 100 °C and the immobilization of both 4-ferrocenylphenyl group and π-conjugated molecular wires were confirmed and quantified by XPS and electrochemical measurements. We reported densely packed monolayer whose surface coverage (Γ), estimated from the electrochemical measurements are in analogue to similar monolayers prepared via thermal or light induced hydrosilylation reactions with alkenes or alkynes. The increase in electrochemical response observed on nanostructured silicon surfaces corresponds well to the increase in surface area, those strongly indicating that this method may be applied for the functionalization of electrodes with a variety of surface topographies.

Tuning the Outward to Inward Swelling in Lithiated Silicon Nanotubes via Surface Oxide Coating

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

Wang, Jiangwei; Luo, Hao; Liu, Yang

2016-09-14

The electrochemically-induced mechanical degradation hinders the application of Si anodes in advanced lithium-ion batteries. Hollow structures and surface coatings have been often used to mitigate the degradation of Si-based anodes. However, the structural change and degradation mechanism during lithiation/delithiation of hollow Si structures with coatings remain unclear. Here, we combine in situ TEM experiment and chemomechanical modeling to study the electrochemically induced swelling of amorphous-Si (a-Si) nanotubes with different thicknesses of surface SiOx layers. Surprisingly, we find that no inward expansion occurs at the inner surface during lithiation of a-Si nanotubes with native oxides. In contrast, inward expansion can bemore » induced by increasing the thickness of SiOx on the outer surface. Moreover, both the sandwich lithiation mechanism and two-stage lithiation process in a-Si nanotubes remain unchanged with the increasing thickness of surface coatings. Our chemomechanical modeling reveals the mechanical confinement effects in lithiated a-Si nanotubes with and without SiOx coatings. This work not only provides insights into the degradation of nanotube anodes with surface coatings, but also sheds light onto the optimal design of hollow anodes for high-performance lithium-ion batteries.« less

Restructuring of an Ir(210) electrode surface by potential cycling

PubMed Central

Soliman, Khaled A; Kolb, Dieter M; Jacob, Timo

2014-01-01

Summary This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s−1 between −0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation. PMID:25247118

Restructuring of an Ir(210) electrode surface by potential cycling.

PubMed

Soliman, Khaled A; Kolb, Dieter M; Kibler, Ludwig A; Jacob, Timo

2014-01-01

This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s(-1) between -0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation.

Enhanced electrochemical etching of ion irradiated silicon by localized amorphization

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

Dang, Z. Y.; Breese, M. B. H.; Lin, Y.

2014-05-12

A tailored distribution of ion induced defects in p-type silicon allows subsequent electrochemical anodization to be modified in various ways. Here we describe how a low level of lattice amorphization induced by ion irradiation influences anodization. First, it superposes a chemical etching effect, which is observable at high fluences as a reduced height of a micromachined component. Second, at lower fluences, it greatly enhances electrochemical anodization by allowing a hole diffusion current to flow to the exposed surface. We present an anodization model, which explains all observed effects produced by light ions such as helium and heavy ions such asmore » cesium over a wide range of fluences and irradiation geometries.« less

Enhancement of surface area and wettability properties of boron doped diamond by femtosecond laser-induced periodic surface structuring

DOE PAGES

Granados, Eduardo; Calderon, Miguel Martinez; Krzywinski, Jacek; ...

2017-08-28

We demonstrate the formation of laser-induced periodic surface structures (LIPSS) in boron-doped diamond (BDD) by irradiation with femtosecond near-IR laser pulses. The results show that the obtained LIPSS are perpendicular to the laser polarization, and the ripple periodicity is on the order of half of the irradiation wavelength. The surface structures and their electrochemical properties were characterized using Raman micro-spectroscopy, in combination with scanning electron and atomic force microscopies. The textured BDD surface showed a dense and large surface area with no change in its structural characteristics. The effective surface area of the textured BDD electrode was approximately 50% largermore » than that of a planar substrate, while wetting tests showed that the irradiated area becomes highly hydrophilic. Lastly, our results indicate that LIPSS texturing of BDD is a straightforward and simple technique for enhancing the surface area and wettability properties of the BDD electrodes, which could enable higher current efficiency and lower energy consumption in the electrochemical oxidation of toxic organics.« less

Enhancement of surface area and wettability properties of boron doped diamond by femtosecond laser-induced periodic surface structuring

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

Granados, Eduardo; Calderon, Miguel Martinez; Krzywinski, Jacek

We demonstrate the formation of laser-induced periodic surface structures (LIPSS) in boron-doped diamond (BDD) by irradiation with femtosecond near-IR laser pulses. The results show that the obtained LIPSS are perpendicular to the laser polarization, and the ripple periodicity is on the order of half of the irradiation wavelength. The surface structures and their electrochemical properties were characterized using Raman micro-spectroscopy, in combination with scanning electron and atomic force microscopies. The textured BDD surface showed a dense and large surface area with no change in its structural characteristics. The effective surface area of the textured BDD electrode was approximately 50% largermore » than that of a planar substrate, while wetting tests showed that the irradiated area becomes highly hydrophilic. Lastly, our results indicate that LIPSS texturing of BDD is a straightforward and simple technique for enhancing the surface area and wettability properties of the BDD electrodes, which could enable higher current efficiency and lower energy consumption in the electrochemical oxidation of toxic organics.« less

Microfluidic chip integrated with flexible PDMS-based electrochemical cytosensor for dynamic analysis of drug-induced apoptosis on HeLa cells.

PubMed

Cao, Jun-Tao; Zhu, Ying-Di; Rana, Rohit Kumar; Zhu, Jun-Jie

2014-01-15

A novel microfluidic platform integrated with a flexible PDMS-based electrochemical cytosensor was developed for real-time monitoring of the proliferation and apoptosis of HeLa cells. The PDMS-gold film, which had a conductive smooth surface and was semi-transparent, facilitated electrochemical measurements and optical microscope observations. We observed distinct increases and decreases in peak current intensity, corresponding to cell proliferation in culture medium and apoptosis in the presence of an anticancer drug, respectively. This electrochemical analysis method permitted real-time, label-free monitoring of cell behavior, and the electrochemical results were confirmed with optical microscopy. The flexible microfluidic electrochemical platform presented here is suitable for on-site monitoring of cell behavior in microenvironments. © 2013 Elsevier B.V. All rights reserved.

Nitridation-driven conductive Li4Ti5O12 for lithium ion batteries.

PubMed

Park, Kyu-Sung; Benayad, Anass; Kang, Dae-Joon; Doo, Seok-Gwang

2008-11-12

To modify oxide structure and introduce a thin conductive film on Li4Ti5O12, thermal nitridation was adopted for the first time. NH3 decomposes surface Li4Ti5O12 to conductive TiN at high temperature, and surprisingly, it also modifies the surface structure in a way to accommodate the single phase Li insertion and extraction. The electrochemically induced Li4+deltaTi5O12 with a TiN coating layer shows great electrochemical properties at high current densities.

Electrochemical impedance spectroscopy investigation on the clinical lifetime of ProTaper rotary file system.

PubMed

Penta, Virgil; Pirvu, Cristian; Demetrescu, Ioana

2014-01-01

The main objective of the current paper is to show that electrochemical impedance spectroscopy (EIS) could be a method for evaluating and predicting of ProTaper rotary file system clinical lifespan. This particular aspect of everyday use of the endodontic files is of great importance in each dental practice and has profound clinical implications. The method used for quantification resides in the electrochemical impedance spectroscopy theory and has in its main focus the characteristics of the surface titanium oxide layer. This electrochemical technique has been adapted successfully to identify the quality of the Ni-Ti files oxide layer. The modification of this protective layer induces changes in corrosion behavior of the alloy modifying the impedance value of the file. In order to assess the method, 14 ProTaper sets utilized on different patients in a dental clinic have been submitted for testing using EIS. The information obtained in regard to the surface oxide layer has offered an indication of use and proves that the said layer evolves with each clinical application. The novelty of this research is related to an electrochemical technique successfully adapted for Ni-Ti file investigation and correlation with surface and clinical aspects.

An ultrasensitive electrochemical biosensor for polynucleotide kinase assay based on gold nanoparticle-mediated lambda exonuclease cleavage-induced signal amplification.

PubMed

Cui, Lin; Li, Yueying; Lu, Mengfei; Tang, Bo; Zhang, Chun-Yang

2018-01-15

Polynucleotide kinase (PNK) plays an essential role in cellular nucleic acid metabolism and the cellular response to DNA damage. However, conventional methods for PNK assay suffer from low sensitivity and involve multiple steps. Herein, we develop a simply electrochemical method for sensitive detection of PNK activity on the basis of Au nanoparticle (AuNP)-mediated lambda exonuclease cleavage-induced signal amplification. We use [Ru(NH 3 ) 6 ] 3+ as the electrochemically active indicator and design two DNA strands (i.e., strand 1 and strand 2) to sense PNK. The assembly of strand 2 on the AuNP surface leads to the formation of AuNP-strand 2 conjugates which can be subsequently immobilized on the gold electrode through the hybridization of strand 1 with strand 2 for the generation of a high electrochemical signal. The presence of PNK induces the phosphorylation of the strand 2-strand 1 hybrid and the subsequent cleavage of double-stranded DNA (dsDNA) by lambda exonuclease, resulting in the release of AuNP-strand 2 conjugates and [Ru(NH 3 ) 6 ] 3+ from the gold electrode surface and consequently the decrease of electrochemical signal. The PNK activity can be simply monitored by the measurement of [Ru(NH 3 ) 6 ] 3+ peak current signal. This assay is very sensitive with a detection limit of as low as 7.762 × 10 -4 UmL -1 and exhibits a large dynamic range from 0.001 to 10UmL -1 . Moreover, this method can be used to screen the PNK inhibitors, and it shows excellent performance in real sample analysis, thus holding great potential for further applications in biological researches and clinic diagnosis. Copyright © 2017 Elsevier B.V. All rights reserved.

Peptide Fragmentation by Corona Discharge Induced Electrochemical Ionization

PubMed Central

Lloyd, John R.; Hess, Sonja

2010-01-01

Fundamental studies have greatly improved our understanding of electrospray, including the underlying electrochemical reactions. Generally regarded as disadvantageous, we have recently shown that corona discharge (CD) can be used as an effective method to create a radical cation species [M]+•, thus optimizing the electrochemical reactions that occur on the surface of the stainless steel (SS) electrospray capillary tip. This technique is known as CD initiated electrochemical ionization (CD-ECI). Here, we report on the fundamental studies using CD-ECI to induce analytically useful in-source fragmentation of a range of molecules that complex transition metals. Compounds that have been selectively fragmented using CD-ECI include enolate forming phenylglycine containing peptides, glycopeptides, nucleosides and phosphopeptides. Collision induced dissociation (CID) or other activation techniques were not necessary for CD-ECI fragmentation. A four step mechanism was proposed: 1. Complexation using either Fe in the SS capillary tip material or Cu(II) as an offline complexation reagent; 2. Electrochemical oxidation of the complexed metal and thus formation of a radical cation (e.g.; Fe - e− → Fe +•); 3. Radical fragmentation of the complexed compound. 4. Electrospray ionization of the fragmented neutrals. Fragmentation patterns resembling b- and y-type ions were observed and allowed the localization of the phosphorylation sites. PMID:20869880

Electrochemical sensors and biosensors based on less aggregated graphene.

PubMed

Bo, Xiangjie; Zhou, Ming; Guo, Liping

2017-03-15

As a novel single-atom-thick sheet of sp 2 hybridized carbon atoms, graphene (GR) has attracted extensive attention in recent years because of its unique and remarkable properties, such as excellent electrical conductivity, large theoretical specific surface area, and strong mechanical strength. However, due to the π-π interaction, GR sheets are inclined to stack together, which may seriously degrade the performance of GR with the unique single-atom layer. In recent years, an increasing number of GR-based electrochemical sensors and biosensors are reported, which may reflect that GR has been considered as a kind of hot and promising electrode material for electrochemical sensor and biosensor construction. However, the active sites on GR surface induced by the irreversible GR aggregations would be deeply secluded inside the stacked GR sheets and therefore are not available for the electrocatalysis. So the alleviation or the minimization of the aggregation level for GR sheets would facilitate the exposure of active sites on GR and effectively upgrade the performance of GR-based electrochemical sensors and biosensors. Less aggregated GR with low aggregation and high dispersed structure can be used in improving the electrochemical activity of GR-based electrochemical sensors or biosensors. In this review, we summarize recent advances and new progress for the development of electrochemical sensors based on less aggregated GR. To achieve such goal, many strategies (such as the intercalation of carbon materials, surface modification, and structural engineering) have been applied to alleviate the aggregation level of GR in order to enhance the performance of GR-based electrochemical sensors and biosensors. Finally, the challenges associated with less aggregated GR-based electrochemical sensors and biosensors as well as related future research directions are discussed. Copyright © 2016 Elsevier B.V. All rights reserved.

A novel quantitative electrochemical method to monitor DNA double-strand breaks caused by a DNA cleavage agent at a DNA sensor.

PubMed

Banasiak, Anna; Cassidy, John; Colleran, John

2018-06-01

To date, DNA cleavage, caused by cleavage agents, has been monitored mainly by gel and capillary electrophoresis. However, these techniques are time-consuming, non-quantitative and require gel stains. In this work, a novel, simple and, importantly, a quantitative method for monitoring the DNA nuclease activity of potential anti-cancer drugs, at a DNA electrochemical sensor, is presented. The DNA sensors were prepared using thiol-modified oligonucleotides that self-assembled to create a DNA monolayer at gold electrode surfaces. The quantification of DNA double-strand breaks is based on calculating the DNA surface coverage, before and after exposure to a DNA cleavage agent. The nuclease properties of a model DNA cleavage agent, copper bis-phenanthroline ([Cu II (phen) 2 ] 2+ ), that can cleave DNA in a Fenton-type reaction, were quantified electrochemically. The DNA surface coverage decreased on average by 21% after subjecting the DNA sensor to a nuclease assay containing [Cu II (phen) 2 ] 2+ , a reductant and an oxidant. This percentage indicates that 6 base pairs were cleaved in the nuclease assay from the immobilised 30 base pair strands. The DNA cleavage can be also induced electrochemically in the absence of a chemical reductant. [Cu II (phen) 2 ] 2+ intercalates between DNA base pairs and, on application of a suitable potential, can be reduced to [Cu I (phen) 2 ] + , with dissolved oxygen acting as the required oxidant. This reduction process is facilitated through DNA strands via long-range electron transfer, resulting in DNA cleavage of 23%. The control measurements for both chemically and electrochemically induced cleavage revealed that DNA strand breaks did not occur under experimental conditions in the absence of [Cu II (phen) 2 ] 2+ . Copyright © 2018 Elsevier B.V. All rights reserved.

Binder-free carbon nanotube electrode for electrochemical removal of chromium.

PubMed

Wang, Haitao; Na, Chongzheng

2014-11-26

Electrochemical treatment of chromium-containing wastewater has the advantage of simultaneously reducing hexavalent chromium (CrVI) and reversibly adsorbing the trivalent product (CrIII), thereby minimizing the generation of waste for disposal and providing an opportunity for resource reuse. The application of electrochemical treatment of chromium is often limited by the available electrochemical surface area (ESA) of conventional electrodes with flat surfaces. Here, we report the preparation and evaluation of carbon nanotube (CNT) electrodes consisting of vertically aligned CNT arrays directly grown on stainless steel mesh (SSM). We show that the 3-D organization of CNT arrays increases ESA up to 13 times compared to SSM. The increase of ESA is correlated with the length of CNTs, consistent with a mechanism of roughness-induced ESA enhancement. The increase of ESA directly benefits CrVI reduction by proportionally accelerating reduction without compromising the electrode's ability to adsorb CrIII. Our results suggest that the rational design of electrodes with hierarchical structures represents a feasible approach to improve the performance of electrochemical treatment of contaminated water.

Heterogeneous Electrochemical Immunoassay of Hippuric Acid on the Electrodeposited Organic Films

PubMed Central

Choi, Young-Bong; Kim, Nam-Hyuk; Kim, Seung-Hoi; Tae, Gun-Sik; Kim, Hyug-Han

2014-01-01

By directly coordinating hippuric acid (HA) to the ferrate (Fe) as an electron transfer mediator, we synthesized a Fe-HA complex, which shows a good electrochemical signal and thus enables the electrochemical immunoanalysis for HA. We electrodeposited organic films containing imidazole groups on the electrode surface and then bonded Ni ion (positive charge) to induce immobilization of Fe-HA (negative charge) through the electrostatic interaction. The heterogeneous competitive immunoassay system relies on the interaction between immobilized Fe-HA antigen conjugate and free HA antigen to its antibody (anti-HA). The electric signal becomes weaker due to the hindered electron transfer reaction when a large-sized HA antibody is bound onto the Fe-HA. However, in the presence of HA, the electric signal increases because free HA competitively reacts with the HA antibody prior to actual reaction and thus prevents the HA antibody from interacting with Fe-HA at the electrode surface. This competition reaction enabled an electrochemical quantitative analysis of HA concentration with a detection limit of 0.5 μg mL−1, and thus allowed us to develop a simple and rapid electrochemical immunosensor. PMID:25313491

A reconfigurable liquid metal antenna driven by electrochemically controlled capillarity

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

Wang, M.; Adams, J. J., E-mail: jjadams2@ncsu.edu; Trlica, C.

2015-05-21

We describe a new electrochemical method for reversible, pump-free control of liquid eutectic gallium and indium (EGaIn) in a capillary. Electrochemical deposition (or removal) of a surface oxide on the EGaIn significantly lowers (or increases) its interfacial tension as a means to induce the liquid metal in (or out) of the capillary. A fabricated prototype demonstrates this method in a reconfigurable antenna application in which EGaIn forms the radiating element. By inducing a change in the physical length of the EGaIn, the operating frequency of the antenna tunes over a large bandwidth. This purely electrochemical mechanism uses low, DC voltagesmore » to tune the antenna continuously and reversibly between 0.66 GHz and 3.4 GHz resulting in a 5:1 tuning range. Gain and radiation pattern measurements agree with electromagnetic simulations of the device, and its measured radiation efficiency varies from 41% to 70% over its tuning range.« less

A Tandem Microscopic-Electrochemical Examination of A Charge-Induced Surface Phase Sequence: Ordered Au(110) in Aqueous Iodide Electrolytes as Probed by Potentiodynamic Scanning Tunneling Microscopy

DTIC Science & Technology

1994-02-01

and Rh(lll)9-12 by STM, and halides on Au(lll) by SXRS. 1 3 ’ 1 4 For several of these systems, especially anion adsorption on gold , the adsorbate...index faces of gold in aqueous solution by means of in- situ STM combined with conventional electrochemical methods. The value of the electrochemical...structure and conversion dynamics. A related description of the Au(lO0)-I- system, along with a comparison with the behavior of the other two low-index gold

Flexible shrink-induced high surface area electrodes for electrochemiluminescent sensing.

PubMed

Pegan, Jonathan D; Ho, Adrienne Y; Bachman, Mark; Khine, Michelle

2013-11-07

Photolithographically defined metallic thin film on commodity shrink-wrap is leveraged to create robust electrodes. By thermally shrinking the film, electrodes are reduced by 20× in footprint for improved resolution and conductivity with >600% enhancements in electrochemically active surface area; as electrochemiluminescent sensors, they demonstrate improved limits of detection.

Co-adsorption of water and oxygen on GaN: Effects of charge transfer and formation of electron depletion layer.

PubMed

Wang, Qi; Puntambekar, Ajinkya; Chakrapani, Vidhya

2017-09-14

Species from ambient atmosphere such as water and oxygen are known to affect electronic and optical properties of GaN, but the underlying mechanism is not clearly known. In this work, we show through careful measurement of electrical resistivity and photoluminescence intensity under various adsorbates that the presence of oxygen or water vapor alone is not sufficient to induce electron transfer to these species. Rather, the presence of both water and oxygen is necessary to induce electron transfer from GaN that leads to the formation of an electron depletion region on the surface. Exposure to acidic gases decreases n-type conductivity due to increased electron transfer from GaN, while basic gases increase n-type conductivity and PL intensity due to reduced charge transfer from GaN. These changes in the electrical and optical properties, as explained using a new electrochemical framework based on the phenomenon of surface transfer doping, suggest that gases interact with the semiconductor surface through electrochemical reactions occurring in an adsorbed water layer present on the surface.

Effect of morphology and defect density on electron transfer of electrochemically reduced graphene oxide

NASA Astrophysics Data System (ADS)

Zhang, Yan; Hao, Huilian; Wang, Linlin

2016-12-01

Electrochemically reduced graphene oxide (ERGO) is widely used to construct electrochemical sensors. Understanding the electron transfer behavior of ERGO is essential for its electrode material applications. In this paper, different morphologies of ERGO were prepared via two different methods. Compared to ERGO/GCEs prepared by electrochemical reduction of pre-deposited GO, more exposed edge planes of ERGO are observed on the surface of ERGO-GCE that was constructed by electrophoretic deposition of GO. The defect densities of ERGO were controlled by tuning the mass or concentration of GO. The electron transfer kinetics (k0) of GCE with different ERGOs was comparatively investigated. Owing to increased surface areas and decreased defect density, the k0 values of ERGO/GCE initially increase and then decrease with incrementing of GO mass. When the morphology and surface real areas of ERGO-GCE are the same, an increased defect density induces an accelerated electron transfer rate. k0 valuesof ERGO-GCEs are about 1 order of magnitude higher than those of ERGO/GCEs due to the difference in the amount of edge planes. This work demonstrates that both defect densities and edge planes of ERGO play crucial roles in electron transfer kinetics.

Development of large-surface Nafion-metal composite actuator and its electrochemical characterization

NASA Astrophysics Data System (ADS)

Noh, Taegeun; Tak, Yong Suk; Nam, Jaedo; Jeon, Jaewook; Kim, Hunmo; Choi, Hyoukryeol; Bae, Sang Sik

2001-07-01

Behaviors of nafion-based actuators are significantly affected by interfacial area between electrode and polymer electrolyte. Replication method was utilized to manufacture a large surface-area composite actuator. Etched aluminum foil was used as a template for replication using liquid nafion solution. Measurement of double layer charging and scanning electron microscopy indicated that interfacial area was greatly increased by replication method. Higher surface area induced a better bending performance of ionic polymer metal composite (IPMC). In parallel, the effect of cations on IPMC was interpreted with constant current experiment, linear sweep voltammetry and electrochemical impedance spectroscopy. For univalent cations, ion size is the most influencing parameter on ionic mobility inside membrane. However, ion-ion interaction affects an ionic mobility for divalent cations.

Nanoarchitectured electrochemical cytosensors for selective detection of leukemia cells and quantitative evaluation of death receptor expression on cell surfaces.

PubMed

Zheng, Tingting; Fu, Jia-Ju; Hu, Lihui; Qiu, Fan; Hu, Minjin; Zhu, Jun-Jie; Hua, Zi-Chun; Wang, Hui

2013-06-04

The variable susceptibility to the tumor necrosis factor-related apoptosis-inducing ligand (TRAIL) treatment observed in various types of leukemia cells is related to the difference in the expression levels of death receptors, DR4 and DR5, on the cell surfaces. Quantifying the DR4/DR5 expression status on leukemia cell surfaces is of vital importance to the development of diagnostic tools to guide death receptor-based leukemia treatment. Taking the full advantages of novel nanobiotechnology, we have developed a robust electrochemical cytosensing approach toward ultrasensitive detection of leukemia cells with detection limit as low as ~40 cells and quantitative evaluation of DR4/DR5 expression on leukemia cell surfaces. The optimization of electron transfer and cell capture processes at specifically tailored nanobiointerfaces and the incorporation of multiple functions into rationally designed nanoprobes provide unique opportunities of integrating high specificity and signal amplification on one electrochemical cytosensor. The high sensitivity and selectivity of this electrochemical cytosensing approach also allows us to evaluate the dynamic alteration of DR4/DR5 expression on the surfaces of living cells in response to drug treatments. Using the TRAIL-resistant HL-60 cells and TRAIL-sensitive Jurkat cells as model cells, we have further verified that the TRAIL susceptibility of various types of leukemia cells is directly correlated to the surface expression levels of DR4/DR5. This versatile electrochemical cytosensing platform is believed to be of great clinical value for the early diagnosis of human leukemia and the evaluation of therapeutic effects on leukemia patients after radiation therapy or drug treatment.

Single crystalline thin films as a novel class of electrocatalysts

DOE PAGES

Snyder, Joshua; Markovic, Nenad; Stamenkovic, Vojislav

2013-01-01

The ubiquitous use of single crystal metal electrodes has garnered invaluable insight into the relationship between surface atomic structure and functional electrochemical properties. But, the sensitivity of their electrochemical response to surface orientation and the amount of precious metal required can limit their use. We present here a generally applicable procedure for producing thin metal films with a large proportion of atomically flat (111) terraces without the use of an epitaxial template. Thermal annealing in a controlled atmosphere induces long-range ordering of magnetron sputtered thin metal films deposited on an amorphous substrate. The ordering transition in these thin metal filmsmore » yields characteristic (111) electrochemical signatures with minimal amount of material and provides an adequate replacement for oriented bulk single crystals. Our procedure can be generalized towards a novel class of practical multimetallic thin film based electrocatalysts with tunable near-surface compositional profile and morphology. Annealing of atomically corrugated sputtered thin film Pt-alloy catalysts yields an atomically smooth structure with highly crystalline, (111)-like ordered and Pt segregated surface that displays superior functional properties, bridging the gap between extended/bulk surfaces and nanoscale systems.« less

Silica decorated on porous activated carbon nanofiber composites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Kim, So Yeun; Kim, Bo-Hye

2016-10-01

A hybrid of silica decorated on porous activated carbon nanofibers (ACNFs) is fabricated in the form of a web via electrospinning and an activation process as an electrode material for electrochemical capacitors in an organic electrolyte. The introduction of PhSiH3 (PS) into the polyacrylonitrile (PAN) solution induces a porous ACNF structure containing silica nanoparticles (NPs) via the spontaneous sol-gel process of PS by steam in the subsequent physical activation process. These inorganic-organic hybrid composites of porous ACNF containing silica NPs show superior specific capacitance and energy density in electrochemical tests, along with good rate capability and excellent cycle life in an organic electrolyte, which is attributed to the combination of ACNF's high surface area and silica's hydrophilicity. The electrochemical performance decreases with increasing PS concentration, and this trend is consistent with the specific surface area results, which reveal the rapid formation of a double layer.

Binding-induced DNA walker for signal amplification in highly selective electrochemical detection of protein.

PubMed

Ji, Yuhang; Zhang, Lei; Zhu, Longyi; Lei, Jianping; Wu, Jie; Ju, Huangxian

2017-10-15

A binding-induced DNA walker-assisted signal amplification was developed for highly selective electrochemical detection of protein. Firstly, the track of DNA walker was constructed by self-assembly of the high density ferrocene (Fc)-labeled anchor DNA and aptamer 1 on the gold electrode surface. Sequentially, a long swing-arm chain containing aptamer 2 and walking strand DNA was introduced onto gold electrode through aptamers-target specific recognition, and thus initiated walker strand sequences to hybridize with anchor DNA. Then, the DNA walker was activated by the stepwise cleavage of the hybridized anchor DNA by nicking endonuclease to release multiple Fc molecules for signal amplification. Taking thrombin as the model target, the Fc-generated electrochemical signal decreased linearly with logarithm value of thrombin concentration ranging from 10pM to 100nM with a detection limit of 2.5pM under the optimal conditions. By integrating the specific recognition of aptamers to target with the enzymatic cleavage of nicking endonuclease, the aptasensor showed the high selectivity. The binding-induced DNA walker provides a promising strategy for signal amplification in electrochemical biosensor, and has the extensive applications in sensitive and selective detection of the various targets. Copyright © 2017 Elsevier B.V. All rights reserved.

Self-consistent modelling of electrochemical strain microscopy in mixed ionic-electronic conductors: Nonlinear and dynamic regimes

DOE PAGES

Varenyk, O. V.; Silibin, M. V.; Kiselev, Dmitri A.; ...

2015-08-19

The frequency dependent Electrochemical Strain Microscopy (ESM) response of mixed ionic-electronic conductors is analyzed within the framework of Fermi-Dirac statistics and the Vegard law, accounting for steric effects from mobile donors. The emergence of dynamic charge waves and nonlinear deformation of the surface in response to bias applied to the tip-surface junction is numerically explored. The 2D maps of the strain and concentration distributions across the mixed ionic-electronic conductor and bias-induced surface displacements are calculated. Furthermore, the obtained numerical results can be applied to quantify the ESM response of Li-based solid electrolytes, materials with resistive switching, and electroactive ferroelectric polymers,more » which are of potential interest for flexible and high-density non-volatile memory devices.« less

Self-consistent modelling of electrochemical strain microscopy in mixed ionic-electronic conductors: Nonlinear and dynamic regimes

NASA Astrophysics Data System (ADS)

Varenyk, O. V.; Silibin, M. V.; Kiselev, D. A.; Eliseev, E. A.; Kalinin, S. V.; Morozovska, A. N.

2015-08-01

The frequency dependent Electrochemical Strain Microscopy (ESM) response of mixed ionic-electronic conductors is analyzed within the framework of Fermi-Dirac statistics and the Vegard law, accounting for steric effects from mobile donors. The emergence of dynamic charge waves and nonlinear deformation of the surface in response to bias applied to the tip-surface junction is numerically explored. The 2D maps of the strain and concentration distributions across the mixed ionic-electronic conductor and bias-induced surface displacements are calculated. The obtained numerical results can be applied to quantify the ESM response of Li-based solid electrolytes, materials with resistive switching, and electroactive ferroelectric polymers, which are of potential interest for flexible and high-density non-volatile memory devices.

Copper Antimonide Nanowire Array Lithium Ion Anodes Stabilized by Electrolyte Additives.

PubMed

Jackson, Everett D; Prieto, Amy L

2016-11-09

Nanowires of electrochemically active electrode materials for lithium ion batteries represent a unique system that allows for intensive investigations of surface phenomena. In particular, highly ordered nanowire arrays produced by electrodeposition into anodic aluminum oxide templates can lead to new insights into a material's electrochemical performance by providing a high-surface-area electrode with negligible volume expansion induced pulverization. Here we show that for the Li-Cu x Sb ternary system, stabilizing the surface chemistry is the most critical factor for promoting long electrode life. The resulting solid electrolyte interphase is analyzed using a mix of electron microscopy, X-ray photoelectron spectroscopy, and lithium ion battery half-cell testing to provide a better understanding of the importance of electrolyte composition on this multicomponent alloy anode material.

Study of reticulated vitreous carbon surface treated by plasma immersion ion implantation for electrodes production

NASA Astrophysics Data System (ADS)

Silva, L. L. G.; Conceição, D. A. S.; Oishi, S. S.; Toth, A.; Ueda, M.

2012-03-01

RVC samples were treated by nitrogen plasma immersion ion implantation (N-PIII) for electrodes production. High-voltage pulses with amplitudes of -3.0 kV or -10.0 kV were applied to the RVC samples while the treatment time was 10, 20 and 30 min. The samples were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The SEM images present an apparent enhancement of the surface roughness after the treatment probably due to the surface sputtering during the PIII process. This observation is in agreement with the specific electrochemical surface area (SESA) of RVC electrodes. An increase was observed of the SESA values for the PIII-treated samples compared to the untreated specimen. Some oxygen and nitrogen containing groups were introduced on the RVC surface after the PIII treatment. Both plasma-induced process: the surface roughening and the introduction of the polar species on the RVC surface are beneficial for the RVC electrodes application.

Probing the electronic transport on the reconstructed Au/Ge(001) surface

PubMed Central

Krok, Franciszek; Kaspers, Mark R; Bernhart, Alexander M; Nikiel, Marek; Jany, Benedykt R; Indyka, Paulina; Wojtaszek, Mateusz; Möller, Rolf

2014-01-01

Summary By using scanning tunnelling potentiometry we characterized the lateral variation of the electrochemical potential µec on the gold-induced Ge(001)-c(8 × 2)-Au surface reconstruction while a lateral current flows through the sample. On the reconstruction and across domain boundaries we find that µec shows a constant gradient as a function of the position between the contacts. In addition, nanoscale Au clusters on the surface do not show an electronic coupling to the gold-induced surface reconstruction. In combination with high resolution scanning electron microscopy and transmission electron microscopy, we conclude that an additional transport channel buried about 2 nm underneath the surface represents a major transport channel for electrons. PMID:25247129

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

Kim, Moonsoo; Kim, Jongmin; Cho, Jaehee

Graphical abstract: The presence of Chlorine in the outer surface resulted in a highly electro-negative surface states and an increase in the vacuum energy level. - Highlights: • We investigated the influence of chlorine surface treatment on ITO properties. • Chlorination induced the change of the electro-static potential in the outer surface. • Chlorine electro-chemical treatment of ITO is a simple, fast and effective technique. - Abstract: In this work, we investigate the influence of a chlorine-based electro-chemical surface treatment on the characteristics of indium tin oxide (ITO) including the work function, chemical composition, and phase transition. The treated ITOsmore » were characterized using X-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS), 4-point probe measurements, and grazing incidence X-ray diffraction (GI-XRD). We confirmed a change of the chemical composition in the near-surface region of the ITO and the formation of indium-chlorine (In-Cl) bonds and surface dipoles (via XPS). In particular, the change of the electro-static potential in the outer surface was caused by chlorination. Due to the vacuum-level shift after the electro-chemical treatment in a dilute hydrochloric acid, the ITO work function was increased by ∼0.43 eV (via UPS); furthermore, the electro-negativity of the chlorine anions attracted electrons to emit them from the hole transport layer (HTL) to the ITO anodes, resulting in an increase of the hole-injection efficiency.« less

Highly reproducible surface-enhanced Raman scattering-active Au nanostructures prepared by simple electrodeposition: origin of surface-enhanced Raman scattering activity and applications as electrochemical substrates.

PubMed

Choi, Suhee; Ahn, Miri; Kim, Jongwon

2013-05-24

The fabrication of effective surface-enhanced Raman scattering (SERS) substrates has been the subject of intensive research because of their useful applications. In this paper, dendritic gold (Au) rod (DAR) structures prepared by simple one-step electrodeposition in a short time were examined as an effective SERS-active substrate. The SERS activity of the DAR surfaces was compared to that of other nanostructured Au surfaces with different morphologies, and its dependence on the structural variation of DAR structures was examined. These comparisonal investigations revealed that highly faceted sharp edge sites present on the DAR surfaces play a critical role in inducing a high SERS activity. The SERS enhancement factor was estimated to be greater than 10(5), and the detection limit of rhodamine 6G at DAR surfaces was 10(-8)M. The DAR surfaces exhibit excellent spot-to-spot and substrate-to-substrate SERS enhancement reproducibility, and their long-term stability is very good. It was also demonstrated that the DAR surfaces can be effectively utilized in electrochemical SERS systems, wherein a reversible SERS behavior was obtained during the cycling to cathodic potential regions. Considering the straightforward preparation of DAR substrates and the clean nature of SERS-active Au surfaces prepared in the absence of additives, we expect that DAR surfaces can be used as cost-effective SERS substrates in analytical and electrochemical applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Disordered array of Au covered Silicon nanowires for SERS biosensing combined with electrochemical detection

NASA Astrophysics Data System (ADS)

Convertino, Annalisa; Mussi, Valentina; Maiolo, Luca

2016-04-01

We report on highly disordered array of Au coated silicon nanowires (Au/SiNWs) as surface enhanced Raman scattering (SERS) probe combined with electrochemical detection for biosensing applications. SiNWs, few microns long, were grown by plasma enhanced chemical vapor deposition on common microscope slides and covered by Au evaporated film, 150 nm thick. The capability of the resulting composite structure to act as SERS biosensor was studied via the biotin-avidin interaction: the Raman signal obtained from this structure allowed to follow each surface modification step as well as to detect efficiently avidin molecules over a broad range of concentrations from micromolar down to the nanomolar values. The metallic coverage wrapping SiNWs was exploited also to obtain a dual detection of the same bioanalyte by electrochemical impedance spectroscopy (EIS). Indeed, the SERS signal and impedance modifications induced by the biomolecule perturbations on the metalized surface of the NWs were monitored on the very same three-electrode device with the Au/SiNWs acting as both working electrode and SERS probe.

Post oxygen treatment characteristics of coke as an anode material for Li-ion batteries.

PubMed

Kim, Jae-Hun; Park, Min-Sik; Jo, Yong Nam; Yu, Ji-Sang; Jeong, Goojin; Kim, Young-Jun

2013-05-01

The effect of a oxygen treatment on the electrochemical characteristics of a soft carbon anode material for Li-ion batteries was investigated. After a coke carbonization process at 1000 degrees C in an argon atmosphere, the samples were treated under a flow of oxygen gas to obtain a mild oxidation effect. After this oxygen treatment, the coke samples exhibited an improved initial coulombic efficiency and cycle performance as compared to the carbonized sample. High-resolution transmission electron microscopy revealed that the carbonized cokes consisted of disordered and nanosized graphene layers and the surface of the modified carbon was significantly changed after the treatment. The chemical state of the cokes was analyzed using X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The enhanced electrochemical properties of the surface modified cokes could be attributed to the mild oxidation effect induced by the oxygen treatment. The mild oxidation process could have led to the elimination of surface imperfections and the reinforcement of a solid electrolyte interphase film, which resulted in the improved electrochemical characteristics.

Can solvent induced surface modifications applied to screen-printed platforms enhance their electroanalytical performance?

PubMed

Blanco, Elias; Foster, Christopher W; Cumba, Loanda R; do Carmo, Devaney R; Banks, Craig E

2016-04-25

In this paper the effect of solvent induced chemical surface enhancements upon graphitic screen-printed electrodes (SPEs) is explored. Previous literature has indicated that treating the working electrode of a SPE with the solvent N,N-dimethylformamide (DMF) offers improvements within the electroanalytical response, resulting in a 57-fold increment in the electrode surface area compared to their unmodified counterparts. The protocol involves two steps: (i) the SPE is placed into DMF for a selected time, and (ii) it is cured in an oven at a selected time and temperature. Beneficial electroanalytical outputs are reported to be due to the increased surface area attributed to the binder within the bulk surface of the SPEs dissolving out during the immersion step (step i). We revisit this exciting concept and explore these solvent induced chemical surface enhancements using edge- and basal-plane like SPEs and a new bespoke SPE, utilising the solvent DMF and explore, in detail, the parameters utilised in steps (i) and (ii). The electrochemical performance following steps (i) and (ii) is evaluated using the outer-sphere redox probe hexaammineruthenium(iii) chloride/0.1 M KCl, where it is found that the largest improvement is obtained using DMF with an immersion time of 10 minutes and a curing time of 30 minutes at 100 °C. Solvent induced chemical surface enhancement upon the electrochemical performance of SPEs is also benchmarked in terms of their electroanalytical sensing of NADH (dihydronicotinamide adenine dinucleotide reduced form) and capsaicin both of which are compared to their unmodified SPE counterparts. In both cases, it is apparent that a marginal improvement in the electroanalytical sensitivity (i.e. gradient of calibration plots) of 1.08-fold and 1.38-fold are found respectively. Returning to the original exciting concept, interestingly it was found that when a poor experimental technique was employed, only then significant increases within the working electrode area are evident. In this case, the insulating layer that defines the working electrode surface, which was not protected from the solvent (step (i)) creates cracks within the insulating layer exposing the underlying carbon connections and thus increasing the electrode area by an unknown quantity. We infer that the origin of the response reported within the literature, where an extreme increase in the electrochemical surface area (57-fold) was reported, is unlikely to be solely due to the binder dissolving but rather poor experimental control over step (i).

High Electrochemical Sensitivity of TiO2- x Nanosheets and an Electron-Induced Mutual Interference Effect toward Heavy Metal Ions Demonstrated Using X-ray Absorption Fine Structure Spectra.

PubMed

Zhou, Wen-Yi; Li, Shan-Shan; Song, Jie-Yao; Jiang, Min; Jiang, Tian-Jia; Liu, Jin-Yun; Liu, Jin-Huai; Huang, Xing-Jiu

2018-04-03

Mutual interference is a severe issue that occurs during the electrochemical detection of heavy metal ions. This limitation presents a notable drawback for its high sensitivity to specific targets. Here, we present a high electrochemical sensitivity of ∼237.1 μA cm -2 μM -1 toward copper(II) [Cu(II)] based on oxygen-deficient titanium dioxide (TiO 2- x ) nanosheets. We fully demonstrated an atomic-level relationship between electrochemical behaviors and the key factors, including the high-energy (001) facet percentage, oxygen vacancy concentration, surface -OH content, and charge carrier density, is fully demonstrated. These four factors were quantified using Raman, electron spin resonance, X-ray photoelectron spectroscopy spectra, and Mott-Schottky plots. In the mutual interference investigation, we selected cadmium(II) [Cd(II)] as the target ion because of the significant difference in its stripping potential (∼700 mV). The results show that the Cd(II) can enhance the sensitivity of TiO 2- x nanosheets toward Cu(II), exhibiting an electron-induced mutual interference effect, as demonstrated by X-ray absorption fine structure spectra.

GaN light-emitting device based on ionic liquid electrolyte

NASA Astrophysics Data System (ADS)

Hirai, Tomoaki; Sakanoue, Tomo; Takenobu, Taishi

2018-06-01

Ionic liquids (ILs) are attractive materials for fabricating unique hybrid devices based on electronics and electrochemistry; thus, IL-gated transistors and organic light-emitting devices of light-emitting electrochemical cells (LECs) are investigated for future low-voltage and high-performance devices. In LECs, voltage application induces the formation of electrochemically doped p–n homojunctions owing to ion rearrangements in composites of semiconductors and electrolytes, and achieves electron–hole recombination for light emission at the homojunctions. In this work, we applied this concept of IL-induced electrochemical doping to the fabrication of GaN-based light-emitting devices. We found that voltage application to the layered IL/GaN structure accumulated electrons on the GaN surface owing to ion rearrangements and improved the conductivity of GaN. The ion rearrangement also enabled holes to be injected by the strong electric field of electric double layers on hole injection contacts. This simultaneous injection of holes and electrons into GaN mediated by ions achieves light emission at a low voltage of around 3.4 V. The light emission from the simple IL/GaN structure indicates the usefulness of an electrochemical technique in generating light emission with great ease of fabrication.

Electrochemically induced disintegration of layer-by-layer-assembled thin films composed of 2-iminobiotin-labeled poly(ethyleneimine) and avidin.

PubMed

Sato, Katsuhiko; Kodama, Daisuke; Naka, Yukihisa; Anzai, Jun-ichi

2006-12-01

A layer-by-layer assembly composed of avidin and 2-iminobiotin-labeled poly(ethyleneimine) (ib-PEI) was prepared on the surface of a platinum (Pt) film-coated quartz resonator, and an electrochemically induced disintegration of the avidin-ib-PEI assembly was studied using a quartz crystal microbalance. The resonance frequency of a five-bilayer (avidin-ib-PEI)5 film-coated quartz resonator was increased upon application of an electric potential to the Pt layer of the quartz resonator, suggesting that the mass on the quartz resonator was decreased as a result of disintegration of the (avidin-ib-PEI)5 film, due to a pH change in the vicinity of the surface of the Pt-coated quartz resonator. It may be that the (avidin-ib-PEI)5 film assembly was decomposed by acidification of the local pH on the surface of the Pt layer, which in turn was induced through electrolysis of water on Pt, because ib-PEI forms complexes with avidin only in basic media. In pH 9 solution, the (avidin-ib-PEI)5 film was decomposed under the influence of an applied potential of 0.6-1.0 V versus Ag/AgCl. The (avidin-ib-PEI)5 film was decomposed almost completely within a minute in a low concentration buffer (1 mM, pH 9), while the decomposition was slower in 10 and 100 mM buffer solutions at the same pH. The decomposition of the assembly was rapid when the electrode potential was applied in pH 9 solutions, while the response was relatively slow in pH 10 and 11 solutions. All the results are rationalized on the basis of an electrochemically induced acidification of the local environment around the (avidin-ib-PEI)5 film on the Pt layer.

Active and stable Ir@Pt core–shell catalysts for electrochemical oxygen reduction

DOE PAGES

Strickler, Alaina L.; Jackson, Ariel; Jaramillo, Thomas F.

2016-12-28

Electrochemical oxygen reduction is an important reaction for many sustainable energy technologies, such as fuel cells and metal–air batteries. Kinetic limitations of this reaction, expensive electrocatalysts, and catalyst instability, however, limit the commercial viability of such devices. Herein, we report an active Ir@Pt core–shell catalyst that combines platinum overlayers with nanostructure effects to tune the oxygen binding to the Pt surface, thereby achieving enhanced activity and stability for the oxygen reduction reaction. Ir@Pt nanoparticles with several shell thicknesses were synthesized in a scalable, inexpensive, one-pot polyol method. Electrochemical analysis demonstrates the activity and stability of the Ir@Pt catalyst, with specificmore » and mass activities increasing to 2.6 and 1.8 times that of commercial Pt/C (TKK), respectively, after 10 000 stability cycles. Furthermore, activity enhancement of the Ir@Pt catalyst is attributed to weakening of the oxygen binding to the Pt surface induced by the Ir core.« less

New insights on laser-induced graphene electrodes for flexible supercapacitors: tunable morphology and physical properties.

PubMed

Lamberti, Andrea; Perrucci, Francesco; Caprioli, Matteo; Serrapede, Mara; Fontana, Marco; Bianco, Stefano; Ferrero, Sergio; Tresso, Elena

2017-04-28

In certain polymers the graphenization of carbon atoms can be obtained by laser writing owing to the easy absorption of long-wavelength radiation, which generates photo-thermal effects. On a polyimide surface this process allows the formation of a nanostructured and porous carbon network known as laser-induced graphene (LIG). Herein we report on the effect of the process parameters on the morphology and physical properties of LIG nanostructures. We show that the scan speed and the frequency of the incident radiation affect the gas evolution, inducing different structure rearrangements, an interesting nitrogen self-doping phenomenon and consequently different conduction properties. The materials were characterized by infrared and Raman spectroscopy, XPS elemental analysis, electron microscopy and electrical/electrochemical measurements. In particular the samples were tested as interdigitated electrodes into electrochemical supercapacitors and the optimized LIG arrangement was tested in parallel and series supercapacitor configurations to allow power exploitation.

Pressure-induced switching in ferroelectrics: Phase-field modeling, electrochemistry, flexoelectric effect, and bulk vacancy dynamics

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

Cao, Ye; Morozovska, Anna; Kalinin, Sergei V.

Pressure-induced polarization switching in ferroelectric thin films has emerged as a powerful method for domain patterning, allowing us to create predefined domain patterns on free surfaces and under thin conductive top electrodes. However, the mechanisms for pressure-induced polarization switching in ferroelectrics remain highly controversial, with flexoelectricity, polarization rotation and suppression, and bulk and surface electrochemical processes all being potentially relevant. Here we classify possible pressure-induced switching mechanisms, perform elementary estimates, and study in depth using phase-field modeling. Finally, we show that magnitudes of these effects are remarkably close and give rise to complex switching diagrams as a function of pressuremore » and film thickness with nontrivial topology or switchable and nonswitchable regions.« less

Pressure-induced switching in ferroelectrics: Phase-field modeling, electrochemistry, flexoelectric effect, and bulk vacancy dynamics

DOE PAGES

Cao, Ye; Morozovska, Anna; Kalinin, Sergei V.

2017-11-01

Pressure-induced polarization switching in ferroelectric thin films has emerged as a powerful method for domain patterning, allowing us to create predefined domain patterns on free surfaces and under thin conductive top electrodes. However, the mechanisms for pressure-induced polarization switching in ferroelectrics remain highly controversial, with flexoelectricity, polarization rotation and suppression, and bulk and surface electrochemical processes all being potentially relevant. Here we classify possible pressure-induced switching mechanisms, perform elementary estimates, and study in depth using phase-field modeling. Finally, we show that magnitudes of these effects are remarkably close and give rise to complex switching diagrams as a function of pressuremore » and film thickness with nontrivial topology or switchable and nonswitchable regions.« less

Morphology, Composition, and Bioactivity of Strontium-Doped Brushite Coatings Deposited on Titanium Implants via Electrochemical Deposition

PubMed Central

Liang, Yongqiang; Li, Haoyan; Xu, Jiang; Li, Xin; Qi, Mengchun; Hu, Min

2014-01-01

Surface modification techniques have been applied to generate titanium implant surfaces that promote osseointegration for use in dental applications. In this study, strontium-doped brushite coatings were deposited on titanium by electrochemical deposition. The phase composition of the coating was investigated by energy dispersive X-ray spectroscopy and X-ray diffraction. The surface morphologies of the coatings were studied through scanning electron microscopy, and the cytocompatibility and bioactivity of the strontium-doped brushite coatings were evaluated using cultured osteoblasts. Osteoblast proliferation was enhanced by the addition of strontium, suggesting a possible mechanism by which strontium incorporation in brushite coatings increased bone formation surrounding the implants. Cell growth was also strongly influenced by the composition of the deposited coatings, with a 10% Sr-doped brushite coating inducing the greatest amount of bone formation among the tested materials. PMID:24901526

Hydrogen-Induced Plastic Deformation in ZnO

NASA Astrophysics Data System (ADS)

Lukáč, F.; Čížek, J.; Vlček, M.; Procházka, I.; Anwand, W.; Brauer, G.; Traeger, F.; Rogalla, D.; Becker, H.-W.

In the present work hydrothermally grown ZnO single crystals covered with Pd over-layer were electrochemically loaded with hydrogen and the influence of hydrogen on ZnO micro structure was investigated by positron annihilation spectroscopy (PAS). Nuclear reaction analysis (NRA) was employed for determination of depth profile of hydrogen concentration in the sample. NRA measurements confirmed that a substantial amount of hydrogen was introduced into ZnO by electrochemical charging. The bulk hydrogen concentration in ZnO determined by NRA agrees well with the concentration estimated from the transported charge using the Faraday's law. Moreover, a subsurface region with enhanced hydrogen concentration was found in the loaded crystals. Slow positron implantation spectroscopy (SPIS) investigations of hydrogen-loaded crystal revealed enhanced concentration of defects in the subsurface region. This testifies hydrogen-induced plastic deformation of the loaded crystal. Absorbed hydrogen causes a significant lattice expansion. At low hydrogen concentrations this expansion is accommodated by elastic straining, but at higher concentrations hydrogen-induced stress exceeds the yield stress in ZnO and plastic deformation of the loaded crystal takes place. Enhanced hydrogen concentration detected in the subsurface region by NRA is, therefore, due to excess hydrogen trapped at open volume defects introduced by plastic deformation. Moreover, it was found that hydrogen-induced plastic deformation in the subsurface layer leads to typical surface modification: formation of hexagonal shape pyramids on the surface due to hydrogen-induced slip in the [0001] direction.

Phase-field modeling of chemical control of polarization stability and switching dynamics in ferroelectric thin films

DOE PAGES

Cao, Ye; Kalinin, Sergei V.

2016-12-15

Phase-field simulation (PFS) has revolutionized the understanding of domain structure and switching behavior in ferroelectric thin films and ceramics. Generally, PFS is based on the solution of (a set of) Landau-Ginzburg-Devonshire equations for a defined order parameter field(s) under physical boundary conditions (BCs) of fixed potential or charge. While well matched to the interfaces in bulk materials and devices, these BCs are generally not applicable to free ferroelectric surfaces. Here, we developed a self-consistent phase-field model with BCs based on electrochemical equilibria. We chose Pb(Zr 0.2Ti 0.8)O 3 ultrathin film consisting of (001) oriented single tetragonal domain ( Pz) asmore » a model system and systematically studied the effects of oxygen partial pressure, temperature, and surface ions on the ferroelectric state and compared it with the case of complete screening. We have further explored the polarization switching induced by the oxygen partial pressure and observed pronounced size effect induced by chemical screening. Finally, our paper thus helps to understand the emergent phenomena in ferroelectric thin films brought about by the electrochemical ionic surface compensations.« less

Phase-field modeling of chemical control of polarization stability and switching dynamics in ferroelectric thin films

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

Cao, Ye; Kalinin, Sergei V.

Phase-field simulation (PFS) has revolutionized the understanding of domain structure and switching behavior in ferroelectric thin films and ceramics. Generally, PFS is based on the solution of (a set of) Landau-Ginzburg-Devonshire equations for a defined order parameter field(s) under physical boundary conditions (BCs) of fixed potential or charge. While well matched to the interfaces in bulk materials and devices, these BCs are generally not applicable to free ferroelectric surfaces. Here, we developed a self-consistent phase-field model with BCs based on electrochemical equilibria. We chose Pb(Zr 0.2Ti 0.8)O 3 ultrathin film consisting of (001) oriented single tetragonal domain ( Pz) asmore » a model system and systematically studied the effects of oxygen partial pressure, temperature, and surface ions on the ferroelectric state and compared it with the case of complete screening. We have further explored the polarization switching induced by the oxygen partial pressure and observed pronounced size effect induced by chemical screening. Finally, our paper thus helps to understand the emergent phenomena in ferroelectric thin films brought about by the electrochemical ionic surface compensations.« less

Dissolution-Induced Nanowire Synthesis on Hot-Dip Galvanized Surface in Supercritical Carbon Dioxide.

PubMed

Kaleva, Aaretti; Saarimaa, Ville; Heinonen, Saara; Nikkanen, Juha-Pekka; Markkula, Antti; Väisänen, Pasi; Levänen, Erkki

2017-07-11

In this study, we demonstrate a rapid treatment method for producing a needle-like nanowire structure on a hot-dip galvanized sheet at a temperature of 50 °C. The processing method involved only supercritical carbon dioxide and water to induce a reaction on the zinc surface, which resulted in growth of zinc hydroxycarbonate nanowires into flower-like shapes. This artificial patina nanostructure predicts high surface area and offers interesting opportunities for its use in industrial high-end applications. The nanowires can significantly improve paint adhesion and promote electrochemical stability for organic coatings, or be converted to ZnO nanostructures by calcining to be used in various semiconductor applications.

Dissolution-Induced Nanowire Synthesis on Hot-Dip Galvanized Surface in Supercritical Carbon Dioxide

PubMed Central

Saarimaa, Ville; Heinonen, Saara; Nikkanen, Juha-Pekka; Markkula, Antti; Väisänen, Pasi; Levänen, Erkki

2017-01-01

In this study, we demonstrate a rapid treatment method for producing a needle-like nanowire structure on a hot-dip galvanized sheet at a temperature of 50 °C. The processing method involved only supercritical carbon dioxide and water to induce a reaction on the zinc surface, which resulted in growth of zinc hydroxycarbonate nanowires into flower-like shapes. This artificial patina nanostructure predicts high surface area and offers interesting opportunities for its use in industrial high-end applications. The nanowires can significantly improve paint adhesion and promote electrochemical stability for organic coatings, or be converted to ZnO nanostructures by calcining to be used in various semiconductor applications. PMID:28696374

Nanoscale mapping of electromechanical response in ionic conductive ceramics with piezoelectric inclusions

DOE PAGES

Seol, Daehee; Seo, Hosung; Jesse, Stephen; ...

2015-08-19

Electromechanical (EM) response in ion conductive ceramics with piezoelectric inclusions was spatially explored using strain-based atomic force microscopy. Since the sample is composed of two dominant phases of ionic and piezoelectric phases, it allows us to explore two different EM responses of electrically induced ionic response and piezoresponse over the same surface. Furthermore, EM response of the ionic phase, i.e., electrochemical strain, was quantitatively investigated from the comparison with that of the piezoelectric phase, i.e., piezoresponse. Finally, these results could provide additional information on the EM properties, including the electrochemical strain at nanoscale.

Nanoscale mapping of electromechanical response in ionic conductive ceramics with piezoelectric inclusions

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

Seol, Daehee; Seo, Hosung; Jesse, Stephen

Electromechanical (EM) response in ion conductive ceramics with piezoelectric inclusions was spatially explored using strain-based atomic force microscopy. Since the sample is composed of two dominant phases of ionic and piezoelectric phases, it allows us to explore two different EM responses of electrically induced ionic response and piezoresponse over the same surface. Furthermore, EM response of the ionic phase, i.e., electrochemical strain, was quantitatively investigated from the comparison with that of the piezoelectric phase, i.e., piezoresponse. Finally, these results could provide additional information on the EM properties, including the electrochemical strain at nanoscale.

Nanoscale mapping of electromechanical response in ionic conductive ceramics with piezoelectric inclusions

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

Seol, Daehee; Seo, Hosung; Kim, Yunseok, E-mail: yunseokkim@skku.edu

Electromechanical (EM) response in ion conductive ceramics with piezoelectric inclusions was spatially explored using strain-based atomic force microscopy. Since the sample is composed of two dominant phases of ionic and piezoelectric phases, it allows us to explore two different EM responses of electrically induced ionic response and piezoresponse over the same surface. Furthermore, EM response of the ionic phase, i.e., electrochemical strain, was quantitatively investigated from the comparison with that of the piezoelectric phase, i.e., piezoresponse. These results could provide additional information on the EM properties, including the electrochemical strain at nanoscale.

Electrochemically hydrogenated TiO2 nanotubes with improved photoelectrochemical water splitting performance

PubMed Central

2013-01-01

One-dimensional anodic titanium oxide (ATO) nanotube arrays hold great potential as photoanode for photoelectrochemical (PEC) water splitting. In this work, we report a facile and eco-friendly electrochemical hydrogenation method to modify the electronic and PEC properties of ATO nanotube films. The hydrogenated ATO (ATO-H) electrodes present a significantly improved photocurrent of 0.65 mA/cm2 in comparison with that of pristine ATO nanotubes (0.29 mA/cm2) recorded under air mass 1.5 global illumination. The incident photon-to-current efficiency measurement suggests that the enhanced photocurrent of ATO-H nanotubes is mainly ascribed to the improved photoactivity in the UV region. We propose that the electrochemical hydrogenation induced surface oxygen vacancies contribute to the substantially enhanced electrical conductivity and photoactivity. PMID:24047205

In situ monitoring magnetism and resistance of nanophase platinum upon electrochemical oxidation.

PubMed

Steyskal, Eva-Maria; Topolovec, Stefan; Landgraf, Stephan; Krenn, Heinz; Würschum, Roland

2013-01-01

Controlled tuning of material properties by external stimuli represents one of the major topics of current research in the field of functional materials. Electrochemically induced property tuning has recently emerged as a promising pathway in this direction making use of nanophase materials with a high fraction of electrode-electrolyte interfaces. The present letter reports on electrochemical property tuning of porous nanocrystalline Pt. Deeper insight into the underlying processes could be gained by means of a direct comparison of the charge-induced response of two different properties, namely electrical resistance and magnetic moment. For this purpose, four-point resistance measurements and SQUID magnetometry were performed under identical in situ electrochemical control focussing on the regime of electrooxidation. Fully reversible variations of the electrical resistance and the magnetic moment of 6% and 1% were observed upon the formation or dissolution of a subatomic chemisorbed oxygen surface layer, respectively. The increase of the resistance, which is directly correlated to the amount of deposited oxygen, is considered to be primarily caused by charge-carrier scattering processes at the metal-electrolyte interfaces. In comparison, the decrease of the magnetic moment upon positive charging appears to be governed by the electric field at the nanocrystallite-electrolyte interfaces due to spin-orbit coupling.

Electrochemical detection of Nanog in cell extracts via target-induced resolution of an electrode-bound DNA pseudoknot.

PubMed

Ma, Jiehua; Li, Chao; Tao, Yaqin; Feng, Chang; Li, Genxi

2016-12-15

Nanog is among the most important indicators of cell pluripotency and self-renew, so detection of Nanog is critical for tumor assessment and monitoring of clinical prognosis. In this work, a novel method for Nanog detection is proposed by using electrochemical technique based on target-induced conformational change of an electrode-bound DNA pseudoknot. In the absence of Nanog, the rigid structure of the pseudoknot will minimize the connection between the redox tag and the electrode, thus reducing the obtained faradaic current. Nevertheless, the Nanog binding may liberate the flexible single-stranded element that transforms the DNA pesudokont into DNA hairpin structure due to steric hindrance effect, thus making the electrochemical tag close to the electrode surface. Consequently, electron transfer can be enhanced and very well electrochemical response can be observed. By using the proposed method, Nanog can be determined in a linear range from 2nM to 25nM with a detection limit of 163 pM. Furthermore, the proposed method can be directly used to assay Nanog not only in purified samples but also in complex media (cell extracts), which shows potential applications in Nanog functional studies as well as clinical diagnosis in the future. Copyright © 2016 Elsevier B.V. All rights reserved.

Rolling chain amplification based signal-enhanced electrochemical aptasensor for ultrasensitive detection of ochratoxin A.

PubMed

Huang, Lin; Wu, Jingjing; Zheng, Lei; Qian, Haisheng; Xue, Feng; Wu, Yucheng; Pan, Daodong; Adeloju, Samuel B; Chen, Wei

2013-11-19

A novel electrochemical aptasensor is described for rapid and ultrasensitive detection of ochratoxin A (OTA) based on signal enhancement with rolling circle amplification (RCA). The primer for RCA was designed to compose of a two-part sequence, one part of the aptamer sequence directed against OTA while the other part was complementary to the capture probe on the electrode surface. In the presence of target OTA, the primer, originally hybridized with the RCA padlock, is replaced to combine with OTA. This induces the inhibition of RCA and decreases the OTA sensing signal obtained with the electrochemical aptasensor. Under the optimized conditions, ultrasensitive detection of OTA was achieved with a limit of detection (LOD) of 0.065 ppt (pg/mL), which is much lower than previously reported. The electrochemical aptasensor was also successfully applied to the determination of OTA in wine samples. This ultrasensitive electrochemical aptasensor is of great practical importance in food safety and could be widely extended to the detection of other toxins by replacing the sequence of the recognition aptamer.

Ultrasensitive one-step rapid detection of ochratoxin A by the folding-based electrochemical aptasensor.

PubMed

Wu, Jingjing; Chu, Huaqin; Mei, Zhanlong; Deng, Yi; Xue, Feng; Zheng, Lei; Chen, Wei

2012-11-13

A one-step electrochemical aptasensor using the thiol- and methylene blue- (MB-) dual-labeled aptamer modified gold electrode for determination of ochratoxin A (OTA) was presented in this research. The aptamer against OTA was covalently immobilized on the surface of the electrode by the self-assembly effect and used as recognition probes for OTA detection by the binding induced folding of the aptamer. Under the optimal conditions, the developed electrochemical aptasensor demonstrated a wide linear range from 0.1 pg mL(-1) to 1000 pg mL(-1) with the limit of detection (LOD) of 0.095 pg mL(-1), which was an extraordinary sensitivity compared with other common methods for OTA detection. Moreover, as a practical application, this proposed electrochemical aptasensor was used to monitor the OTA level in red wine samples without any special pretreatment and with satisfactory results obtained. Study results showed that this electrochemical aptasensor could be a potential useful platform for on-site OTA measurement in real complex samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study.

PubMed

Jovanovič, Primož; Hodnik, Nejc; Ruiz-Zepeda, Francisco; Arčon, Iztok; Jozinović, Barbara; Zorko, Milena; Bele, Marjan; Šala, Martin; Šelih, Vid Simon; Hočevar, Samo; Gaberšček, Miran

2017-09-13

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO 2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

Principles and applications of laser-induced liquid-phase jet-chemical etching

NASA Astrophysics Data System (ADS)

Stephen, Andreas; Metev, Simeon; Vollertsen, Frank

2003-11-01

In this treatment method laser radiation, which is guided from a coaxially expanding liquid jet-stream, locally initiates a thermochemical etching reaction on a metal surface, which leads to selective material removal at high resolution and quality of the treated surface as well as low thermal influence on the workpiece. Electrochemical investigations were performed under focused laser irradiation using a cw-Nd:YAG laser with a maximum power of 15 W and a simultaneous impact of the liquid jet-stream consisting of phosphoric acid with a maximum flow rate of 20 m/s. The time resolved measurements of the electrical potential difference against an electrochemical reference electrode were correlated with the specific processing parameters and corresponding etch rates to identify processing conditions for temporally stable and enhanced chemical etching reactions. Applications of laser-induced liquid-phase jet-chemical etching in the field of sensor technology, micromechanics and micrmoulding technology are presented. This includes the microstructuring of thin film systems, cutting of foils of shape memory alloys or the generation of structures with defined shape in bulk material.

Influence of aggressive ions on the degradation behavior of biomedical magnesium alloy in physiological environment.

PubMed

Xin, Yunchang; Huo, Kaifu; Tao, Hu; Tang, Guoyi; Chu, Paul K

2008-11-01

Various electrochemical approaches, including potentiodynamic polarization, open circuit potential evolution and electrochemical impedance spectroscopy (EIS), are employed to investigate the degradation behavior of biomedical magnesium alloy under the influence of aggressive ions, such as chloride, phosphate, carbonate and sulfate, in a physiological environment. The synergetic effects and mutual influence of these ions on the degradation behavior of Mg are revealed. Our results demonstrate that chloride ions can induce porous pitting corrosion. In the presence of phosphates, the corrosion rate decreases and the formation of pitting corrosion is significantly delayed due to precipitation of magnesium phosphate. Hydrogen carbonate ions are observed to stimulate the corrosion of magnesium alloy during the early immersion stage but they can also induce rapid passivation on the surface. This surface passivation behavior mainly results from the fast precipitation of magnesium carbonate in the corrosion product layer that can subsequently inhibit pitting corrosion completely. Sulfate ions are also found to stimulate magnesium dissolution. These results improve our understanding on the degradation mechanism of surgical magnesium in the physiological environment.

Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries

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

Weinrich, Henning; Come, Jérémy; Tempel, Hermann

Iron-air cells provide a promising and resource-efficient alternative battery concept with superior area specific power density characteristics compared to state-of-the-art Li-air batteries and potentially superior energy density characteristics compared to present Li-ion batteries. Understanding charge-transfer reactions at the anode-electrolyte interface is the key to develop high-performance cells. By employing in-situ electrochemical atomic force microscopy (in-situ EC-AFM), in-depth insight into the electrochemically induced surface reaction processes on iron in concentrated alkaline electrolyte is obtained. The results highlight the formation and growth of the redox-layer on iron over the course of several oxidation/reduction cycles. By this means, a direct correlation between topographymore » changes and the corresponding electrochemical reactions at the nanoscale could unambiguously be established. Here in this paper, the twofold character of the nanoparticulate redox-layer in terms of its passivating character and its contribution to the electrochemical reactions is elucidated. Furthermore, the evolution of single nanoparticles on the iron electrode surface is evaluated in unprecedented and artifact-free detail. Based on the dedicated topography analysis, a detailed structural model for the evolution of the redox-layer which is likewise elementary for corrosion science and battery research is derived.« less

Structural Evolution of Li xNi yMn zCo 1-y-zO 2 Cathode Materials during High-Rate Charge and Discharge

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

Hwang, Sooyeon; Jo, Eunmi; Chung, Kyung Yoon

Ni-rich lithium transition metal oxides have received significant attention due to their high capacities and rate capabilities determined via theoretical calculations. Although the structural properties of these materials are strongly correlated with the electrochemical performance, their structural stability during the high-rate electrochemical reactions has not been fully evaluated yet. In this work, transmission electron microscopy is used to investigate the crystallographic and electronic structural modifications of Ni-based cathode materials at a high charge/discharge rate of 10 C. It is found that the high-rate electrochemical reactions induce structural inhomogeneity near the surface of Ni-rich cathode materials, which limits Li transport andmore » reduces their capacities. Furthermore, this study establishes a correlation between the high-rate electrochemical performance of the Ni-based materials and their structural evolution, which can provide profound insights for designing novel cathode materials having both high energy and power densities.« less

Structural Evolution of Li xNi yMn zCo 1-y-zO 2 Cathode Materials during High-Rate Charge and Discharge

DOE PAGES

Hwang, Sooyeon; Jo, Eunmi; Chung, Kyung Yoon; ...

2017-11-08

Ni-rich lithium transition metal oxides have received significant attention due to their high capacities and rate capabilities determined via theoretical calculations. Although the structural properties of these materials are strongly correlated with the electrochemical performance, their structural stability during the high-rate electrochemical reactions has not been fully evaluated yet. In this work, transmission electron microscopy is used to investigate the crystallographic and electronic structural modifications of Ni-based cathode materials at a high charge/discharge rate of 10 C. It is found that the high-rate electrochemical reactions induce structural inhomogeneity near the surface of Ni-rich cathode materials, which limits Li transport andmore » reduces their capacities. Furthermore, this study establishes a correlation between the high-rate electrochemical performance of the Ni-based materials and their structural evolution, which can provide profound insights for designing novel cathode materials having both high energy and power densities.« less

Interfacial nano-mixing in a miniaturised platform enables signal enhancement and in situ detection of cancer biomarkers.

PubMed

Wuethrich, Alain; Sina, Abu Ali Ibn; Ahmed, Mostak; Lin, Ting-Yun; Carrascosa, Laura G; Trau, Matt

2018-06-14

Interfacial biosensing performs the detection of biomolecules at the bare-metal interface for disease diagnosis by comparing how biological species derived from patients and healthy individuals interact with bare metal surfaces. This technique retrieves clinicopathological information without complex surface functionalisation which is a major limitation of conventional techniques. However, it is still challenging to detect subtle molecular changes by interfacial biosensing, and the detection often requires prolonged sensing times due to the slow diffusion process of the biomolecules towards the sensor surface. Herein, we report on a novel strategy for interfacial biosensing which involves in situ electrochemical detection under the action of an electric field-induced nanoscopic flow at nanometre distance to the sensing surface. This nanomixing significantly increases target adsorption, reduces sensing time, and enables the detection of small molecular changes with enhanced sensitivity. Using a multiplex electrochemical microdevice that enables nanomixing and in situ label-free electrochemical detection, we demonstrate the detection of multiple cancer biomarkers on the same device. We present data for the detection of aberrant phosphorylation in the EGFR protein and hypermethylation in the EN1 gene region. Our method significantly shortens the assay period (from 40 min and 20 min to 3 minutes for protein and DNA, respectively), increases the sensitivity by up to two orders of magnitude, and improves detection specificity.

A Hierarchical Phosphorus Nanobarbed Nanowire Hybrid: Its Structure and Electrochemical Properties.

PubMed

Zhao, Dan; Li, Beibei; Zhang, Jinying; Li, Xin; Xiao, Dingbin; Fu, Chengcheng; Zhang, Lihui; Li, Zhihui; Li, Jun; Cao, Daxian; Niu, Chunming

2017-06-14

Nanostructured phosphorus-carbon composites are promising materials for Li-ion and Na-ion battery anodes. A hierarchical phosphorus hybrid, SiC@graphene@P, has been synthesized by the chemical vapor deposition of phosphorus on the surfaces of barbed nanowires, where the barbs are vertically grown graphene nanosheets and the cores are SiC nanowires. A temperature-gradient vaporization-condensation method has been used to remove the unhybridized phosphorus particles formed by homogeneous nucleation. The vertically grown barb shaped graphene nanosheets and a high concentration of edge carbon atoms induced a fibrous red phosphorus (f-RP) growth with its {001} planes in parallel to {002} planes of nanographene sheets and led to a strong interpenetrated interface interaction between phosphorus and the surfaces of graphene nanosheets. This hybridization has been demonstrated to significantly enhance the electrochemical performances of phosphorus.

The role of surface charging during the coadsorption of mercaptohexanol to DNA layers on gold: direct observation of desorption and layer reorientation.

PubMed

Arinaga, K; Rant, U; Tornow, M; Fujita, S; Abstreiter, G; Yokoyama, N

2006-06-20

We study the coadsorption of mercaptohexanol onto preimmobilized oligonucleotide layers on gold. Monitoring the position of the DNA relative to the surface by optical means directly shows the mercaptohexanol-induced desorption of DNA and the reorientation of surface-tethered strands in situ and in real time. By simultaneously recording the electrochemical electrode potential, we are able to demonstrate that changes in the layer conformation are predominantly of electrostatic origin and can be reversed by applying external bias to the substrate.

Elucidating the role of methyl viologen as a scavenger of photoactivated electrons from photosystem I under aerobic and anaerobic conditions.

PubMed

Bennett, Tyler; Niroomand, Hanieh; Pamu, Ravi; Ivanov, Ilia; Mukherjee, Dibyendu; Khomami, Bamin

2016-03-28

We present detailed electrochemical investigations into the role of dissolved O2 in electrolyte solutions in scavenging photoactivated electrons from a uniform photosystem I (PS I) monolayer assembled on alkanethiolate SAM (self-assembled monolayer)/Au surfaces while using methyl viologen (MV(2+)) as the redox mediator. To this end, we report results for direct measurements of light induced photocurrent from uniform monolayer assemblies of PS I on C9 alkanethiolate SAM/Au surfaces. These measurements, apart from demonstrating the ability of dissolved O2 in the electrolyte medium to act as an electron scavenger, also reveal its essential role in driving the solution-phase methyl viologen to initiate light-induced directional electron transfer from an electron donor surface (Au) via surface assembled PS I trimers. Specifically, our systematic electrochemical measurements have revealed that the dissolved O2 in aqueous electrolyte solutions form a complex intermediate species with MV that plays the essential role in mediating redox pathways for unidirectional electron transfer processes. This critical insight into the redox-mediated electron transfer pathways allows for rational design of electron scavengers through systematic tuning of mediator combinations that promote such intermediate formation. Our current findings facilitate the incorporation of PS I-based bio-hybrid constructs as photo-anodes in future photoelectrochemical cells and bio-electronic devices.

Pulse electrochemical meso/micro/nano ultraprecision machining technology.

PubMed

Lee, Jeong Min; Kim, Young Bin; Park, Jeong Woo

2013-11-01

This study demonstrated meso/micro/nano-ultraprecision machining through electrochemical reactions using intermittent DC pulses. The experiment focused on two machining methods: (1) pulse electrochemical polishing (PECP) of stainless steel, and (2) pulse electrochemical nano-patterning (PECNP) on a silicon (Si) surface, using atomic force microscopy (AFM) for fabrication. The dissolution reaction at the stainless steel surface following PECP produced a very clean, smooth workpiece. The advantages of the PECP process included improvements in corrosion resistance, deburring of the sample surface, and removal of hydrogen from the stainless steel surface as verified by time-of-flight secondary-ion mass spectrometry (TOF-SIMS). In PECNP, the electrochemical reaction generated within water molecules produced nanoscale oxide textures on a Si surface. Scanning probe microscopy (SPM) was used to evaluate nanoscale-pattern processing on a Si wafer surface produced by AFM-PECNP For both processes using pulse electrochemical reactions, three-dimensional (3-D) measurements and AFM were used to investigate the changes on the machined surfaces. Preliminary results indicated the potential for advancing surface polishing techniques and localized micro/nano-texturing technology using PECP and PECNP processes.

An investigation on the biotribocorrosion behaviour of CoCrMo alloy grafted with polyelectrolyte brush.

PubMed

Zhang, Hong-Yu; Zhu, Yu-Jiao; Hu, Xiang-Yu; Sun, Yan-Fang; Sun, Yu-Long; Han, Jian-Min; Yan, Yu; Zhou, Ming

2014-01-01

Surface grafting of polyelectrolyte brush, such as 3-sulfopropyl methacrylate potassium salt (SPMK), on hip implant materials has been reported to reduce the wear of the orthopaedic bearing surface. However, the biotribocorrosion behaviour of the SPMK brush has not been taken into consideration in previous research. In the present study, SPMK was grafted on Co28Cr6Mo alloy through photo-induced polymerization, and the biotribocorrosion behaviour was investigated by a series of frictional-electrochemical tests using a universal materials tester combined with an electrochemical measurement (three-electrode) system. Co28Cr6Mo disk and polyethylene (PE) pin were used as the contact pair, and the lubricants were 0.9% saline solution (NaCl) and 0.9% saline solution coupled with 25% bovine serum albumin (BSA). The results showed that SPMK was successfully grafted on Co28Cr6Mo alloy, which was confirmed by the comparison of Raman spectroscopy and static contact angle of the samples before and after surface modification. The greatly reduced electrochemical parameters such as corrosion current and pitting potential indicated that the corrosion rate of Co28Cr6Mo alloy was significantly reduced following SPMK grafting. Additionally, the frictional-electrochemical coupled measurement performed under reciprocating sliding demonstrated that the lowest corrosion current was obtained for the SPMK-grafted Co28Cr6Mo disk, with 0.9% NaCl coupled with 25% BSA as the electrolyte. It is indicated from the present study that SPMK polyelectrolyte brush can greatly improve the anti-biotribocorrosion properties of Co28Cr6Mo alloy, and thus has potential application on surface modification of hip implant materials.

Mechanism of Electrochemical Delamination of Two-Dimensional Materials from Their Native Substrates by Bubbling

PubMed Central

Sun, Jie; Fan, Xing; Guo, Weiling; Liu, Lihui; Liu, Xin; Deng, Jun; Xu, Chen

2015-01-01

A capacitor-based circuit model is proposed to explain the electrochemical delamination of two-dimensional materials from their native substrates where produced gas bubbles squeeze into the interface. The delamination is actually the electric breakdown of the capacitor formed between the solution and substrate. To facilitate the procedure, the backside of the ubstrate has to be shielded so that the capacitor breakdown voltage can be reached. The screening effect can be induced either by nonreactive ions around the electrode or, more effectively, by an undetachable insulator. This mechanism serves as a guideline for the surface science and applications involving the bubbling delamination. PMID:26694406

Mechanism of Electrochemical Delamination of Two-Dimensional Materials from Their Native Substrates by Bubbling.

PubMed

Sun, Jie; Fan, Xing; Guo, Weiling; Liu, Lihui; Liu, Xin; Deng, Jun; Xu, Chen

2015-12-16

A capacitor-based circuit model is proposed to explain the electrochemical delamination of two-dimensional materials from their native substrates where produced gas bubbles squeeze into the interface. The delamination is actually the electric breakdown of the capacitor formed between the solution and substrate. To facilitate the procedure, the backside of the ubstrate has to be shielded so that the capacitor breakdown voltage can be reached. The screening effect can be induced either by nonreactive ions around the electrode or, more effectively, by an undetachable insulator. This mechanism serves as a guideline for the surface science and applications involving the bubbling delamination.

The role of AlF3 coatings in improving electrochemical cycling of Li-enriched nickel-manganese oxide electrodes for Li-ion batteries.

PubMed

Sun, Yang-Kook; Lee, Min-Joon; Yoon, Chong S; Hassoun, Jusef; Amine, Khalil; Scrosati, Bruno

2012-03-02

A Li[Li(0.19)Ni(0.16)Co(0.08)Mn(0.57)]O(2) cathode was coated with AlF(3) on the surface. The AlF(3)-coating enhanced the overall electrochemical characteristics of the electrode while overcoming the typical shortcomings of lithium-enriched cathodes. This improvement was attributed to the transformation of the initial electrode layer to a spinel phase, induced by the Li chemical leaching effect of the AlF(3) coating layer. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene coatings for protection against microbiologically induced corrosion

NASA Astrophysics Data System (ADS)

Krishnamurthy, Ajay

Microbiologically induced corrosion (MIC) is a special form of electrochemical corrosion where micro-organisms affect the local environmental conditions at the metal-electrolyte interface by forming a stable biofilm. The biofilm introduces localized concentration cells, which accelerate the electrochemical corrosion rates. MIC has been found to affect many industrial systems such as sewage waste water pipes, heat exchangers, ships, underwater pipes etc. It has been traditionally eradicated by physical, biochemical and surface protection methods. The cleaning methods and the biocidal deliveries are required periodically and don't provide a permanent solution to the problem. Further, the use of biocides has been harshly criticized by environmentalists due to safety concerns associated with their usage. Surface based coatings have their own drawback of rapid degradation under harsh microbial environments. This has led to the exploration of thin, robust, inert, conformal passivation coatings for the protection of metallic surfaces from microbiologically induced corrosion. Graphene is a 2D arrangement of carbon atoms in a hexagonal honeycomb lattice. The carbon atoms are bonded to one another by sp2 hybridization and each layer of the carbon ring arrangement spans to a thickness of less than a nm. Due to its unique 2D arrangement of carbon atoms, graphene exhibits interesting in-plane and out of plane properties that have led to it being considered as the material for the future. Its excellent thermal, mechanical, electrical and optical properties are being explored in great depth to understand and realize potential applications in various technological realms. Early studies have shown the ability of bulk and monolayer graphene to protect metallic surfaces from air oxidation and solution based galvanic corrosion processes for short periods. However, the role of graphene in resisting MIC is yet to be determined, particularly over the long time spans characteristic of this form of corrosion. Chapter 1 introduces the basics of microbiologically induced corrosion and graphene. A comprehensive review of literature is used to discuss the role of micro-organisms, their impact on corrosion and their eradication. The conflicting results behind the use of graphene as a coating material are evaluated using the available literature and its future as an effective MIC resistant coating is then discussed. Chapter 2 is a study of the effectiveness of graphene based coatings for passivating metal surfaces against microbial induced corrosion. The effectiveness of graphene is evaluated against a bare metal electrode and a regular carbon based electrode using Cyclic Voltammetry (CV), Electrochemical Impedance Spectroscopy (EIS), Spectrophotometry and Scanning Electron Microscopy (SEM). Results indicate 3-orders-of-magnitude lower corrosion currents in the graphene coated electrode and about two orders of magnitude higher impedance to interfacial electrochemical reactions. After establishing the superiority of graphene over bare metal electrode, further studies were conducted to compare its performance over other state of the art polymer coatings such as parylene and polyurethane. This study is discussed in detail in Chapter 3. Quantitatively, graphene outperforms the polymer coated electrodes by offering close to two orders of magnitude higher MIC resistance, while qualitatively, optical images indicate severe oxidation in both the polymer coated metal structures. The chapter is concluded with discussions on the unparalleled corrosion resistance provided by graphene based coatings. The success/failure of coating techniques is not purely dictated by their ability to protect the surface, but also by the ease of coating application onto any given surface. Chapter 4 explains the methods by which high quality graphene can be used to protect surfaces that are not conducive to graphene growth and the problems associated with the current transfer techniques. A Raman Spectroscopy based surface mapping is performed to understand the defect peak intensities across the surface and the reasons for coating failure when using the state-of-the-art transfer techniques is discussed.

The possibility of multi-layer nanofabrication via atomic force microscope-based pulse electrochemical nanopatterning

NASA Astrophysics Data System (ADS)

Kim, Uk Su; Morita, Noboru; Lee, Deug Woo; Jun, Martin; Park, Jeong Woo

2017-05-01

Pulse electrochemical nanopatterning, a non-contact scanning probe lithography process using ultrashort voltage pulses, is based primarily on an electrochemical machining process using localized electrochemical oxidation between a sharp tool tip and the sample surface. In this study, nanoscale oxide patterns were formed on silicon Si (100) wafer surfaces via electrochemical surface nanopatterning, by supplying external pulsed currents through non-contact atomic force microscopy. Nanoscale oxide width and height were controlled by modulating the applied pulse duration. Additionally, protruding nanoscale oxides were removed completely by simple chemical etching, showing a depressed pattern on the sample substrate surface. Nanoscale two-dimensional oxides, prepared by a localized electrochemical reaction, can be defined easily by controlling physical and electrical variables, before proceeding further to a layer-by-layer nanofabrication process.

Correlation between optical properties surface morphology of porous silicon electrodeposited by Fe3+ ion

NASA Astrophysics Data System (ADS)

Mabrouk, Asma; Lorrain, N.; Haji, M. L.; Oueslati, Meherzi

2015-01-01

In this paper, we analyze the photoluminescence spectra (PL) of porous silicon (PS) layer which is elaborated by electrochemical etching and passivated by Fe3+ ions (PSF) via current density, electro-deposition and temperature measurements. We observe unusual surface morphology of PSF surface and anomalous emission behavior. The PSF surface shows regular distribution of cracks, leaving isolated regions or ;platelets; of nearly uniform thickness. These cracks become more pronounced for high current densities. The temperature dependence of the PL peak energy (EPL) presents anomalous behaviors, i.e., the PL peak energy shows a successive red/blue/redshift (S-shaped behavior) with increasing temperature that we attribute to the existence of strong potential fluctuations induced by the electrochemical etching of PS layers. A competition process between localized and delocalized excitons is used to discuss these PL properties. In this case, the potential confinement plays a key role on the enhancement of PL intensity in PSF. To explain the temperature dependence of the PL intensity, we have proposed a recombination model based on the tunneling and dissociation of excitons.

Tribological performance of titanium samples oxidized by fs-laser radiation, thermal heating, or electrochemical anodization

NASA Astrophysics Data System (ADS)

Kirner, S. V.; Slachciak, N.; Elert, A. M.; Griepentrog, M.; Fischer, D.; Hertwig, A.; Sahre, M.; Dörfel, I.; Sturm, H.; Pentzien, S.; Koter, R.; Spaltmann, D.; Krüger, J.; Bonse, J.

2018-04-01

Commercial grade-1 titanium samples (Ti, 99.6%) were treated using three alternative methods, (i) femtosecond laser processing, (ii) thermal heat treatment, and (iii) electrochemical anodization, respectively, resulting in the formation of differently conditioned superficial titanium oxide layers. The laser processing (i) was carried out by a Ti:sapphire laser (pulse duration 30 fs, central wavelength 790 nm, pulse repetition rate 1 kHz) in a regime of generating laser-induced periodic surface structures (LIPSS). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning setup for the processing of several square-millimeters large surface areas covered homogeneously by these nanostructures. The differently oxidized titanium surfaces were characterized by optical microscopy, micro Raman spectroscopy, variable angle spectroscopic ellipsometry, and instrumented indentation testing. The tribological performance was characterized in the regime of mixed friction by reciprocating sliding tests against a sphere of hardened steel in fully formulated engine oil as lubricant. The specific tribological performance of the differently treated surfaces is discussed with respect to possible physical and chemical mechanisms.

Post-mortem characterization of fs laser-generated micro-pillars in Li(Ni1/3Mn1/3Co1/3)O2 electrodes by laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Smyrek, P.; Zheng, Y.; Seifert, H. J.; Pfleging, W.

2016-03-01

NMC thick films were prepared by tape-casting and subsequent ultrafast laser-structuring. The lithium distribution in electrochemically cycled and unstructured or fs laser-structured NMC cathodes was investigated by using Laser-Induced Breakdown Spectroscopy (LIBS). The main goal is to develop an optimized three dimensional cell architecture with improved electrochemical properties based on studies of the homogeneity of the local State-of-Charge. LIBS experiments were carried out using a LIBS workstation equipped with a mode-locked diode pumped solid state Nd:YAG laser operating at a wavelength of 1063 nm. The element distribution was investigated using two different techniques: element mapping and element depth-profiling of the unstructured / fs laser-structured electrode surface. Results achieved from post-mortem studies using LIBS will be presented.

Compression-Induced Conformation and Orientation Changes in an n-Alkane Monolayer on a Au(111) Surface.

PubMed

Endo, Osamu; Nakamura, Masashi; Amemiya, Kenta; Ozaki, Hiroyuki

2017-04-25

The influence of the preparation method and adsorbed amount of n-tetratetracontane (n-C 44 H 90 ) on its orientation in a monolayer on the Au(111) surface is studied by near carbon K-edge X-ray absorption fine structure spectroscopy (C K-NEXAFS), scanning tunneling microscopy (STM) under ultrahigh vacuum, and infrared reflection-absorption spectroscopy (IRAS) at the electrochemical interface in sulfuric acid solution. The n-C 44 H 90 molecules form self-assembled lamellar structures with the chain axis parallel to the surface, as observed by STM. For small amounts adsorbed, the carbon plane is parallel to the surface (flat-on orientation). An increase in the adsorbed amount by ∼10-20% induces compression of the lamellar structure either along the lamellar axis or alkyl chain axis. The compressed molecular arrangement is observed by STM, and induced conformation and orientation changes are confirmed by in situ IRAS and C K-NEXAFS.

Kinetic mechanism for modeling of electrochemical reactions.

PubMed

Cervenka, Petr; Hrdlička, Jiří; Přibyl, Michal; Snita, Dalimil

2012-04-01

We propose a kinetic mechanism of electrochemical interactions. We assume fast formation and recombination of electron donors D- and acceptors A+ on electrode surfaces. These mediators are continuously formed in the electrode matter by thermal fluctuations. The mediators D- and A+, chemically equivalent to the electrode metal, enter electrochemical interactions on the electrode surfaces. Electrochemical dynamics and current-voltage characteristics of a selected electrochemical system are studied. Our results are in good qualitative agreement with those given by the classical Butler-Volmer kinetics. The proposed model can be used to study fast electrochemical processes in microsystems and nanosystems that are often out of the thermal equilibrium. Moreover, the kinetic mechanism operates only with the surface concentrations of chemical reactants and local electric potentials, which facilitates the study of electrochemical systems with indefinable bulk.

Reagentless, Structure-Switching, Electrochemical Aptamer-Based Sensors

NASA Astrophysics Data System (ADS)

Schoukroun-Barnes, Lauren R.; Macazo, Florika C.; Gutierrez, Brenda; Lottermoser, Justine; Liu, Juan; White, Ryan J.

2016-06-01

The development of structure-switching, electrochemical, aptamer-based sensors over the past ˜10 years has led to a variety of reagentless sensors capable of analytical detection in a range of sample matrices. The crux of this methodology is the coupling of target-induced conformation changes of a redox-labeled aptamer with electrochemical detection of the resulting altered charge transfer rate between the redox molecule and electrode surface. Using aptamer recognition expands the highly sensitive detection ability of electrochemistry to a range of previously inaccessible analytes. In this review, we focus on the methods of sensor fabrication and how sensor signaling is affected by fabrication parameters. We then discuss recent studies addressing the fundamentals of sensor signaling as well as quantitative characterization of the analytical performance of electrochemical aptamer-based sensors. Although the limits of detection of reported electrochemical aptamer-based sensors do not often reach that of gold-standard methods such as enzyme-linked immunosorbent assays, the operational convenience of the sensor platform enables exciting analytical applications that we address. Using illustrative examples, we highlight recent advances in the field that impact important areas of analytical chemistry. Finally, we discuss the challenges and prospects for this class of sensors.

Microfluidic electrochemical device and process for chemical imaging and electrochemical analysis at the electrode-liquid interface in-situ

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

Yu, Xiao-Ying; Liu, Bingwen; Yang, Li

2016-03-01

A microfluidic electrochemical device and process are detailed that provide chemical imaging and electrochemical analysis under vacuum at the surface of the electrode-sample or electrode-liquid interface in-situ. The electrochemical device allows investigation of various surface layers including diffuse layers at selected depths populated with, e.g., adsorbed molecules in which chemical transformation in electrolyte solutions occurs.

Surface engineered porous silicon for stable, high performance electrochemical supercapacitors

PubMed Central

Oakes, Landon; Westover, Andrew; Mares, Jeremy W.; Chatterjee, Shahana; Erwin, William R.; Bardhan, Rizia; Weiss, Sharon M.; Pint, Cary L.

2013-01-01

Silicon materials remain unused for supercapacitors due to extreme reactivity of silicon with electrolytes. However, doped silicon materials boast a low mass density, excellent conductivity, a controllably etched nanoporous structure, and combined earth abundance and technological presence appealing to diverse energy storage frameworks. Here, we demonstrate a universal route to transform porous silicon (P-Si) into stable electrodes for electrochemical devices through growth of an ultra-thin, conformal graphene coating on the P-Si surface. This graphene coating simultaneously passivates surface charge traps and provides an ideal electrode-electrolyte electrochemical interface. This leads to 10–40X improvement in energy density, and a 2X wider electrochemical window compared to identically-structured unpassivated P-Si. This work demonstrates a technique generalizable to mesoporous and nanoporous materials that decouples the engineering of electrode structure and electrochemical surface stability to engineer performance in electrochemical environments. Specifically, we demonstrate P-Si as a promising new platform for grid-scale and integrated electrochemical energy storage. PMID:24145684

Surface engineered porous silicon for stable, high performance electrochemical supercapacitors.

PubMed

Oakes, Landon; Westover, Andrew; Mares, Jeremy W; Chatterjee, Shahana; Erwin, William R; Bardhan, Rizia; Weiss, Sharon M; Pint, Cary L

2013-10-22

Silicon materials remain unused for supercapacitors due to extreme reactivity of silicon with electrolytes. However, doped silicon materials boast a low mass density, excellent conductivity, a controllably etched nanoporous structure, and combined earth abundance and technological presence appealing to diverse energy storage frameworks. Here, we demonstrate a universal route to transform porous silicon (P-Si) into stable electrodes for electrochemical devices through growth of an ultra-thin, conformal graphene coating on the P-Si surface. This graphene coating simultaneously passivates surface charge traps and provides an ideal electrode-electrolyte electrochemical interface. This leads to 10-40X improvement in energy density, and a 2X wider electrochemical window compared to identically-structured unpassivated P-Si. This work demonstrates a technique generalizable to mesoporous and nanoporous materials that decouples the engineering of electrode structure and electrochemical surface stability to engineer performance in electrochemical environments. Specifically, we demonstrate P-Si as a promising new platform for grid-scale and integrated electrochemical energy storage.

Surface engineered porous silicon for stable, high performance electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Oakes, Landon; Westover, Andrew; Mares, Jeremy W.; Chatterjee, Shahana; Erwin, William R.; Bardhan, Rizia; Weiss, Sharon M.; Pint, Cary L.

2013-10-01

Silicon materials remain unused for supercapacitors due to extreme reactivity of silicon with electrolytes. However, doped silicon materials boast a low mass density, excellent conductivity, a controllably etched nanoporous structure, and combined earth abundance and technological presence appealing to diverse energy storage frameworks. Here, we demonstrate a universal route to transform porous silicon (P-Si) into stable electrodes for electrochemical devices through growth of an ultra-thin, conformal graphene coating on the P-Si surface. This graphene coating simultaneously passivates surface charge traps and provides an ideal electrode-electrolyte electrochemical interface. This leads to 10-40X improvement in energy density, and a 2X wider electrochemical window compared to identically-structured unpassivated P-Si. This work demonstrates a technique generalizable to mesoporous and nanoporous materials that decouples the engineering of electrode structure and electrochemical surface stability to engineer performance in electrochemical environments. Specifically, we demonstrate P-Si as a promising new platform for grid-scale and integrated electrochemical energy storage.

Time resolved impedance spectroscopy analysis of lithium phosphorous oxynitride - LiPON layers under mechanical stress

NASA Astrophysics Data System (ADS)

Glenneberg, Jens; Bardenhagen, Ingo; Langer, Frederieke; Busse, Matthias; Kun, Robert

2017-08-01

In this paper we present investigations on the morphological and electrochemical changes of lithium phosphorous oxynitride (LiPON) under mechanically bent conditions. Therefore, two types of electrochemical cells with LiPON thin films were prepared by physical vapor deposition. First, symmetrical cells with two blocking electrodes (Cu/LiPON/Cu) were fabricated. Second, to simulate a more application-related scenario cells with one blocking and one non-blocking electrode (Cu/LiPON/Li/Cu) were analyzed. In order to investigate mechanical distortion induced transport property changes in LiPON layers the cells were deposited on a flexible polyimide substrate. Morphology of the as-prepared samples and deviations from the initial state after applying external stress by bending the cells over different radii were investigated by Focused Ion Beam- Scanning Electron Microscopy (FIB-SEM) cross-section and surface images. Mechanical stress induced changes in the impedance were evaluated by time-resolved electrochemical impedance spectroscopy (EIS). Due to the formation of a stable, ion-conducting solid electrolyte interphase (SEI), cells with lithium show decreased impedance values. Furthermore, applying mechanical stress to the cells results in a further reduction of the electrolyte resistance. These results are supported by finite element analysis (FEA) simulations.

Low-dimensional carbon and MXene-based electrochemical capacitor electrodes.

PubMed

Yoon, Yeoheung; Lee, Keunsik; Lee, Hyoyoung

2016-04-29

Due to their unique structure and outstanding intrinsic physical properties such as extraordinarily high electrical conductivity, large surface area, and various chemical functionalities, low-dimension-based materials exhibit great potential for application in electrochemical capacitors (ECs). The electrical properties of electrochemical capacitors are determined by the electrode materials. Because energy charge storage is a surface process, the surface properties of the electrode materials greatly influence the electrochemical performance of the cell. Recently, graphene, a single layer of sp(2)-bonded carbon atoms arrayed into two-dimensional carbon nanomaterial, has attracted wide interest as an electrode material for electrochemical capacitor applications due to its unique properties, including a high electrical conductivity and large surface area. Several low-dimensional materials with large surface areas and high conductivity such as onion-like carbons (OLCs), carbide-derived carbons (CDCs), carbon nanotubes (CNTs), graphene, metal hydroxide, transition metal dichalcogenides (TMDs), and most recently MXene, have been developed for electrochemical capacitors. Therefore, it is useful to understand the current issues of low-dimensional materials and their device applications.

Surface modifications of hydrogen storage alloy by heavy ion beams with keV to MeV irradiation energies

NASA Astrophysics Data System (ADS)

Abe, Hiroshi; Tokuhira, Shinnosuke; Uchida, Hirohisa; Ohshima, Takeshi

2015-12-01

This study deals with the effect of surface modifications induced from keV to MeV heavy ion beams on the initial reaction rate of a hydrogen storage alloy (AB5) in electrochemical process. The rare earth based alloys like this sample alloy are widely used as a negative electrode of Ni-MH (Nickel-Metal Hydride) battery. We aimed to improve the initial reaction rate of hydrogen absorption by effective induction of defects such as vacancies, dislocations, micro-cracks or by addition of atoms into the surface region of the metal alloys. Since defective layer near the surface can easily be oxidized, the conductive oxide layer is formed on the sample surface by O+ beams irradiation, and the conductive oxide layer might cause the improvement of initial reaction rate of hydriding. This paper demonstrates an effective surface treatment of heavy ion irradiation, which induces catalytic activities of rare earth oxides in the alloy surface.

Functionalized Solid Electrodes for Electrochemical Biosensing of Purine Nucleobases and Their Analogues: A Review

PubMed Central

Sharma, Vimal Kumar; Jelen, Frantisek; Trnkova, Libuse

2015-01-01

Interest in electrochemical analysis of purine nucleobases and few other important purine derivatives has been growing rapidly. Over the period of the past decade, the design of electrochemical biosensors has been focused on achieving high sensitivity and efficiency. The range of existing electrochemical methods with carbon electrode displays the highest rate in the development of biosensors. Moreover, modification of electrode surfaces based on nanomaterials is frequently used due to their extraordinary conductivity and surface to volume ratio. Different strategies for modifying electrode surfaces facilitate electron transport between the electrode surface and biomolecules, including DNA, oligonucleotides and their components. This review aims to summarize recent developments in the electrochemical analysis of purine derivatives, as well as discuss different applications. PMID:25594595

Corrosive effects of fluoride on titanium under artificial biofilm.

PubMed

Fukushima, Azusa; Mayanagi, Gen; Sasaki, Keiichi; Takahashi, Nobuhiro

2018-01-01

This study aimed to investigate the effect of sodium fluoride (NaF) on titanium corrosion using a biofilm model, taking environmental pH into account. Streptococcus mutans cells were used as the artificial biofilm, and pH at the bacteria-titanium interface was monitored after the addition of 1% glucose with NaF (0, 225 or 900ppmF) at 37°C for 90min. In an immersion test, the titanium samples were immersed in the NaF solution (0, 225 or 900ppm F; pH 4.2 or 6.5) for 30 or 90min. Before and after pH monitoring or immersion test, the electrochemical properties of the titanium surface were measured using a potentiostat. The amount of titanium eluted into the biofilm or the immersion solution was measured using inductively coupled plasma mass spectrometry. The color difference (ΔE*ab) and gloss of the titanium surface were determined using a spectrophotometer. After incubation with biofilm, pH was maintained at around 6.5 in the presence of NaF. There was no significant change in titanium surface and elution, regardless of the concentration of NaF. After immersion in 900ppm NaF solution at pH 4.2, corrosive electrochemical change was induced on the surface, titanium elution and ΔE*ab were increased, and gloss was decreased. NaF induces titanium corrosion in acidic environment in vitro, while NaF does not induce titanium corrosion under the biofilm because fluoride inhibits bacterial acid production. Neutral pH fluoridated agents may still be used to protect the remaining teeth, even when titanium-based prostheses are worn. Copyright © 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Electrochemical Behavior of TiO(x)C(y) as Catalyst Support for Direct Ethanol Fuel Cells at Intermediate Temperature: From Planar Systems to Powders.

PubMed

Calvillo, Laura; García, Gonzalo; Paduano, Andrea; Guillen-Villafuerte, Olmedo; Valero-Vidal, Carlos; Vittadini, Andrea; Bellini, Marco; Lavacchi, Alessandro; Agnoli, Stefano; Martucci, Alessandro; Kunze-Liebhäuser, Julia; Pastor, Elena; Granozzi, Gaetano

2016-01-13

To achieve complete oxidation of ethanol (EOR) to CO2, higher operating temperatures (often called intermediate-T, 150-200 °C) and appropriate catalysts are required. We examine here titanium oxycarbide (hereafter TiOxCy) as a possible alternative to standard carbon-based supports to enhance the stability of the catalyst/support assembly at intermediate-T. To test this material as electrocatalyst support, a systematic study of its behavior under electrochemical conditions was carried out. To have a clear description of the chemical changes of TiOxCy induced by electrochemical polarization of the material, a special setup that allows the combination of X-ray photoelectron spectroscopy and electrochemical measurements was used. Subsequently, an electrochemical study was carried out on TiOxCy powders, both at room temperature and at 150 °C. The present study has revealed that TiOxCy is a sufficiently conductive material whose surface is passivated by a TiO2 film under working conditions, which prevents the full oxidation of the TiOxCy and can thus be considered a stable electrode material for EOR working conditions. This result has also been confirmed through density functional theory (DFT) calculations on a simplified model system. Furthermore, it has been experimentally observed that ethanol molecules adsorb on the TiOxCy surface, inhibiting its oxidation. This result has been confirmed by using in situ Fourier transform infrared spectroscopy (FTIRS). The adsorption of ethanol is expected to favor the EOR in the presence of suitable catalyst nanoparticles supported on TiOxCy.

Highly sensitive electrochemical nuclear factor kappa B aptasensor based on target-induced dual-signal ratiometric and polymerase-assisted protein recycling amplification strategy.

PubMed

Peng, Kanfu; Xie, Pan; Yang, Zhe-Han; Yuan, Ruo; Zhang, Keqin

2018-04-15

In this work, an amplified electrochemical ratiometric aptasensor for nuclear factor kappa B (NF-κB) assay based on target binding-triggered ratiometric signal readout and polymerase-assisted protein recycling amplification strategy is described. To demonstrate the effect of "signal-off" and "signal-on" change for the dual-signal electrochemical ratiometric readout, the thiol-hairpin DNA (SH-HD) hybridizes with methylene blue (MB)-modified protection DNA (MB-PD) to form capture probes, which is rationally introduced for the construction of the assay platform. On the interface, the probes can specifically bind to target NF-κB and expose a toehold region which subsequently hybridizes with the ferrocene (Fc)-modified DNA strand to take the Fc group to the electrode surface, accompanied by displacing MB-PD to release the MB group from the electrode surface, leading to the both "signal-on" of Fc (I Fc ) and "signal-off" of MB (I MB ). In order to improve the sensitivity of the electrochemical aptasensor, phi29-assisted target protein recycling amplification strategy was designed to achieve an amplified ratiometric signal. With the above advantages, the prepared aptasensor exhibits a wide linear range of 0.1pgmL -1 to 15ngmL -1 with a low detection limit of 0.03pgmL -1 . This strategy provides a simple and ingenious approach to construct ratiometric electrochemical aptasensor and shows promising potential applications in multiple disease marker detection by changing the recognition probe. Copyright © 2017. Published by Elsevier B.V.

Surface Wave Metrology for Copper/Low-k Interconnects

NASA Astrophysics Data System (ADS)

Gostein, M.; Maznev, A. A.; Mazurenko, A.; Tower, J.

2005-09-01

We review recent advances in the application of laser-induced surface acoustic wave metrology to issues in copper/low-k interconnect development and manufacturing. We illustrate how the metrology technique can be used to measure copper thickness uniformity on a range of features from solid pads to arrays of lines, focusing on specific processing issues in copper electrochemical deposition (ECD) and chemical-mechanical polishing (CMP). In addition, we review recent developments in surface wave metrology for the characterization of low-k dielectric elastic modulus, including the ability to measure within-wafer uniformity of elastic modulus and to characterize porous, anisotropic films.

Preparation of superhydrophobic titanium surfaces via electrochemical etching and fluorosilane modification

NASA Astrophysics Data System (ADS)

Lu, Yao; Xu, Wenji; Song, Jinlong; Liu, Xin; Xing, Yingjie; Sun, Jing

2012-12-01

The preparation of superhydrophobic surfaces on hydrophilic metal substrates depends on both surface microstructures and low surface energy modification. In this study, a simple and inexpensive electrochemical method for preparing robust superhydrophobic titanium surfaces is reported. The neutral sodium chloride solution is used as electrolyte. Fluoroalkylsilane (FAS) was used to reduce the surface energy of the electrochemically etched surface. Scanning electron microscopy (SEM) images, energy-dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR) spectra, and contact angle measurement are performed to characterize the morphological features, chemical composition, and wettability of the titanium surfaces. Stability and friction tests indicate that the prepared titanium surfaces are robust. The analysis of electrolyte, reaction process, and products demonstrates that the electrochemical processing is very inexpensive and environment-friendly. This method is believed to be easily adaptable for use in large-scale industry productions to promote the application of superhydrophobic titanium surfaces in aviation, aerospace, shipbuilding, and the military industry.

Nanoscale electrochemical patterning reveals the active sites for catechol oxidation at graphite surfaces.

PubMed

Patel, Anisha N; McKelvey, Kim; Unwin, Patrick R

2012-12-19

Graphite-based electrodes (graphite, graphene, and nanotubes) are used widely in electrochemistry, and there is a long-standing view that graphite step edges are needed to catalyze many reactions, with the basal surface considered to be inert. In the present work, this model was tested directly for the first time using scanning electrochemical cell microscopy reactive patterning and shown to be incorrect. For the electro-oxidation of dopamine as a model process, the reaction rate was measured at high spatial resolution across a surface of highly oriented pyrolytic graphite. Oxidation products left behind in a pattern defined by the scanned electrochemical cell served as surface-site markers, allowing the electrochemical activity to be correlated directly with the graphite structure on the nanoscale. This process produced tens of thousands of electrochemical measurements at different locations across the basal surface, unambiguously revealing it to be highly electrochemically active, with step edges providing no enhanced activity. This new model of graphite electrodes has significant implications for the design of carbon-based biosensors, and the results are additionally important for understanding electrochemical processes on related sp(2)-hybridized materials such as pristine graphene and nanotubes.

Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

PubMed

Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

2016-10-26

Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

Studies of electrode structures and dynamics using coherent X-ray scattering and imaging

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

You, H.; Liu, Y.; Ulvestad, A.

2017-08-01

Electrochemical systems studied in situ with advanced surface X-ray scattering techniques are reviewed. The electrochemical systems covered include interfaces of single-crystals and nanocrystals with respect to surface modification, aqueous dissolution, surface reconstruction, and electrochemical double layers. An emphasis will be given on recent results by coherent X-ray techniques such as X-ray photon correlation spectroscopy, Bragg coherent diffraction imaging, and surface ptychography.

Probing Local Ionic Dynamics in Functional Oxides: From Nanometer to Atomic Scale

NASA Astrophysics Data System (ADS)

Kalinin, Sergei

2014-03-01

Vacancy-mediated electrochemical reactions in oxides underpin multiple applications ranging from electroresistive memories, to chemical sensors to energy conversion systems such as fuel cells. Understanding the functionality in these systems requires probing reversible (oxygen reduction/evolution reaction) and irreversible (cathode degradation and activation, formation of conductive filaments) electrochemical processes. In this talk, I summarize recent advances in probing and controlling these transformations locally on nanometer level using scanning probe microscopy. The localized tip concentrates the electric field in the nanometer scale volume of material, inducing local transition. Measured simultaneously electromechanical response (piezoresponse) or current (conductive AFM) provides the information on the bias-induced changes in material. Here, I illustrate how these methods can be extended to study local electrochemical transformations, including vacancy dynamics in oxides such as titanates, LaxSr1-xCoO3, BiFeO3, and YxZr1-xO2. The formation of electromechanical hysteresis loops and their bias-, temperature- and environment dependences provide insight into local electrochemical mechanisms. In materials such as lanthanum-strontium cobaltite, mapping both reversible vacancy motion and vacancy ordering and static deformation is possible, and can be corroborated by post mortem STEM/EELS studies. In ceria, a broad gamut of electrochemical behaviors is observed as a function of temperature and humidity. The possible strategies for elucidation ionic motion at the electroactive interfaces in oxides using high-resolution electron microscopy and combined ex-situ and in-situ STEM-SPM studies are discussed. In the second part of the talk, probing electrochemical phenomena on in-situ grown surfaces with atomic resolution is illustrated. I present an approach based on the multivariate statistical analysis of the coordination spheres of individual atoms to reveal preferential structures and symmetries. The relevant statistical techniques including k-means clustering, principal component analysis, and Baesian unmixing are briefly intriduced. This approach is illustrated for several systems, including chemical phase identification, mapping ferroic variants, and probing topological and structural defects, and provides real space view on surface atomic processes. Research supported (SVK) by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division and partially performed at the Center for Nanophase Materials Sciences (AK, SJ), a DOE-BES user facility.

Electrochemical writing on edible polysaccharide films for intelligent food packaging.

PubMed

Wu, Si; Wang, Wenqi; Yan, Kun; Ding, Fuyuan; Shi, Xiaowen; Deng, Hongbing; Du, Yumin

2018-04-15

Polysaccharide films used as intelligent food packaging possess the advantages of renewability, safety and biodegradability. Printing on the polysaccharidic food packaging is challenging due to the high demand for edible-ink and the need for a suitable printing technique. In this work, we propose an electrochemical method for writing on polysaccharide film. Unlike conventional printing, this electrochemical writing process relies on the pH responsive color change of anthocyanin embedded in the chitosan/agarose hydrogel. By biasing a negative potential to a stainless wire (used as a pen) contacting the surface of the chitosan/agarose/ATH hydrogel, the locally generated pH change induced the color change of ATH and wrote programmed information on the hydrogel. We demonstrate the writing can be temporary in the hydrogel but stable when the hydrogel is dried. We further demonstrate that the written film is applicable for the detection of the spoilage of crucian fish. The reported electrochemical writing process provides a novel method for printing information on polysaccharide film and great potential for intelligent food packaging. Copyright © 2018 Elsevier Ltd. All rights reserved.

Characterization of Copper Corrosion Products in Drinking Water by Combining Electrochemical and Surface Analyses

EPA Science Inventory

This study focuses on the application of electrochemical approaches to drinking water copper corrosion problems. Applying electrochemical approaches combined with copper solubility measurements, and solid surface analysis approaches were discussed. Tafel extrapolation and Electro...

Characterization of Copper Corrosion Products Formed in Drinking Water by Combining Electrochemical and Surface Analyses

EPA Science Inventory

This study focuses on the application of electrochemical approaches to drinking water copper corrosion problems. Applying electrochemical approaches combined with copper solubility measurements, and solid surface analysis approaches were discussed. Tafel extrapolation and Electro...

Potential-sensing electrochemical atomic force microscopy for in operando analysis of water-splitting catalysts and interfaces

NASA Astrophysics Data System (ADS)

Nellist, Michael R.; Laskowski, Forrest A. L.; Qiu, Jingjing; Hajibabaei, Hamed; Sivula, Kevin; Hamann, Thomas W.; Boettcher, Shannon W.

2018-01-01

Heterogeneous electrochemical phenomena, such as (photo)electrochemical water splitting to generate hydrogen using semiconductors and/or electrocatalysts, are driven by the accumulated charge carriers and thus the interfacial electrochemical potential gradients that promote charge transfer. However, measurements of the "surface" electrochemical potential during operation are not generally possible using conventional electrochemical techniques, which measure/control the potential of a conducting electrode substrate. Here we show that the nanoscale conducting tip of an atomic force microscope cantilever can sense the surface electrochemical potential of electrocatalysts in operando. To demonstrate utility, we measure the potential-dependent and thickness-dependent electronic properties of cobalt (oxy)hydroxide phosphate (CoPi). We then show that CoPi, when deposited on illuminated haematite (α-Fe2O3) photoelectrodes, acts as both a hole collector and an oxygen evolution catalyst. We demonstrate the versatility of the technique by comparing surface potentials of CoPi-decorated planar and mesoporous haematite and discuss viability for broader application in the study of electrochemical phenomena.

Synergistic effect of tungsten carbide and palladium on graphene for promoted ethanol electrooxidation.

PubMed

Yang, Jun; Xie, Ying; Wang, Ruihong; Jiang, Baojiang; Tian, Chungui; Mu, Guang; Yin, Jie; Wang, Bo; Fu, Honggang

2013-07-24

The synergistic effect of WC and Pd has large benefit for ethanol electrooxidation. The small-sized Pd nanoparticles (NPs) decorated tungsten carbide on graphene (Pd-WC/GN) will be a promising anode catalyst for the direct ethanol fuel cells. The density functional theory (DFT) calculations reveal that the strong interaction exists at the interface between Pd and WC, which induces the electron transfer from WC to Pd. Fortunately, the nanoscale architecture of Pd-WC/GN has been successfully fabricated in our experiments. X-ray photoelectron spectrum further confirms the existence of electron transfer from WC to Pd in a Pd-WC/GN nanohybrid. Notably, electrochemical tests show that the Pd-WC/GN catalyst exhibits low onset potential, a large electrochemical surface area, high activity, and stability for ethanol electrooxidation in alkaline solution compared with Pd/graphene and Pd/commercial Vulcan 72R carbon catalysts. The enhancement can be attributed to the synergistic effect of Pd and WC on graphene. At the interface between Pd and WC, the electron transfer from WC to Pd leads to the increased electron densities of surface Pd, which is available for weakening adsorption of intermediate oxygen-containing species such as CO and activating catalyst. Meanwhile, the increased tungsten oxide induced by electron transfer can facilitate the effective removal of intermediate species adsorbed on the Pd surface through a bifunctional mechanism or hydrogen spillover effect.

Plasmonic Imaging of Electrochemical Reactions of Single Nanoparticles.

PubMed

Fang, Yimin; Wang, Hui; Yu, Hui; Liu, Xianwei; Wang, Wei; Chen, Hong-Yuan; Tao, N J

2016-11-15

Electrochemical reactions are involved in many natural phenomena, and are responsible for various applications, including energy conversion and storage, material processing and protection, and chemical detection and analysis. An electrochemical reaction is accompanied by electron transfer between a chemical species and an electrode. For this reason, it has been studied by measuring current, charge, or related electrical quantities. This approach has led to the development of various electrochemical methods, which have played an essential role in the understanding and applications of electrochemistry. While powerful, most of the traditional methods lack spatial and temporal resolutions desired for studying heterogeneous electrochemical reactions on electrode surfaces and in nanoscale materials. To overcome the limitations, scanning probe microscopes have been invented to map local electrochemical reactions with nanometer resolution. Examples include the scanning electrochemical microscope and scanning electrochemical cell microscope, which directly image local electrochemical reaction current using a scanning electrode or pipet. The use of a scanning probe in these microscopes provides high spatial resolution, but at the expense of temporal resolution and throughput. This Account discusses an alternative approach to study electrochemical reactions. Instead of measuring electron transfer electrically, it detects the accompanying changes in the reactant and product concentrations on the electrode surface optically via surface plasmon resonance (SPR). SPR is highly surface sensitive, and it provides quantitative information on the surface concentrations of reactants and products vs time and electrode potential, from which local reaction kinetics can be analyzed and quantified. The plasmonic approach allows imaging of local electrochemical reactions with high temporal resolution and sensitivity, making it attractive for studying electrochemical reactions in biological systems and nanoscale materials with high throughput. The plasmonic approach has two imaging modes: electrochemical current imaging and interfacial impedance imaging. The former images local electrochemical current associated with electrochemical reactions (faradic current), and the latter maps local interfacial impedance, including nonfaradic contributions (e.g., double layer charging). The plasmonic imaging technique can perform voltammetry (cyclic or square wave) in an analogous manner to the traditional electrochemical methods. It can also be integrated with bright field, dark field, and fluorescence imaging capabilities in one optical setup to provide additional capabilities. To date the plasmonic imaging technique has found various applications, including mapping of heterogeneous surface reactions, analysis of trace substances, detection of catalytic reactions, and measurement of graphene quantum capacitance. The plasmonic and other emerging optical imaging techniques (e.g., dark field and fluorescence microscopy), together with the scanning probe-based electrochemical imaging and single nanoparticle analysis techniques, provide new capabilities for one to study single nanoparticle electrochemistry with unprecedented spatial and temporal resolutions. In this Account, we focus on imaging of electrochemical reactions at single nanoparticles.

Surface morphology and electrochemical studies on polyaniline/CuO nano composites

NASA Astrophysics Data System (ADS)

Ashokkumar, S. P.; Vijeth, H.; Yesappa, L.; Niranjana, M.; Vandana, M.; Basappa, M.; Devendrappa, H.

2018-05-01

An electrochemically synthesized Polyaniline (PANI) and Polyaniline/copper oxide (PCN) nano composite have studied the morphology and electrochemical properties. The composite is characterized by X-ray diffraction (XRD) and surface morphology was studied using FESEM and electrochemical behavior is studied using cyclic voltammetry (CV) technique. The CV curves shows rectangular shaped curve and they have contribution to electrical double layer capacitance (EDCL).

Methods and systems for in-situ electroplating of electrodes

DOEpatents

Zappi, Guillermo Daniel; Zarnoch, Kenneth Paul; Huntley, Christian Andrew; Swalla, Dana Ray

2015-06-02

The present techniques provide electrochemical devices having enhanced electrodes with surfaces that facilitate operation, such as by formation of a porous nickel layer on an operative surface, particularly of the cathode. The porous metal layer increases the surface area of the electrode, which may result in increasing the efficiency of the electrochemical devices. The formation of the porous metal layer is performed in situ, that is, after the assembly of the electrodes into an electrochemical device. The in situ process offers a number of advantages, including the ability to protect the porous metal layer on the electrode surface from damage during assembly of the electrochemical device. The enhanced electrode and the method for its processing may be used in any number of electrochemical devices, and is particularly well suited for electrodes in an electrolyzer useful for splitting water into hydrogen and oxygen.

Peroxide induced volatile and non-volatile switching behavior in ZnO-based electrochemical metallization memory cell

NASA Astrophysics Data System (ADS)

Mangasa Simanjuntak, Firman; Chandrasekaran, Sridhar; Pattanayak, Bhaskar; Lin, Chun-Chieh; Tseng, Tseung-Yuen

2017-09-01

We explore the use of cubic-zinc peroxide (ZnO2) as a switching material for electrochemical metallization memory (ECM) cell. The ZnO2 was synthesized with a simple peroxide surface treatment. Devices made without surface treatment exhibits a high leakage current due to the self-doped nature of the hexagonal-ZnO material. Thus, its switching behavior can only be observed when a very high current compliance is employed. The synthetic ZnO2 layer provides a sufficient resistivity to the Cu/ZnO2/ZnO/ITO devices. The high resistivity of ZnO2 encourages the formation of a conducting bridge to activate the switching behavior at a lower operation current. Volatile and non-volatile switching behaviors with sufficient endurance and an adequate memory window are observed in the surface-treated devices. The room temperature retention of more than 104 s confirms the non-volatility behavior of the devices. In addition, our proposed device structure is able to work at a lower operation current among other reported ZnO-based ECM cells.

Corrosion resistance of BIS 2062-grade steel coated with nano-metal-oxide mixtures of iron, cerium, and titanium in the marine environment

NASA Astrophysics Data System (ADS)

Ashraf, P. Muhamed; Anuradha, R.

2018-02-01

BIS 2062-grade carbon steel is extensively used for fishing boat construction. The steel is highly susceptible to corrosion on the hull and welding joints under marine environment. Here, we demonstrate the application of a novel multifunctional nano-metal-oxide mixture comprised of iron, titanium, and cerium as a marine coating to prevent corrosion. The electrochemical performance of nano-metal-oxide mixture coatings, applied over boat-building steel, was evaluated at 3.5% NaCl medium. The nano-mixture surface coatings showed an efficient corrosion resistance with increased polarization resistance of 6043 Ω cm2 and low corrosion current density of 3.53 × 10-6 A cm-2. The electrochemical impedance spectral data exhibited improvement in the polarization resistance of outermost surface and internal layers. The coating responded faster recovery to normal state when subjected to an induced stress over the coating. The nano-material in the coating behaves as a semiconductor; this enhanced electronic activity over the surface of the steel.

X-ray off-specular reflectivity studies of electrochemical pitting of Cu surfaces in sodium bicarbonate solution

NASA Astrophysics Data System (ADS)

Feng, Y. P.; Sinha, S. K.; Melendres, C. A.; Lee, D. D.

1996-02-01

We have studied the electrochemically-induced pitting process on a Cu electrode in NaHCO 3 solution using in-situ X-ray off-specular reflectivity measurements. The morphology and growth dynamics of the localized corrosion sites or pits were studied as the applied potential was varied from the cathodic region where the Cu surface is relatively free of oxide films to the anodic region where surface roughening occurs by general corrosion with concomitant formation of an oxide film. Quantitative analysis of the experimental results indicates that early pitting proceeds in favor of nucleation of pit clusters over individual pit growth. It was found that the lateral distribution of the pits is not random but exhibits a short-range order as evidenced by the appearance of a side peak in the transverse off-specular reflectivity. The position, height, and width of the peak was modeled to yield the average size, nearest-neighbor distance (within any one of the clusters), and over-all density of the pits averaged over the entire illuminated surface. In addition, measurements of the longitudinal off-specular reflectivity indicate a bimodal depth distribution for the pits, suggesting a “film breaking” type of pitting mechanism.

A Study on Corrosion Inhibitor for Mild Steel in Ethanol Fuel Blend

PubMed Central

Vu, Nguyen Si Hoai; Hien, Pham Van; Man, Tran Van; Hanh Thu, Vu Thi; Tri, Mai Dinh

2017-01-01

The main aim of this study is to investigate Aganonerion polymorphum leaf-ethyl acetate extract (APL-EAE) and its inhibiting effect for steel in ethanol fuel blend. The immersion test, electrochemical and surface analysis techniques were successfully carried out in this research. Scanning electron microscope images indicated that the ethanol fuel blend induced pitting corrosion of steel. Remarkably, the surface of the sample containing 1000 ppm APL-EAE is smoother than the others submerged in different conditions. The electrochemical impedance spectroscopy result shows that APL-EAE has formed a good protective layer, preventing corrosive factors from hitting the steel surface. The potentiodynamic polarization data argue that the corrosion inhibition efficiency was strengthened with the increase of APL-EAE concentration. The Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy demonstrated less intensity of Fe peaks, higher intensity of C1s peak and the appearance of organic peaks (N1s, P2p, O1s) from specimens with and without APL-EAE addition. Therefore, the results suggest the formation of the protective film on steel surface and affirm that APL-EAE has served as an effective corrosion inhibitor for steel in ethanol fuel blend. PMID:29301224

SEM method for direct visual tracking of nanoscale morphological changes of platinum based electrocatalysts on fixed locations upon electrochemical or thermal treatments.

PubMed

Zorko, Milena; Jozinović, Barbara; Bele, Marjan; Hodnik, Nejc; Gaberšček, Miran

2014-05-01

A general method for tracking morphological surface changes on a nanometer scale with scanning electron microscopy (SEM) is introduced. We exemplify the usefulness of the method by showing consecutive SEM images of an identical location before and after the electrochemical and thermal treatments of platinum-based nanoparticles deposited on a high surface area carbon. Observations reveal an insight into platinum based catalyst degradation occurring during potential cycling treatment. The presence of chloride clearly increases the rate of degradation. At these conditions the dominant degradation mechanism seems to be the platinum dissolution with some subsequent redeposition on the top of the catalyst film. By contrast, at the temperature of 60°C, under potentiostatic conditions some carbon corrosion and particle aggregation was observed. Temperature treatment simulating the annealing step of the synthesis reveals sintering of small platinum based composite aggregates into uniform spherical particles. The method provides a direct proof of induced surface phenomena occurring on a chosen location without the usual statistical uncertainty in usual, random SEM observations across relatively large surface areas. Copyright © 2014 Elsevier B.V. All rights reserved.

A Study on Corrosion Inhibitor for Mild Steel in Ethanol Fuel Blend.

PubMed

Vu, Nguyen Si Hoai; Hien, Pham Van; Man, Tran Van; Hanh Thu, Vu Thi; Tri, Mai Dinh; Nam, Nguyen Dang

2017-12-31

The main aim of this study is to investigate Aganonerion polymorphum leaf-ethyl acetate extract (APL-EAE) and its inhibiting effect for steel in ethanol fuel blend. The immersion test, electrochemical and surface analysis techniques were successfully carried out in this research. Scanning electron microscope images indicated that the ethanol fuel blend induced pitting corrosion of steel. Remarkably, the surface of the sample containing 1000 ppm APL-EAE is smoother than the others submerged in different conditions. The electrochemical impedance spectroscopy result shows that APL-EAE has formed a good protective layer, preventing corrosive factors from hitting the steel surface. The potentiodynamic polarization data argue that the corrosion inhibition efficiency was strengthened with the increase of APL-EAE concentration. The Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy demonstrated less intensity of Fe peaks, higher intensity of C 1s peak and the appearance of organic peaks (N 1s , P 2p , O 1s ) from specimens with and without APL-EAE addition. Therefore, the results suggest the formation of the protective film on steel surface and affirm that APL-EAE has served as an effective corrosion inhibitor for steel in ethanol fuel blend.

Liquid gallium and the eutectic gallium indium (EGaIn) alloy: Dielectric functions from 1.24 to 3.1 eV by electrochemical reduction of surface oxides

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

Morales, Daniel; Yu, Zhiyuan; Dickey, Michael D., E-mail: mddickey@ncsu.edu, E-mail: aspnes@ncsu.edu

Liquid metals based on gallium are promising materials for soft, stretchable, and shape reconfigurable electromagnetic devices. The behavior of these metals relates directly to the thicknesses of their surface oxide layers, which can be determined nondestructively by ellipsometry if their dielectric functions ε are known. This paper reports on the dielectric functions of liquid gallium and the eutectic gallium indium (EGaIn) alloy from 1.24 to 3.1 eV at room temperature, measured by spectroscopic ellipsometry. Overlayer-induced artifacts, a continuing problem in optical measurements of these highly reactive metals, are eliminated by applying an electrochemically reductive potential to the surface of the metalmore » immersed in an electrolyte. This technique enables measurements at ambient conditions while avoiding the complications associated with removing overlayers in a vacuum environment. The dielectric responses of both metals are closely represented by the Drude model. The EGaIn data suggest that in the absence of an oxide the surface is In-enriched, consistent with the previous vacuum-based studies. Possible reasons for discrepancies with previous measurements are discussed.« less

High-performance Supercapacitors Based on Electrochemical-induced Vertical-aligned Carbon Nanotubes and Polyaniline Nanocomposite Electrodes

NASA Astrophysics Data System (ADS)

Wu, Guan; Tan, Pengfeng; Wang, Dongxing; Li, Zhe; Peng, Lu; Hu, Ying; Wang, Caifeng; Zhu, Wei; Chen, Su; Chen, Wei

2017-03-01

Supercapacitors, which store electrical energy through reversible ion on the surface of conductive electrodes have gained enormous attention for variously portable energy storage devices. Since the capacitive performance is mainly determined by the structural and electrochemical properties of electrodes, the electrodes become more crucial to higher performance. However, due to the disordered microstructure and low electrochemical activity of electrode for ion tortuous migration and accumulation, the supercapacitors present relatively low capacitance and energy density. Here we report a high-performance supercapacitor based on polyaniline/vertical-aligned carbon nanotubes (PANI/VA-CNTs) nanocomposite electrodes where the vertical-aligned-structure is formed by the electrochemical-induction (0.75 V). The supercapacitor displays large specific capacitance of 403.3 F g-1, which is 6 times higher than disordered CNTs in HClO4 electrolyte. Additionally, the supercapacitor can also present high specific capacitance (314.6 F g-1), excellent cycling stability (90.2% retention after 3000 cycles at 4 A g-1) and high energy density (98.1 Wh kg-1) in EMIBF4 organic electrolyte. The key to high-performance lies in the vertical-aligned-structure providing direct path channel for ion faster diffusion and high electrochemical capacitance of polyaniline for ion more accommodation.

High-performance Supercapacitors Based on Electrochemical-induced Vertical-aligned Carbon Nanotubes and Polyaniline Nanocomposite Electrodes.

PubMed

Wu, Guan; Tan, Pengfeng; Wang, Dongxing; Li, Zhe; Peng, Lu; Hu, Ying; Wang, Caifeng; Zhu, Wei; Chen, Su; Chen, Wei

2017-03-08

Supercapacitors, which store electrical energy through reversible ion on the surface of conductive electrodes have gained enormous attention for variously portable energy storage devices. Since the capacitive performance is mainly determined by the structural and electrochemical properties of electrodes, the electrodes become more crucial to higher performance. However, due to the disordered microstructure and low electrochemical activity of electrode for ion tortuous migration and accumulation, the supercapacitors present relatively low capacitance and energy density. Here we report a high-performance supercapacitor based on polyaniline/vertical-aligned carbon nanotubes (PANI/VA-CNTs) nanocomposite electrodes where the vertical-aligned-structure is formed by the electrochemical-induction (0.75 V). The supercapacitor displays large specific capacitance of 403.3 F g -1 , which is 6 times higher than disordered CNTs in HClO 4 electrolyte. Additionally, the supercapacitor can also present high specific capacitance (314.6 F g -1 ), excellent cycling stability (90.2% retention after 3000 cycles at 4 A g -1 ) and high energy density (98.1 Wh kg -1 ) in EMIBF 4 organic electrolyte. The key to high-performance lies in the vertical-aligned-structure providing direct path channel for ion faster diffusion and high electrochemical capacitance of polyaniline for ion more accommodation.

High-performance Supercapacitors Based on Electrochemical-induced Vertical-aligned Carbon Nanotubes and Polyaniline Nanocomposite Electrodes

PubMed Central

Wu, Guan; Tan, Pengfeng; Wang, Dongxing; Li, Zhe; Peng, Lu; Hu, Ying; Wang, Caifeng; Zhu, Wei; Chen, Su; Chen, Wei

2017-01-01

Supercapacitors, which store electrical energy through reversible ion on the surface of conductive electrodes have gained enormous attention for variously portable energy storage devices. Since the capacitive performance is mainly determined by the structural and electrochemical properties of electrodes, the electrodes become more crucial to higher performance. However, due to the disordered microstructure and low electrochemical activity of electrode for ion tortuous migration and accumulation, the supercapacitors present relatively low capacitance and energy density. Here we report a high-performance supercapacitor based on polyaniline/vertical-aligned carbon nanotubes (PANI/VA-CNTs) nanocomposite electrodes where the vertical-aligned-structure is formed by the electrochemical-induction (0.75 V). The supercapacitor displays large specific capacitance of 403.3 F g−1, which is 6 times higher than disordered CNTs in HClO4 electrolyte. Additionally, the supercapacitor can also present high specific capacitance (314.6 F g−1), excellent cycling stability (90.2% retention after 3000 cycles at 4 A g−1) and high energy density (98.1 Wh kg−1) in EMIBF4 organic electrolyte. The key to high-performance lies in the vertical-aligned-structure providing direct path channel for ion faster diffusion and high electrochemical capacitance of polyaniline for ion more accommodation. PMID:28272474

[Electrochemical detection of toxin gene in Listeria monocytogenes].

PubMed

Wu, Ling-Wei; Liu, Quan-Jun; Wu, Zhong-Wei; Lu, Zu-Hong

2010-05-01

Listeria monocytogenes (LM) is a food-borne pathogen inducing listeriosis, an illness characterized by encephalitis, septicaemia, and meningitis. Listeriolysin O (LLO) is absolutely required for virulence by L. monocytogenes, and is found only in virulent strains of the species. One of the best ways to detect and confirm the pathogen is detection of one of the virulence factors, LLO, produced by the microorganism. This paper focused on the electrical method used to detect the LLO toxin gene in food products and organism without labeling the target DNA. The electrochemical sensor was obtained by immobilizing single-stranded oligonucleotides onto the gold electrode with the mercaptan activated by N-hydroxysulfosuccinimide (NHS) and N-(3-dimethylamion)propyl-N'-ethyl carbodiimidehydrochloride (EDC). The hy-bridization reaction that occurred on the electrode surface was evidenced by Cyclic Voltammetry (CV) analysis using [Co(phen)3](ClO4)3 as an indicator. The covalently immobilized single-stranded DNA could selectively hybridize to its complementary DNA in solution to form double-stranded DNA on the gold surface. A significant increase of the peak cur-rent of Cyclic Voltammetry (CV) upon hybridization of immobilized ssDNA with PCR amplification products in the solu-tion was observed. This peak current change was used to monitor the amount of PCR amplification products. Factors deter-mining the sensitivity of the electrochemical assay, such as DNA target concentration and hybridization conditions, were investigated. The coupling of DNA to the electrochemical sensors has the potential of the quantitative evaluation of gene.

In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

PubMed

Chen, Daqun; Hu, Weihua

2017-04-18

Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization

NASA Astrophysics Data System (ADS)

Sulyma, Christopher Michael

This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu lines and Ta barriers in the fabrication of semiconductor devices. It is shown that in non-alkaline solutions of H2O2, the SA-promoted surface complexes of Cu and Ta can potentially support chemically enhanced material removal in low-pressure CMP of surface topographies overlying fragile low-k dielectrics. ADS can suppress Cu dissolution without significantly affecting the surface chemistry of Ta. Chapter 6 discusses anodic corrosion of Ta, which is examined as a possible route to voltage induced removal of Ta for potential applications in electrochemical mechanical planarization (ECMP) of diffusion barriers. This strategy involves electro-oxidation of Ta in the presence of NO3- anions to form mechanically weak surface oxide films, followed by removal of the oxide layers by moderate mechanical abrasion. This NO3 - system is compared with a reference solution of Br -. In both electrolytes, the voltammetric currents of anodic oxidation exhibit oscillatory behaviors in the initial cycles of slow (5 mV s-1) voltage scans. The frequencies of these current oscillations are show signature attributes of localized pitting or general surface corrosion caused by Br- or NO3 -, respectively. Scanning electron microscopy, cyclic voltammetry, polarization resistance measurements, and time resolved Fourier transform impedance spectroscopy provide additional details about these corrosion mechanism. Apart from their relevance in the context of ECMP, the results also address certain fundamental aspects of pitting and general corrosions. The general protocols necessary to combine and analyze the results of D.C. and A.C. electrochemical measurements involving such valve metal corrosion systems are discussed in detail. In chapter 7 potassium salts of certain oxyanions (nitrate, sulfate and phosphate in particular) are shown to serve as effective surface-modifying agents in chemically enhanced, low-pressure chemical mechanical planarization (CMP) of Ta and TaN barrier layers for interconnect structures. The surface reactions that form the basis of this CMP strategy are investigated here in detail using the electrochemical techniques of cyclic voltammetry, open circuit potential analysis, polarization resistance measurements, and Fourier transform impedance spectroscopy. The results suggest that forming structurally weak oxide layers on the CMP samples is a key to achieving the goal of chemically controlled CMP of Ta/TaN at low down-pressures. (Abstract shortened by UMI.)

Catalysts for electrochemical generation of oxygen

NASA Technical Reports Server (NTRS)

Hagans, P.; Yeager, E.

1979-01-01

Several aspects of the electrolytic evolution of oxygen for use in life support systems are analyzed including kinetic studies of various metal and nonmetal electrode materials, the formation of underpotential films on electrodes, and electrode surface morphology and the use of single crystal metals. In order to investigate the role of surface morphology to electrochemical reactions, a low energy electron diffraction and an Auger electron spectrometer are combined with an electrochemical thin-layer cell allowing initial characterization of the surface, reaction run, and then a comparative surface analysis.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries.

PubMed

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M

2014-08-29

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

NASA Astrophysics Data System (ADS)

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

2014-08-01

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

PubMed Central

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

2014-01-01

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses. PMID:25168309

Selectively-etched nanochannel electrophoretic and electrochemical devices

DOEpatents

Surh, Michael P.; Wilson, William D.; Barbee, Jr., Troy W.; Lane, Stephen M.

2004-11-16

Nanochannel electrophoretic and electrochemical devices having selectively-etched nanolaminates located in the fluid transport channel. The normally flat surfaces of the nanolaminate having exposed conductive (metal) stripes are selectively-etched to form trenches and baffles. The modifications of the prior utilized flat exposed surfaces increase the amount of exposed metal to facilitate electrochemical redox reaction or control the exposure of the metal surfaces to analytes of large size. These etched areas variously increase the sensitivity of electrochemical detection devices to low concentrations of analyte, improve the plug flow characteristic of the channel, and allow additional discrimination of the colloidal particles during cyclic voltammetry.

Selectively-etched nanochannel electrophoretic and electrochemical devices

DOEpatents

Surh, Michael P [Livermore, CA; Wilson, William D [Pleasanton, CA; Barbee, Jr., Troy W.; Lane, Stephen M [Oakland, CA

2006-06-27

Nanochannel electrophoretic and electrochemical devices having selectively-etched nanolaminates located in the fluid transport channel. The normally flat surfaces of the nanolaminate having exposed conductive (metal) stripes are selectively-etched to form trenches and baffles. The modifications of the prior utilized flat exposed surfaces increase the amount of exposed metal to facilitate electrochemical redox reaction or control the exposure of the metal surfaces to analytes of large size. These etched areas variously increase the sensitivity of electrochemical detection devices to low concentrations of analyte, improve the plug flow characteristic of the channel, and allow additional discrimination of the colloidal particles during cyclic voltammetry.

Role of additives in formation of solid-electrolyte interfaces on carbon electrodes and their effect on high-voltage stability.

PubMed

Qu, Weiguo; Dorjpalam, Enkhtuvshin; Rajagopalan, Ramakrishnan; Randall, Clive A

2014-04-01

The in situ modification of a lithium hexafluorophosphate-based electrolyte using a molybdenum oxide catalyst and small amount of water (1 vol %) yields hydrolysis products such as mono-, di-, and alkylfluorophosphates. The electrochemical stability of ultrahigh-purity, high-surface-area carbon electrodes derived from polyfurfuryl alcohol was tested using the modified electrolyte. Favorable modification of the solid electrolyte interface (SEI) layer on the activated carbon electrode increased the cyclable electrochemical voltage window (4.8-1.2 V vs. Li/Li(+)). The chemical modification of the SEI layer induced by electrolyte additives was characterized by using X-ray photoelectron spectroscopy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supported Silver Nanoparticle and Near-Interface Solution Dynamics in a Deep Eutectic Solvent

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

Hammons, Joshua A.; Ustarroz, Jon; Muselle, Thibault

2016-01-28

Type III deep eutectic solvents (DES) have attracted significant interest as both environmentally friendly and functional solvents that are, in some ways, advantageous to traditional aqueous systems. While these solvents continue to produce remarkable thin films and nanoparticle assemblies, their interactions with metallic surfaces are complex and difficult to manipulate. In this study, the near-surface region (2–600 nm) of a carbon surface is investigated immediately following silver nanoparticle nucleation and growth. This is accomplished, in situ, using a novel grazing transmission small-angle X-ray scattering approach with simultaneous voltammetry and electrochemical impedance spectroscopy. With this physical and electrochemical approach, the timemore » evolution of three distinct surface interaction phenomena is observed: aggregation and coalescence of Ag nanoparticles, multilayer perturbations induced by nonaggregated Ag nanoparticles, and a stepwise transport of dissolved Ag species from the carbon surface. The multilayer perturbations contain charge-separated regions of positively charged choline-ethylene and negatively charged Ag and Cl species. Both aggregation-coalescence and the stepwise decrease in Ag precursor near the surface are observed to be very slow (~2 h) processes, as both ion and particle transport are significantly impeded in a DES as compared to aqueous electrolytes. Finally, altogether, this study shows how the unique chemistry of the DES changes near the surface and in the presence of nanoparticles that adsorb the constituent species.« less

Specific anion effects on copper surface through electrochemical treatment: Enhanced photoelectrochemical CO2 reduction activity of derived nanostructures induced by chaotropic anions

NASA Astrophysics Data System (ADS)

Navaee, Aso; Salimi, Abdollah

2018-05-01

Copper derivatives are the most prominent CO2 reduction electrocatalyst. Herein, the metallic copper has been electrochemically treated with some of common ionic salts such as N3bar, HPO2bar, S2bar, Fbar, Clbar, Brbar and Ibar based on the dissolution of a metallic working electrode in an aqueous solution to derive the surface roughness incorporated with nanostructures. Diverse surface morphology can be obtained when the ionic radii of anions are changed. Surface study reveals various roughness shapes based on the size and polarity of the anions, where the ions with higher ionic radii have higher impact on the Cu surface. In comparison, polyatomic oxyanion such as HPO2bar even with large ionic radii do not have enough strength to create the surface roughness than that of oxygen-free anions with large ionic radii. The photoelectrochemical behavior of the modified surfaces toward CO2 reduction is studied at a wide potential window in bicarbonate aqueous solution. Based on our investigations, treated surfaces by Ibar, Clbar and S2bargive a more surface roughness, while Ibar and N3bar offer higher catalytic activity toward CO2 reduction due to possible complexing ability of these anions with Cu cations, followed by formation of the co-catalyst semiconductor and facilitate electron transfer. This methodology can be applied to investigate the effect of ions on transition metals along with obtaining different surface morphologies tailored to different applications.

Preparation and characterization of hierarchical porous carbons derived from solid leather waste for supercapacitor applications.

PubMed

Konikkara, Niketha; Kennedy, L John; Vijaya, J Judith

2016-11-15

Utilization of crust leather waste (CLW) as precursors for the preparation of hierarchical porous carbons (HPC) were investigated. HPCs were prepared from CLW by pre-carbonization followed by chemical activation using KOH at relatively high temperatures. Textural properties of HPC's showed an extent of micro-and mesoporosity with maximum BET surface area of 716m(2)/g. Inducements of graphitic planes in leather waste derived carbons were observed from X-ray diffraction and HR-TEM analysis. Microstructure, thermal behavior and surface functional groups were identified using FT-Raman, thermo gravimetric analysis and FT-IR techniques. HPCs were evaluated for electrochemical properties by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) and electrochemical impedance spectroscopy (EIS) by three electrode system. CLC9 sample showed a maximum capacitance of 1960F/g in 1M KCl electrolyte. Results achieved from rectangular curves of CV, GCD symmetric curves and Nyquist plots show that the leather waste carbon is suitable to fabricate supercapacitors as it possess high specific capacitance and electrochemical cycle stability. The present study proposes an effective method for solid waste management in leather industry by the way of converting toxic leather waste to new graphitic porous carbonaceous materials as a potential candidate for energy storage devices. Copyright © 2016 Elsevier B.V. All rights reserved.

Local electric and electro-chemical investigations of cyanobacteria films

NASA Astrophysics Data System (ADS)

Marlière, C.; Ramonda, M.; de Wit, R.

2009-12-01

Carbonate reservoirs are submitted to microbial metabolic processes promoting either the precipitation or the dissolution of calcium carbonate, especially in network of fractures and fault zones. Such phenomena may act as a seal during fault zone evolution and, later, reservoir production, modifying greatly the connectivity of fractures, permeability structure and drainage in the vicinity of otherwise major fluid conduits. Several laboratory studies have demonstrated the utility of geophysical methods such as complex electrical conductivity ones for the investigation of microbial-induced changes in porous geologic media. The primary suggestion of these studies was that temporal variations in the geophysical signatures corresponded with microbial-induced changes in the geologic media. However these variations of electric signal could be due to the combined effects of surface and volume contributions in the studied geologic medium. Surface effects such as attachment of the bacteria on substrate surface or reactions of carbonate precipitation/dissolution are crucial for concerns about local seal or opening or, more generally, modification in connectivity of fracture or porosity network in reservoirs. That is why we have launched a new study in order to clearly distinguish surface effects from volume one in electrical responses mediated by biogenic material. The surface processes of cell growth, attachment onto substrate surfaces and the reactions of carbonate precipitation/dissolution are studied by local (at sub-micrometric scales) methods such as atomic force microscopy (AFM) and scanning electrochemical potential microscopy (SECM) probing. These methods are carried out with living biological specimen under in situ conditions. Our first studies have been done by AFM in tunnelling mode on cyanobacteria (from CaCO3 rich sediments from a hyper saline lake). The immobilized bacteria have been scanned in ambient gaseous atmosphere by the nanometric AFM tip. In these conditions the cyanobacteria are recovered by a micrometric film of water. Both the roughness signal and electric current flowing from the tip to the substrate through the sample have simultaneously been measured for different values of electrical voltage. The measured electrical signals are weak but well above the noise level. Our observations of the local variations of the electro-chemical signal at a high spatial resolution (at sub-micrometer level) and at short acquisition times will be presented and discussed in detail.

Chlorhexidine possesses unique cytotoxic actions in rat thymic lymphocytes: Its relation with electrochemical property of membranes.

PubMed

Nonami, Kayo; Saitoh, Shohei; Nishimura-Danjobara, Yumiko; Ishida, Shiro; Oyama, Yasuo

2016-12-01

Chlorhexidine (CHX) is an antibacterial agent used in various types of pharmaceutical products. Therefore, CHX is easily found around us. Owing to its positive charge, the electrochemical property of cell membranes was assumed to be a key point of cytotoxic action of CHX. Depolarization of membranes attenuated the cytotoxic action of CHX in rat thymic lymphocytes. CHX interfered with annexin V binding to membranes. Manipulations to induce exposure of phosphatidylserine on the outer membrane surface augmented the cytotoxic action of CHX, indicating that changes in the electrochemical property of membranes affected the cytotoxic action of CHX. Hence, CHX might kill cells physiologically undergoing apoptosis, resulting instead in necrotic cell death. However, the threshold CHX concentration in this in vitro study was slightly higher than blood CHX concentrations observed clinically. Therefore, these results may support the safety of CHX use although CHX possesses unique cytotoxic actions described in this study. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of SnO2 pillared carbon using long chain alkylamine grafted graphene oxide: an efficient anode material for lithium ion batteries

NASA Astrophysics Data System (ADS)

Reddy, M. Jeevan Kumar; Ryu, Sung Hun; Shanmugharaj, A. M.

2015-12-01

With the objective of developing new advanced composite materials that can be used as anodes for lithium ion batteries (LIBs), herein we describe the synthesis of SnO2 pillared carbon using various alkylamine (hexylamine; dodecylamine and octadecylamine) grafted graphene oxides and butyl trichlorotin precursors followed by its calcination at 500 °C for 2 h. While the grafted alkylamine induces crystalline growth of SnO2 pillars, thermal annealing of alkylamine grafted graphene oxide results in the formation of amorphous carbon coated graphene. Field emission scanning electron microscopy (FE-SEM) results reveal the successful formation of SnO2 pillared carbon on the graphene surface. X-ray diffraction (XRD), transmission electron microscopy (TEM) and Raman spectroscopy characterization corroborates the formation of rutile SnO2 crystals on the graphene surface. A significant rise in the BET surface area is observed for SnO2 pillared carbon, when compared to pristine GO. Electrochemical characterization studies of SnO2 pillared carbon based anode materials showed an enhanced lithium storage capacity and fine cyclic performance in comparison with pristine GO. The initial specific capacities of SnO2 pillared carbon are observed to be 1379 mA h g-1, 1255 mA h g-1 and 1360 mA h g-1 that decrease to 750 mA h g-1, 643 mA h g-1 and 560 mA h g-1 depending upon the chain length of grafted alkylamine on the graphene surface respectively. Electrochemical impedance spectral analysis reveals that the exchange current density of SnO2 pillared carbon based electrodes is higher, corroborating its enhanced electrochemical activity in comparison with GO based electrodes.With the objective of developing new advanced composite materials that can be used as anodes for lithium ion batteries (LIBs), herein we describe the synthesis of SnO2 pillared carbon using various alkylamine (hexylamine; dodecylamine and octadecylamine) grafted graphene oxides and butyl trichlorotin precursors followed by its calcination at 500 °C for 2 h. While the grafted alkylamine induces crystalline growth of SnO2 pillars, thermal annealing of alkylamine grafted graphene oxide results in the formation of amorphous carbon coated graphene. Field emission scanning electron microscopy (FE-SEM) results reveal the successful formation of SnO2 pillared carbon on the graphene surface. X-ray diffraction (XRD), transmission electron microscopy (TEM) and Raman spectroscopy characterization corroborates the formation of rutile SnO2 crystals on the graphene surface. A significant rise in the BET surface area is observed for SnO2 pillared carbon, when compared to pristine GO. Electrochemical characterization studies of SnO2 pillared carbon based anode materials showed an enhanced lithium storage capacity and fine cyclic performance in comparison with pristine GO. The initial specific capacities of SnO2 pillared carbon are observed to be 1379 mA h g-1, 1255 mA h g-1 and 1360 mA h g-1 that decrease to 750 mA h g-1, 643 mA h g-1 and 560 mA h g-1 depending upon the chain length of grafted alkylamine on the graphene surface respectively. Electrochemical impedance spectral analysis reveals that the exchange current density of SnO2 pillared carbon based electrodes is higher, corroborating its enhanced electrochemical activity in comparison with GO based electrodes. Electronic supplementary information (ESI) available: XPS, FE-SEM, FE-TEM, TGA FT-IR, EIS, CV of and charge discharge profiles of RGO-SnO2 composites. See DOI: 10.1039/c5nr06680h

Electrochemically induced maskless metal deposition on micropore wall.

PubMed

Liu, Jie; Hébert, Clément; Pham, Pascale; Sauter-Starace, Fabien; Haguet, Vincent; Livache, Thierry; Mailley, Pascal

2012-05-07

By applying an external electric field across a micropore via an electrolyte, metal ions in the electrolyte can be reduced locally onto the inner wall of the micropore, which was fabricated in a silica-covered silicon membrane. This maskless metal deposition on the silica surface is a result of the pore membrane polarization in the electric field. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CoMn2O4 Spinel Hierarchical Microspheres Assembled with Porous Nanosheets as Stable Anodes for Lithium-ion Batteries

PubMed Central

Hu, Lin; Zhong, Hao; Zheng, Xinrui; Huang, Yimin; Zhang, Ping; Chen, Qianwang

2012-01-01

Herein, we report the feasibility to enhance the capacity and stability of CoMn2O4 anode materials by fabricating hierarchical mesoporous structure. The open space between neighboring nanosheets allows for easy diffusion of the electrolyte. The hierarchical microspheres assembled with nanosheets can ensure that every nanosheet participates in the electrochemical reaction, because every nanosheet is contacted with the electrolyte solution. The hierarchical structure and well interconnected pores on the surface of nanosheets will enhance the CoMn2O4/electrolyte contact area, shorten the Li+ ion diffusion length in the nanosheets, and accommodate the strain induced by the volume change during the electrochemical reaction. The last, hierarchical architecture with spherical morphology possesses relatively low surface energy, which results in less extent of self-aggregation during charge/discharge process. As a result, CoMn2O4 hierarchical microspheres can achieve a good cycle ability and high rate capability. PMID:23248749

Gate-Induced Metal–Insulator Transition in MoS 2 by Solid Superionic Conductor LaF 3

DOE PAGES

Wu, Chun-Lan; Yuan, Hongtao; Li, Yanbin; ...

2018-03-23

Electric-double-layer (EDL) gating with liquid electrolyte has been a powerful tool widely used to explore emerging interfacial electronic phenomena. Due to the large EDL capacitance, a high carrier density up to 10 14 cm –2 can be induced, directly leading to the realization of field-induced insulator to metal (or superconductor) transition. However, the liquid nature of the electrolyte has created technical issues including possible side electrochemical reactions or intercalation, and the potential for huge strain at the interface during cooling. In addition, the liquid coverage of active devices also makes many surface characterizations and in situ measurements challenging. Here, wemore » demonstrate an all solid-state EDL device based on a solid superionic conductor LaF 3, which can be used as both a substrate and a fluorine ionic gate dielectric to achieve a wide tunability of carrier density without the issues of strain or electrochemical reactions and can expose the active device surface for external access. Based on LaF 3 EDL transistors (EDLTs), we observe the metal–insulator transition in MoS 2. Interestingly, the well-defined crystal lattice provides a more uniform potential distribution in the substrate, resulting in less interface electron scattering and therefore a higher mobility in MoS 2 transistors. Finally, this result shows the powerful gating capability of LaF 3 solid electrolyte for new possibilities of novel interfacial electronic phenomena.« less

Electrochemically exfoliated graphene anodes with enhanced biocurrent production in single-chamber air-breathing microbial fuel cells.

PubMed

Najafabadi, Amin Taheri; Ng, Norvin; Gyenge, Előd

2016-07-15

Microbial fuel cells (MFCs) present promising options for environmentally sustainable power generation especially in conjunction with waste water treatment. However, major challenges remain including low power density, difficult scale-up, and durability of the cell components. This study reports enhanced biocurrent production in a membrane-free MFC, using graphene microsheets (GNs) as anode and MnOx catalyzed air cathode. The GNs are produced by ionic liquid assisted simultaneous anodic and cathodic electrochemical exfoliation of iso-molded graphite electrodes. The GNs produced by anodic exfoliation increase the MFC peak power density by over 300% compared to plain carbon cloth (i.e., 2.85Wm(-2) vs 0.66Wm(-2), respectively), and by 90% compared to conventional carbon black (i.e., Vulcan XC-72) anode. These results exceed previously reported power densities for graphene-containing MFC anodes. The fuel cell polarization results are corroborated by electrochemical impedance spectroscopy indicating three times lower charge transfer resistance for the GN anode. Material characterizations suggest that the best performing GN samples were of relatively smaller size (~500nm), with higher levels of ionic liquid induced surface functionalization during the electrochemical exfoliation process. Copyright © 2016 Elsevier B.V. All rights reserved.

Photoelectrochemical Degradation of Organic Compounds Coupled with Molecular Hydrogen Generation Using Electrochromic TiO2 Nanotube Arrays.

PubMed

Koo, Min Seok; Cho, Kangwoo; Yoon, Jeyong; Choi, Wonyong

2017-06-06

Vertically aligned TiO 2 nanotube arrays (TNTs) were prepared by electrochemical anodization, and then cathodically polarized with dark blue coloration for the dual-functional photoelectrochemical water treatment of organic substrates degradation and accompanying H 2 generation. The resulting Blue-TNTs (inner diameter: ∼40 nm; length: ∼9 μm) showed negligible shift in X-ray diffraction pattern compared with the intact TNTs, but the X-ray photoelectron spectra indicated a partial reduction of Ti 4+ to Ti 3+ on the surface. The electrochemical analyses of Blue-TNTs revealed a marked enhancement in donor density and electrical conductivity by orders of magnitude. Degradations of test organic substrates on Blue-TNTs were compared with the intact TNTs in electrochemical (EC), photocatalytic (PC), and photoelectrochemical (PEC) conditions (potential bias: 1.64 V NHE ; λ > 320 nm). The degradation of 4-chlorophenol was greatly enhanced on Blue-TNTs particularly in PEC condition, whereas the PC activities of the Blue- and intact TNTs were similar. The potential bias of 1.64 V NHE did not induce any noticeable activity in EC condition. Similar trends were observed for the degradation of humic acid and fulvic acid, where main working oxidants were found to be the surface hydroxyl radical as confirmed by hydroxyl radical probe and scavenger tests. H 2 generation coupled with the organic degradation was observed only in PEC condition, where the H 2 generation rate with Blue-TNTs was more than doubled from that of intact TNTs. Such superior PEC activity was not observed when a common TiO 2 nanoparticle film was used as a photoanode. The enhanced electric conductivity of Blue-TNTs coupled with a proper band bending in PEC configuration seemed to induce a highly synergic enhancement.

Growth, structure and stability of sputter-deposited MoS2 thin films.

PubMed

Kaindl, Reinhard; Bayer, Bernhard C; Resel, Roland; Müller, Thomas; Skakalova, Viera; Habler, Gerlinde; Abart, Rainer; Cherevan, Alexey S; Eder, Dominik; Blatter, Maxime; Fischer, Fabian; Meyer, Jannik C; Polyushkin, Dmitry K; Waldhauser, Wolfgang

2017-01-01

Molybdenum disulphide (MoS 2 ) thin films have received increasing interest as device-active layers in low-dimensional electronics and also as novel catalysts in electrochemical processes such as the hydrogen evolution reaction (HER) in electrochemical water splitting. For both types of applications, industrially scalable fabrication methods with good control over the MoS 2 film properties are crucial. Here, we investigate scalable physical vapour deposition (PVD) of MoS 2 films by magnetron sputtering. MoS 2 films with thicknesses from ≈10 to ≈1000 nm were deposited on SiO 2 /Si and reticulated vitreous carbon (RVC) substrates. Samples deposited at room temperature (RT) and at 400 °C were compared. The deposited MoS 2 was characterized by macro- and microscopic X-ray, electron beam and light scattering, scanning and spectroscopic methods as well as electrical device characterization. We find that room-temperature-deposited MoS 2 films are amorphous, of smooth surface morphology and easily degraded upon moderate laser-induced annealing in ambient conditions. In contrast, films deposited at 400 °C are nano-crystalline, show a nano-grained surface morphology and are comparatively stable against laser-induced degradation. Interestingly, results from electrical transport measurements indicate an unexpected metallic-like conduction character of the studied PVD MoS 2 films, independent of deposition temperature. Possible reasons for these unusual electrical properties of our PVD MoS 2 thin films are discussed. A potential application for such conductive nanostructured MoS 2 films could be as catalytically active electrodes in (photo-)electrocatalysis and initial electrochemical measurements suggest directions for future work on our PVD MoS 2 films.

Growth, structure and stability of sputter-deposited MoS2 thin films

PubMed Central

Bayer, Bernhard C; Resel, Roland; Müller, Thomas; Skakalova, Viera; Habler, Gerlinde; Abart, Rainer; Cherevan, Alexey S; Eder, Dominik; Blatter, Maxime; Fischer, Fabian; Meyer, Jannik C; Polyushkin, Dmitry K; Waldhauser, Wolfgang

2017-01-01

Molybdenum disulphide (MoS2) thin films have received increasing interest as device-active layers in low-dimensional electronics and also as novel catalysts in electrochemical processes such as the hydrogen evolution reaction (HER) in electrochemical water splitting. For both types of applications, industrially scalable fabrication methods with good control over the MoS2 film properties are crucial. Here, we investigate scalable physical vapour deposition (PVD) of MoS2 films by magnetron sputtering. MoS2 films with thicknesses from ≈10 to ≈1000 nm were deposited on SiO2/Si and reticulated vitreous carbon (RVC) substrates. Samples deposited at room temperature (RT) and at 400 °C were compared. The deposited MoS2 was characterized by macro- and microscopic X-ray, electron beam and light scattering, scanning and spectroscopic methods as well as electrical device characterization. We find that room-temperature-deposited MoS2 films are amorphous, of smooth surface morphology and easily degraded upon moderate laser-induced annealing in ambient conditions. In contrast, films deposited at 400 °C are nano-crystalline, show a nano-grained surface morphology and are comparatively stable against laser-induced degradation. Interestingly, results from electrical transport measurements indicate an unexpected metallic-like conduction character of the studied PVD MoS2 films, independent of deposition temperature. Possible reasons for these unusual electrical properties of our PVD MoS2 thin films are discussed. A potential application for such conductive nanostructured MoS2 films could be as catalytically active electrodes in (photo-)electrocatalysis and initial electrochemical measurements suggest directions for future work on our PVD MoS2 films. PMID:28685112

Constructing superhydrophobic WO3@TiO2 nanoflake surface beyond amorphous alloy against electrochemical corrosion on iron steel

NASA Astrophysics Data System (ADS)

Yu, S. Q.; Ling, Y. H.; Wang, R. G.; Zhang, J.; Qin, F.; Zhang, Z. J.

2018-04-01

To eliminate harmful localized corrosion, a new approach by constructing superhydrophobic WO3@TiO2 hierarchical nanoflake surface beyond FeW amorphous alloy formed on stainless steel was proposed. Facile dealloying and liquid deposition was employed at low temperature to form a nanostructured layer composing inner WO3 nanoflakes coated with TiO2 nanoparticles (NPs) layer. After further deposition of PFDS on nanoflakes, the contact angle reached 162° while the corrosion potential showed a negative shift of 230 mV under illumination, resulting in high corrosion resistance in 3.5 wt% NaCl solution. The tradeoff between superhydrophobic surface and photo-electro response was investigated. It was found that this surface feature makes 316 SS be immune to localized corrosion and a pronounced photo-induced process of electron storage/release as well as the stability of the functional layer were detected with or without illumination, and the mechanism behind this may be related to the increase of surface potential due to water repellence and the delayed cathodic protection of semiconducting coating derived mainly from the valence state changes of WO3. This study demonstrates a simple and low-cost electrochemical approach for protection of steel and novel means to produce superhydrophobic surface and cathodic protection with controllable electron storage/release on engineering scale.

Nanostructured surfaces for analysis of anticancer drug and cell diagnosis based on electrochemical and SERS tools.

PubMed

El-Said, Waleed A; Yoon, Jinho; Choi, Jeong-Woo

2018-01-01

Discovering new anticancer drugs and screening their efficacy requires a huge amount of resources and time-consuming processes. The development of fast, sensitive, and nondestructive methods for the in vitro and in vivo detection of anticancer drugs' effects and action mechanisms have been done to reduce the time and resources required to discover new anticancer drugs. For the in vitro and in vivo detection of the efficiency, distribution, and action mechanism of anticancer drugs, the applications of electrochemical techniques such as electrochemical cell chips and optical techniques such as surface-enhanced Raman spectroscopy (SERS) have been developed based on the nanostructured surface. Research focused on electrochemical cell chips and the SERS technique have been reviewed here; electrochemical cell chips based on nanostructured surfaces have been developed for the in vitro detection of cell viability and the evaluation of the effects of anticancer drugs, which showed the high capability to evaluate the cytotoxic effects of several chemicals at low concentrations. SERS technique based on the nanostructured surface have been used as label-free, simple, and nondestructive techniques for the in vitro and in vivo monitoring of the distribution, mechanism, and metabolism of different anticancer drugs at the cellular level. The use of electrochemical cell chips and the SERS technique based on the nanostructured surface should be good tools to detect the effects and action mechanisms of anticancer drugs.

Nanostructured surfaces for analysis of anticancer drug and cell diagnosis based on electrochemical and SERS tools

NASA Astrophysics Data System (ADS)

El-Said, Waleed A.; Yoon, Jinho; Choi, Jeong-Woo

2018-04-01

Discovering new anticancer drugs and screening their efficacy requires a huge amount of resources and time-consuming processes. The development of fast, sensitive, and nondestructive methods for the in vitro and in vivo detection of anticancer drugs' effects and action mechanisms have been done to reduce the time and resources required to discover new anticancer drugs. For the in vitro and in vivo detection of the efficiency, distribution, and action mechanism of anticancer drugs, the applications of electrochemical techniques such as electrochemical cell chips and optical techniques such as surface-enhanced Raman spectroscopy (SERS) have been developed based on the nanostructured surface. Research focused on electrochemical cell chips and the SERS technique have been reviewed here; electrochemical cell chips based on nanostructured surfaces have been developed for the in vitro detection of cell viability and the evaluation of the effects of anticancer drugs, which showed the high capability to evaluate the cytotoxic effects of several chemicals at low concentrations. SERS technique based on the nanostructured surface have been used as label-free, simple, and nondestructive techniques for the in vitro and in vivo monitoring of the distribution, mechanism, and metabolism of different anticancer drugs at the cellular level. The use of electrochemical cell chips and the SERS technique based on the nanostructured surface should be good tools to detect the effects and action mechanisms of anticancer drugs.

High-performance and versatile electrochemical aptasensor based on self-supported nanoporous gold microelectrode and enzyme-induced signal amplification.

PubMed

Shi, Lei; Rong, Xiaojiao; Wang, Yan; Ding, Shiming; Tang, Wanying

2018-04-15

Herein, novel and versatile electrochemical aptasensors were constructed on a self-supported nanoporous gold (np-Au) microelectrode, integrating with an exonuclease III (Exo III) induced signal amplification strategy. Self-supported np-Au microelectrode with 3D bicontinuous nanoporous structures possesses tremendously large specific area, clean surface, high stability and biocompatibility, bringing about significant advantages in both molecular recognition and signal response. As paradigms, two analytes of bisphenol A (BPA) and ochratoxin A (OTA) were selected to demonstrate the superiority and versatility of designed aptasensors. Trace amounts of mDNA (associated with BPA or OTA concentration) hybridized with cDNA strands assembled on np-Au microelectrode, activating the cleavage reaction with Exo III. Thus, cDNA was digested and mDNA was released to undergo a new hybridization and cleavage cycle. Finally, residual cDNA strands were recognized by methylene blue labelled rDNA/AuNPs with the assistance of hDNA to generate the electrochemical signals, which were used to quantitatively monitor targets. Under the optimized conditions, prepared aptasensors exhibited wide linear ranges (25pg/mL to 2ng/mL for BPA, 10pg/mL to 5ng/mL for OTA) with ultralow detection limits (10pg/mL for BPA, 5pg/mL for OTA), excellent selectivity and stability, and reliable detection in real samples. This work opens a new horizon for constructing promising electrochemical aptasensors for environmental monitoring, medical diagnostics and food safety. Copyright © 2017 Elsevier B.V. All rights reserved.

Enhanced electrochemical nanoring electrode for analysis of cytosol in single cells.

PubMed

Zhuang, Lihong; Zuo, Huanzhen; Wu, Zengqiang; Wang, Yu; Fang, Danjun; Jiang, Dechen

2014-12-02

A microelectrode array has been applied for single cell analysis with relatively high throughput; however, the cells were typically cultured on the microelectrodes under cell-size microwell traps leading to the difficulty in the functionalization of an electrode surface for higher detection sensitivity. Here, nanoring electrodes embedded under the microwell traps were fabricated to achieve the isolation of the electrode surface and the cell support, and thus, the electrode surface can be modified to obtain enhanced electrochemical sensitivity for single cell analysis. Moreover, the nanometer-sized electrode permitted a faster diffusion of analyte to the surface for additional improvement in the sensitivity, which was evidenced by the electrochemical characterization and the simulation. To demonstrate the concept of the functionalized nanoring electrode for single cell analysis, the electrode surface was deposited with prussian blue to detect intracellular hydrogen peroxide at a single cell. Hundreds of picoamperes were observed on our functionalized nanoring electrode exhibiting the enhanced electrochemical sensitivity. The success in the achievement of a functionalized nanoring electrode will benefit the development of high throughput single cell electrochemical analysis.

Electrochemical Responsive Superhydrophilic Surfaces of Polythiophene Derivatives towards Cell Capture and Release.

PubMed

Hao, Yuwei; Li, Yingying; Zhang, Feilong; Cui, Haijun; Hu, Jinsong; Meng, Jingxin; Wang, Shutao

2018-03-23

Highly efficient cell capture and release with low background are urgently required for early diagnosis of diseases such as cancer. Herein, we report an electrochemical responsive superhydrophilic surface exhibiting specific cell capture and release with high yields and extremely low nonspecific adhesion. Through electrochemical deposition, 3-substituted thiophene derivatives are deposited onto indium tin oxide (ITO) nanowire arrays with 4-n-nonylbenzeneboronic acid (BA) as dopant, fabricating the electrochemical responsive superhydrophilic surfaces. The molecular recognition between sialic acids over-expressed on the cell membrane and doped BAs endows the electrochemical responsive surfaces with the ability to capture and release targeted cancer cells. By adjusting the substituent group of thiophene derivatives, the surface wettability can be readily regulated and further utilized for reducing nonspecific cell adhesion. Significantly, the released cells still maintain a high proliferation ability, which indicates that the applied potential does not significantly harm the cells. Therefore, these results may provide a new strategy to achieve advanced functions of biomedical materials, such as low nonspecific adhesion. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of silver tips for scanning tunneling microscope induced luminescence.

PubMed

Zhang, C; Gao, B; Chen, L G; Meng, Q S; Yang, H; Zhang, R; Tao, X; Gao, H Y; Liao, Y; Dong, Z C

2011-08-01

We describe a reliable fabrication procedure of silver tips for scanning tunneling microscope (STM) induced luminescence experiments. The tip was first etched electrochemically to yield a sharp cone shape using selected electrolyte solutions and then sputter cleaned in ultrahigh vacuum to remove surface oxidation. The tip status, in particular the tip induced plasmon mode and its emission intensity, can be further tuned through field emission and voltage pulse. The quality of silver tips thus fabricated not only offers atomically resolved STM imaging, but more importantly, also allows us to perform challenging "color" photon mapping with emission spectra taken at each pixel simultaneously during the STM scan under relatively small tunnel currents and relatively short exposure time.

Effects of water plasma immersion ion implantation on surface electrochemical behavior of NiTi shape memory alloys in simulated body fluids

NASA Astrophysics Data System (ADS)

Liu, X. M.; Wu, S. L.; Chu, Paul K.; Chung, C. Y.; Chu, C. L.; Yeung, K. W. K.; Lu, W. W.; Cheung, K. M. C.; Luk, K. D. K.

2007-01-01

Water plasma immersion ion implantation (PIII) was conducted on orthopedic NiTi shape memory alloy to enhance the surface electrochemical characteristics. The surface composition of the NiTi alloy before and after H 2O-PIII was determined by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) was utilized to determine the roughness and morphology of the NiTi samples. Potentiodynamic polarization tests and electrochemical impedance spectroscopy (EIS) were carried out to investigate the surface electrochemical behavior of the control and H 2O-PIII NiTi samples in simulated body fluids (SBF) at 37 °C as well as the mechanism. The H 2O-PIII NiTi sample showed a higher breakdown potential ( Eb) than the control sample. Based on the AFM results, two different physical models with related equivalent electrical circuits were obtained to fit the EIS data and explain the surface electrochemical behavior of NiTi in SBF. The simulation results demonstrate that the higher resistance of the oxide layer produced by H 2O-PIII is primarily responsible for the improvement in the surface corrosion resistance.

Catalysts for electrochemical generation of oxygen

NASA Technical Reports Server (NTRS)

Hagans, P.; Yeager, E.

1978-01-01

Single crystal surfaces of platinum and gold and transition metal oxides of the spinel type were studied to find more effective catalysts for the electrolytic evolution of oxygen and to understand the mechanism and kinetics for the electrocatalysis in relation to the surface electronic and lattice properties of the catalyst. The single crystal studies involve the use of low energy electron diffraction (LEED) and Auger electron spectroscopy as complementary tools to the electrochemical measurements. Modifications to the transfer system and to the thin-layer electrochemical cell used to facilitate the transfer between the ultrahigh vacuum environment of the electron surface physics equipment and the electrochemical environment with a minimal possibility of changes in the surface structure, are described. The electrosorption underpotential deposition of Pb onto the Au(111), (100) and (110) single crystal surfaces with the thin-layer cell-LEED-Auger system is discussed as well as the synthesis of spinels for oxygen evolution studies.

Lubricant-impregnated surfaces for electrochemical applications, and devices and systems using same

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

Solomon, Brian Richmond; Chen, Xinwei; Chiang, Yet-Ming

In certain embodiments, the invention relates to an electrochemical device having a liquid lubricant impregnated surface. At least a portion of the interior surface of the electrochemical device includes a portion that includes a plurality of solid features disposed therein. The plurality of solid features define a plurality of regions therebetween. A lubricant is disposed in the plurality of regions which retain the liquid lubricant in the plurality of regions during operation of the device. An electroactive phase comes in contact with at least the portion of the interior surface. The liquid lubricant impregnated surface introduces a slip at themore » surface when the electroactive phase flows along the surface. The electroactive phase may be a yield stress fluid.« less

Controlled Atmosphere High Temperature SPM for electrochemical measurements

NASA Astrophysics Data System (ADS)

Vels Hansen, K.; Sander, C.; Koch, S.; Mogensen, M.

2007-03-01

A new controlled atmosphere high temperature SPM has been designed and build for the purpose of performing electrochemical measurements on solid oxide fuel cell materials. The first tests show that images can be obtained at a surface temperature of 465°C in air with a standard AFM AC probe. The aim is to produce images at a surface temperature of 800°C with electrically conducting ceramic probes as working electrodes that can be positioned at desired locations at the surface for electrochemical measurements.

Poly(vinyl Alcohol) Borate Gel Polymer Electrolytes Prepared by Electrodeposition and Their Application in Electrochemical Supercapacitors.

PubMed

Jiang, Mengjin; Zhu, Jiadeng; Chen, Chen; Lu, Yao; Ge, Yeqian; Zhang, Xiangwu

2016-02-10

Gel polymer electrolytes (GPEs) have been studied for preparing flexible and compact electrochemical energy storage devices. However, the preparation and use of GPEs are complex, and most GPEs prepared through traditional methods do not have good wettability with the electrodes, which retard them from achieving their performance potential. In this study, these problems are addressed by conceiving and implementing a simple, but effective, method of electrodepositing poly(vinyl alcohol) potassium borate (PVAPB) GPEs directly onto the surfaces of active carbon electrodes for electrochemical supercapacitors. PVAPB GPEs serve as both the electrolyte and the separator in the assembled supercapacitors, and their scale and shape are determined solely by the geometry of the electrodes. PVAPB GPEs have good bonding to the active electrode materials, leading to excellent and stable electrochemical performance of the supercapacitors. The electrochemical performance of PVAPB GPEs and supercapacitors can be manipulated simply by adjusting the concentration of KCl salt used during the electrodeposition process. With a 0.9 M KCl concentration, the as-prepared supercapacitors deliver a specific capacitance of 65.9 F g(-1) at a current density of 0.1 A g(-1) and retain more than 95% capacitance after 2000 charge/discharge cycles at a current density of 1 A g(-1). These supercapacitors also exhibit intelligent high voltage self-protection function due to the electrolysis-induced cross-linking effect of PVAPB GPEs.

A sensitive electrochemical biosensor for detection of protein kinase A activity and inhibitors based on Phos-tag and enzymatic signal amplification.

PubMed

Yin, Huanshun; Wang, Mo; Li, Bingchen; Yang, Zhiqing; Zhou, Yunlei; Ai, Shiyun

2015-01-15

A simple, highly sensitive and selective electrochemical assay is developed for the detection of protein kinase A (PKA) activity based on the specific recognition utility of Phos-tag for kinase-induced phosphopeptides and enzymatic signal amplification. When the substrate peptide was phosphorylated by PKA reaction, they could specifically bind with Phos-tag-biotin in the presence of Zn(2+) through the formation of a specific noncovalent complex with the phosphomonoester dianion in phosphorylated peptides. Through the further specific interaction between biotin and avidin, avidin functionalized horseradish peroxidase (HRP) can be captured on the electrode surface. Under the catalytic effect of HRP, a sensitive electrochemical signal for benzoquinone was obtained, which was related to PKA activity. Under the optimal experiment conditions, the proposed electrochemical method presented dynamic range from 0.5 to 25 unit/mL with low detection limit of 0.15 unit/mL. This new detection strategy was also successfully applied to analyze the inhibition effect of inhibitors (ellagic acid and H-89) on PKA activity and monitored the PKA activity in cell lysates. Therefore, this Phos-tag-based electrochemical assay offers an alternative platform for PKA activity assay and inhibitor screening, and thus it might be a valuable tool for development of targeted therapy and clinical diagnosis. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of humic substances on electrochemical degradation of trichloroethylene in limestone aquifers

PubMed Central

Rajic, Ljiljana; Fallahpour, Noushin; Nazari, Roya; Alshawabkeh, Akram N.

2015-01-01

In this study we investigate the influence of humic substances (HS) on electrochemical transformation of trichloroethylene (TCE) in groundwater from limestone aquifers. A laboratory flow-through column with an electrochemical reactor that consists of a palladized iron foam cathode followed by a MMO anode was used to induce TCE electro-reduction in groundwater. Up to 82.9% TCE removal was achieved in the absence of HS. Presence of 1, 2, 5, and 10 mgTOC L−1 reduced TCE removal to 70.9%, 61.4%, 51.8% and 19.5%, respectively. The inverse correlation between HS content and TCE removal was linear. Total organic carbon (TOC), dissolved organic carbon (DOC) and absorption properties (A=254 nm, 365 nm and 436 nm) normalized to DOC, were monitored during treatment to understand the behavior and impacts of HS under electrochemical processes. Changes in all parameters occurred mainly after contact with the cathode, which implies that the HS are reacting either directly with electrons from the cathode or with H2 formed at the cathode surface. Since hydrodechlorination is the primary TCE reduction mechanism in this setup, reactions of the HS with the cathode limit transformation of TCE. The presence of limestone gravel reduced the impact of HS on TCE removal. The study concludes that presence of humic substances adversely affects TCE removal from contaminated groundwater by electrochemical reduction using palladized cathodes. PMID:26549889

Electrochemical Deposition of Niobium onto the Surface of Copper Using a Novel Choline Chloride-Based Ionic Liquid

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

Wixtroma, Alex I.; Buhlera, Jessica E.; Reece, Charles E.

2013-06-01

Recent research has shown that choline chloride-based solutions can be used to replace acid-based electrochemical polishing solutions. In this study niobium metal was successfully deposited on the surface of copper substrate via electrochemical deposition using a novel choline chloride-based ionic liquid. The niobium metal used for deposition on the Cu had been dissolved in the solution from electrochemical polishing of a solid niobium piece prior to the deposition. The visible coating on the surface of the Cu was analyzed using scanning electron microscopy (SEM) and electron dispersive x-ray spectroscopy (EDX). This deposition method effectively recycles previously dissolved niobium from electrochemicalmore » polishing.« less

Nanocomposite protective coatings for battery anodes

DOEpatents

Lemmon, John P; Xiao, Jie; Liu, Jun

2014-01-21

Modified surfaces on metal anodes for batteries can help resist formation of malfunction-inducing surface defects. The modification can include application of a protective nanocomposite coating that can inhibit formation of surface defects. such as dendrites, on the anode during charge/discharge cycles. For example, for anodes having a metal (M'), the protective coating can be characterized by products of chemical or electrochemical dissociation of a nanocomposite containing a polymer and an exfoliated compound (M.sub.a'M.sub.b''X.sub.c). The metal, M', comprises Li, Na, or Zn. The exfoliated compound comprises M' among lamella of M.sub.b''X.sub.c, wherein M'' is Fe, Mo, Ta, W, or V, and X is S, O, or Se.

Characterization of immobilization methods of antiviral antibodies in serum for electrochemical biosensors

NASA Astrophysics Data System (ADS)

Huy, Tran Quang; Hanh, Nguyen Thi Hong; Van Chung, Pham; Anh, Dang Duc; Nga, Phan Thi; Tuan, Mai Anh

2011-06-01

In this paper, we describes different methods to immobilize Japanese encephalitis virus (JEV) antibodies in human serum onto the interdigitated surface of a microelectrode sensor for optimizing electrochemical detection: (1) direct covalent binding to the silanized surface, (2) binding to the silanized surface via a cross-linker of glutaraldehyde (GA), (3) binding to glutaraldehyde/silanized surface via goat anti-human IgG polyclonal antibody and (4) binding to glutaraldehyde/silanized surface via protein A (PrA). Field emission scanning electron microscopy, Fourier transform infrared spectrometry, and fluorescence microscopy are used to verify the characteristics of antibodies on the interdigitated surface after the serum antibodies immobilization. The analyzed results indicate that the use of protein A is an effective choice for immobilization and orientation of antibodies in serum for electrochemical biosensors. This study provides an advantageous immobilization method of serum containing antiviral antibodies to develop electrochemical biosensors for preliminary screening of viruses in clinical samples from outbreaks.

Selectivity and Sensitivity of Ultrathin Monolayer Electrodes

NASA Astrophysics Data System (ADS)

Cheng, Quan

The objective of this work is to build a molecular architecture on the electrode surface with a well-defined morphology and desirable electrochemical characteristics. The goal is accomplished by means of self-assembly of thioctic acid, a sulfur-terminated organic molecule with a short alkyl chain and a hydrophilic carboxylic headgroup, on a gold electrode. Characterization of the monolayer structure and the electrochemical response of the monolayer electrodes is performed by means of capacitance measurements and voltammetry. Investigation of the capacitance of the self-assembled monolayers provides insight into the macroscopic permeability of the films and reveals that penetration of solvent/ions into the thioctic acid monolayer film occurs extensively. Voltammetric results demonstrate that permselectivity of the monolayer electrode can be obtained as a result of the induced electrostatic interactions between the monolayer interface and the electroactive species. Measurement of the voltammetric response of the redox probes at the monolayers as a function of the electrolyte concentration and composition is used to qualitatively analyze the effect of electrolyte on response. A model describing the role of the interfacial charge in the electrochemical response of the monolayers as a function of the solution composition and surface smoothness is proposed. A strategy is developed to further explore the applications of the monolayer electrodes to control the electrochemical response of the biological molecules such as catecholamines. The ability to control the surface hydrophobicity of the monolayer electrodes through coadsorption of thioctic acid and hexanethiol, to display different electrochemical properties towards biological molecules is tested. The optimum conditions for detection of the biological molecules on the monolayer electrodes are discussed. In order to pursue selective analysis in microenvironments, the thioctic acid monolayer formed on the ultramicroelectrodes (UME) is investigated, demonstrating high permselectivity and high sensitivity of the monolayer modified UMEs. Because of the more effective mass transport to the UMEs, effects of electrolyte on the monolayer response can be characterized facilely. Amperometric pH sensing on the thioctic acid UMEs using a redox mediator is discussed. Finally, the thioctic acid monolayer microelectrode is applied to investigate direct electrochemistry of a redox protein, cytochrome c. A sketch for developing a biosensor via mediation effects using the monolayer assembly is proposed.

Synthesis of SnO2 pillared carbon using long chain alkylamine grafted graphene oxide: an efficient anode material for lithium ion batteries.

PubMed

Reddy, M Jeevan Kumar; Ryu, Sung Hun; Shanmugharaj, A M

2016-01-07

With the objective of developing new advanced composite materials that can be used as anodes for lithium ion batteries (LIBs), herein we describe the synthesis of SnO2 pillared carbon using various alkylamine (hexylamine; dodecylamine and octadecylamine) grafted graphene oxides and butyl trichlorotin precursors followed by its calcination at 500 °C for 2 h. While the grafted alkylamine induces crystalline growth of SnO2 pillars, thermal annealing of alkylamine grafted graphene oxide results in the formation of amorphous carbon coated graphene. Field emission scanning electron microscopy (FE-SEM) results reveal the successful formation of SnO2 pillared carbon on the graphene surface. X-ray diffraction (XRD), transmission electron microscopy (TEM) and Raman spectroscopy characterization corroborates the formation of rutile SnO2 crystals on the graphene surface. A significant rise in the BET surface area is observed for SnO2 pillared carbon, when compared to pristine GO. Electrochemical characterization studies of SnO2 pillared carbon based anode materials showed an enhanced lithium storage capacity and fine cyclic performance in comparison with pristine GO. The initial specific capacities of SnO2 pillared carbon are observed to be 1379 mA h g(-1), 1255 mA h g(-1) and 1360 mA h g(-1) that decrease to 750 mA h g(-1), 643 mA h g(-1) and 560 mA h g(-1) depending upon the chain length of grafted alkylamine on the graphene surface respectively. Electrochemical impedance spectral analysis reveals that the exchange current density of SnO2 pillared carbon based electrodes is higher, corroborating its enhanced electrochemical activity in comparison with GO based electrodes.

Assessment of Boron Doped Diamond Electrode Quality and Application to In Situ Modification of Local pH by Water Electrolysis.

PubMed

Read, Tania L; Macpherson, Julie V

2016-01-06

Boron doped diamond (BDD) electrodes have shown considerable promise as an electrode material where many of their reported properties such as extended solvent window, low background currents, corrosion resistance, etc., arise from the catalytically inert nature of the surface. However, if during the growth process, non-diamond-carbon (NDC) becomes incorporated into the electrode matrix, the electrochemical properties will change as the surface becomes more catalytically active. As such it is important that the electrochemist is aware of the quality and resulting key electrochemical properties of the BDD electrode prior to use. This paper describes a series of characterization steps, including Raman microscopy, capacitance, solvent window and redox electrochemistry, to ascertain whether the BDD electrode contains negligible NDC i.e. negligible sp(2) carbon. One application is highlighted which takes advantage of the catalytically inert and corrosion resistant nature of an NDC-free surface i.e. stable and quantifiable local proton and hydroxide production due to water electrolysis at a BDD electrode. An approach to measuring the local pH change induced by water electrolysis using iridium oxide coated BDD electrodes is also described in detail.

Assessment of Boron Doped Diamond Electrode Quality and Application to In Situ Modification of Local pH by Water Electrolysis

PubMed Central

Read, Tania L.; Macpherson, Julie V.

2016-01-01

Boron doped diamond (BDD) electrodes have shown considerable promise as an electrode material where many of their reported properties such as extended solvent window, low background currents, corrosion resistance, etc., arise from the catalytically inert nature of the surface. However, if during the growth process, non-diamond-carbon (NDC) becomes incorporated into the electrode matrix, the electrochemical properties will change as the surface becomes more catalytically active. As such it is important that the electrochemist is aware of the quality and resulting key electrochemical properties of the BDD electrode prior to use. This paper describes a series of characterization steps, including Raman microscopy, capacitance, solvent window and redox electrochemistry, to ascertain whether the BDD electrode contains negligible NDC i.e. negligible sp2 carbon. One application is highlighted which takes advantage of the catalytically inert and corrosion resistant nature of an NDC-free surface i.e. stable and quantifiable local proton and hydroxide production due to water electrolysis at a BDD electrode. An approach to measuring the local pH change induced by water electrolysis using iridium oxide coated BDD electrodes is also described in detail. PMID:26779959

Nanoporous carbon actuator and methods of use thereof

DOEpatents

Biener, Juergen [San Leandro, CA; Baumann, Theodore F [Discovery Bay, CA; Shao, Lihua [Karlsruhe, DE; Weissmueller, Joerg [Stutensee, DE

2012-07-31

An electrochemically driveable actuator according to one embodiment includes a nanoporous carbon aerogel composition capable of exhibiting charge-induced reversible strain when wetted by an electrolyte and a voltage is applied thereto. An electrochemically driven actuator according to another embodiment includes a nanoporous carbon aerogel composition wetted by an electrolyte; and a mechanism for causing charge-induced reversible strain of the composition. A method for electrochemically actuating an object according to one embodiment includes causing charge-induced reversible strain of a nanoporous carbon aerogel composition wetted with an electrolyte to actuate the object by the strain.

Contact electrification induced interfacial reactions and direct electrochemical nanoimprint lithography in n-type gallium arsenate wafer† †Electronic supplementary information (ESI) available: Electrochemical measurements of the interfaces, optimization of the contact force and temperature of ECNL, XPS analysis, and more examples of ECNL on n-GaAs. See DOI: 10.1039/c6sc04091h Click here for additional data file.

PubMed Central

Zhang, Jie; Zhang, Lin; Wang, Wei; Han, Lianhuan; Jia, Jing-Chun; Tian, Zhao-Wu; Tian, Zhong-Qun

2017-01-01

Although metal assisted chemical etching (MacEtch) has emerged as a versatile micro-nanofabrication method for semiconductors, the chemical mechanism remains ambiguous in terms of both thermodynamics and kinetics. Here we demonstrate an innovative phenomenon, i.e., the contact electrification between platinum (Pt) and an n-type gallium arsenide (100) wafer (n-GaAs) can induce interfacial redox reactions. Because of their different work functions, when the Pt electrode comes into contact with n-GaAs, electrons will move from n-GaAs to Pt and form a contact electric field at the Pt/n-GaAs junction until their electron Fermi levels (E F) become equal. In the presence of an electrolyte, the potential of the Pt/electrolyte interface will shift due to the contact electricity and induce the spontaneous reduction of MnO4 – anions on the Pt surface. Because the equilibrium of contact electrification is disturbed, electrons will transfer from n-GaAs to Pt through the tunneling effect. Thus, the accumulated positive holes at the n-GaAs/electrolyte interface make n-GaAs dissolve anodically along the Pt/n-GaAs/electrolyte 3-phase interface. Based on this principle, we developed a direct electrochemical nanoimprint lithography method applicable to crystalline semiconductors. PMID:28451347

Environmental TEM study of electron beam induced electro-chemistry of Pr₀̣₆₄Ca₀̣₃₆MnO₃ catalysts for oxygen evolution

DOE PAGES

Mildner, Stephanie; Beleggia, Marco; Mierwaldt, Daniel; ...

2015-03-12

Environmental Transmission Electron Microscopy (ETEM) studies offer great potential for gathering atomic scale information on the electronic state of electrodes in contact with reactants but also pose big challenges due to the impact of the high energy electron beam. In this article, we present an ETEM study of a Pr₀̣₆₄Ca₀̣₃₆MnO₃ (PCMO) thin film electro-catalyst for water splitting and oxygen evolution in contact with water vapor. We show by means of off-axis electron holography and electrostatic modeling that the electron beam gives rise to a positive electric sample potential due to secondary electron emission. The value of the electric potential dependsmore » on the primary electron flux, the sample -conductivity and grounding, and gas properties. We present evidence that two observed electro-chemical reactions are driven by a beam induced electrostatic potential of the order of a volt. The first reaction is an anodic electrochemical oxidation reaction of oxygen depleted amorphous PCMO which results in recrystallization of the perovskite structure. The second reaction is oxygen evolution which can be detected by the oxidation of a silane additive and formation of SiO 2–x at catalytically active surfaces. Recently published in-situ XANES observation of subsurface oxygen vacancy formation during oxygen evolution at a positive potential [³²] is confirmed in this work. The quantification of beam induced potentials is an important step for future controlled electro-chemical experiments in an ETEM.« less

A combined electrochemical-irradiation treatment of highly colored and polluted industrial wastewater

NASA Astrophysics Data System (ADS)

Barrera-Díaz, C.; Ureña-Nuñez, F.; Campos, E.; Palomar-Pardavé, M.; Romero-Romo, M.

2003-07-01

This study reports on the attainment of optimal conditions for two electrolytic methods to treat wastewater: namely, electrocoagulation and particle destabilization of a highly polluted industrial wastewater, and electrochemically induced oxidation induced by in situ generation of Fenton's reactive. Additionally, a combined method that consisted of electrochemical treatment plus γ-irradiation was carried out. A typical composition of the industrial effluent treated was COD 3400 mg/l, color 3750 Pt/Co units, and fecal coliforms 21000 MPN/ml. The best removal efficiency was obtained with electrochemical oxidation induced in situ , that resulted in the reduction of 78% for the COD, 86% color and 99.9% fecal coliforms removal. A treatment sequence was designed and carried out, such that after both electrochemical processes, a γ-irradiation technique was used to complete the procedure. The samples were irradiated with various doses in an ALC γ-cell unit provided with a Co-60 source. The removal efficiency obtained was 95% for the COD values, 90% color and 99.9% for fecal coliforms.

Electrodeposition of Highly Porous Pt Nanoparticles Studied by Quantitative 3D Electron Tomography: Influence of Growth Mechanisms and Potential Cycling on the Active Surface Area.

PubMed

Ustarroz, Jon; Geboes, Bart; Vanrompay, Hans; Sentosun, Kadir; Bals, Sara; Breugelmans, Tom; Hubin, Annick

2017-05-17

Nanoporous Pt nanoparticles (NPs) are promising fuel cell catalysts due to their large surface area and increased electrocatalytic activity toward the oxygen reduction reaction (ORR). Herein, we report on the influence of the growth mechanisms on the surface properties of electrodeposited Pt dendritic NPs with large surface areas. The electrochemically active surface was studied by hydrogen underpotential deposition (H UPD) and compared for the first time to high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) quantitative 3D electron tomography of individual nanoparticles. Large nucleation overpotential leads to a large surface coverage of roughened spheroids, which provide a large roughness factor (R f ) but low mass-specific electrochemically active surface area (EASA). Lowering the nucleation overpotential leads to highly porous Pt NPs with pores stretching to the center of the structure. At the expense of smaller R f , the obtained EASA values of these structures are in the range of those of large surface area supported fuel cell catalysts. The active surface area of the Pt dendritic NPs was measured by electron tomography, and it was found that the potential cycling in the H adsorption/desorption and Pt oxidation/reduction region, which is generally performed to determine the EASA, leads to a significant reduction of that surface area due to a partial collapse of their dendritic and porous morphology. Interestingly, the extrapolation of the microscopic tomography results in macroscopic electrochemical parameters indicates that the surface properties measured by H UPD are comparable to the values measured on individual NPs by electron tomography after the degradation caused by the H UPD measurement. These results highlight that the combination of electrochemical and quantitative 3D surface analysis techniques is essential to provide insights into the surface properties, the electrochemical stability, and, hence, the applicability of these materials. Moreover, it indicates that care must be taken with widely used electrochemical methods of surface area determination, especially in the case of large surface area and possibly unstable nanostructures, since the measured surface can be strongly affected by the measurement itself.

Dynamic Electrochemical Control of Cell Capture-and-Release Based on Redox-Controlled Host-Guest Interactions.

PubMed

Gao, Tao; Li, Liudi; Wang, Bei; Zhi, Jun; Xiang, Yang; Li, Genxi

2016-10-18

Artificial control of cell adhesion on smart surface is an on-demand technique in areas ranging from tissue engineering, stem cell differentiation, to the design of cell-based diagnostic system. In this paper, we report an electrochemical system for dynamic control of cell catch-and-release, which is based on the redox-controlled host-guest interaction. Experimental results reveal that the interaction between guest molecule (ferrocene, Fc) and host molecule (β-cyclodextrin, β-CD) is highly sensitive to electrochemical stimulus. By applying a reduction voltage, the uncharged Fc can bind to β-CD that is immobilized at the electrode surface. Otherwise, it is disassociated from the surface as a result of electrochemical oxidation, thus releasing the captured cells. The catch-and-release process on this voltage-responsive surface is noninvasive with the cell viability over 86%. Moreover, because Fc can act as an electrochemical probe for signal readout, the integration of this property has further extended the ability of this system to cell detection. Electrochemical signal has been greatly enhanced for cell detection by introducing branched polymer scaffold that are carrying large quantities of Fc moieties. Therefore, a minimum of 10 cells can be analyzed. It is anticipated that such redox-controlled system can be an important tool in biological and biomedical research, especially for electrochemical stimulated tissue engineering and cell-based clinical diagnosis.

Anomalous low strain induced by surface charge in nanoporous gold with low relative density.

PubMed

Liu, Feng; Ye, Xing-Long; Jin, Hai-Jun

2017-07-26

The surface stress induced axial strain in a fiber-like solid is larger than its radical strain, and is also greater than the radical strain in similar-sized spherical solids. It is thus envisaged that the surface-induced macroscopic dimension change (i.e., actuation strain) in nanoporous gold (NPG) increases with decreasing relative density, or alternatively, with an increasing ratio between volumes of fiber-like ligaments and sphere-like nodes. In this study, electrochemical actuations of NPG with similar structure sizes, same (oxide-covered) surface state but different relative densities were characterized in situ in response to surface charging/discharging. We found that the actuation strain amplitude did not increase, but decreased dramatically with decreasing relative density of NPG, in contrast to the above prediction. The actuation strain decreased abruptly when the relative density of NPG was decreased to below 0.25, when the Au content in the AuAg precursor was below 20 at%. Further studies indicate that this anomalous behavior cannot be explained by potential- or size-dependences of the elasticity, the structure difference arising from different dealloying rates, or additional strain induced by the external load during dilatometry experiments. In NPG with low relative density, mutual movements of nano-ligaments may occur in the pore space and disconnected regions, which may compensate the local strain in ligaments and account for the anomalous low actuation strain in macroscopic NPG samples.

Electrochemical surface-enhanced Raman scattering measurement on ligand capped PbS quantum dots at gap of Au nanodimer

NASA Astrophysics Data System (ADS)

Li, Xiaowei; Minamimoto, Hiro; Murakoshi, Kei

2018-05-01

The vibrational characteristics of ligand-capped lead sulfide (PbS) quantum dots (QDs) were clarified via electrochemical surface-enhanced Raman spectroscopy (EC-SERS) using a hybridized system of gold (Au) nanodimers and PbS QDs under electrochemical potential control. Enhanced electromagnetic field caused by the coupling of QDs with plasmonic Au nanodimers allowed the characteristic behavior of the ligand oleic acid (OA) on the PbS QD surface to be detected under electrochemical potential control. Binding modes between the QDs and OA molecules were characterized using synchronous two-dimensional correlation spectra at distinct electrochemical potentials, confirming that the bidentate bridging mode was probably the most stable mode even under relatively negative potential polarization. Changes in binding modes and molecular orientations resulted in fluctuations in EC-SERS spectra. The present observations strongly recommend the validity of the QD-plasmonic nanostructure coupled system for sensitive molecular detection via EC-SERS.

Aptamer-based electrochemical sensors with aptamer-complementary DNA oligonucleotides as probe.

PubMed

Lu, Ying; Li, Xianchan; Zhang, Limin; Yu, Ping; Su, Lei; Mao, Lanqun

2008-03-15

This study describes a facile and general strategy for the development of aptamer-based electrochemical sensors with a high specificity toward the targets and a ready regeneration feature. Very different from the existing strategies for the development of electrochemical aptasensors with the aptamers as the probes, the strategy proposed here is essentially based on the utilization of the aptamer-complementary DNA (cDNA) oligonucleotides as the probes for electrochemical sensing. In this context, the sequences at both ends of the cDNA are tailor-made to be complementary and both the redox moiety (i.e., ferrocene in this study) and thiol group are labeled onto the cDNA. The labeled cDNA are hybridized with their respective aptamers (i.e., ATP- and thrombin-binding aptamers in this study) to form double-stranded DNA (ds-DNA) and the electrochemical aptasensors are prepared by self-assembling the labeled ds-DNA onto Au electrodes. Upon target binding, the aptamers confined onto electrode surface dissociate from their respective cDNA oligonucleotides into the solution and the single-stranded cDNA could thus tend to form a hairpin structure through the hybridization of the complementary sequences at both its ends. Such a conformational change of the cDNA resulting from the target binding-induced dissociation of the aptamers essentially leads to the change in the voltammetric signal of the redox moiety labeled onto the cDNA and thus constitutes the mechanism for the electrochemical aptasensors for specific target sensing. The aptasensors demonstrated here with the cDNA as the probe are readily regenerated and show good responses toward the targets. This study may offer a new and relatively general approach to electrochemical aptasensors with good analytical properties and potential applications.

Preparation of anti-adhesion surfaces on aluminium substrates of rubber plastic moulds using a coupling method of liquid plasma and electrochemical machining

NASA Astrophysics Data System (ADS)

Meng, Jianbing; Dong, Xiaojuan; Wei, Xiuting; Yin, Zhanmin

2014-03-01

Hard anti-adhesion surfaces, with low roughness and wear resistance, on aluminium substrates of rubber plastic moulds were fabricated via a new coupling method of liquid plasma and electrochemical machining. With the aid of liquid plasma thermal polishing and electrochemical anodic dissolution, micro/nano-scale binary structures were prepared as the base of the anti-adhesion surfaces. The anti-adhesion behaviours of the resulting aluminium surfaces were analysed by a surface roughness measuring instrument, a scanning electron microscope (SEM), a Fourier-transform infrared spectrophotometer (FTIR), an X-ray diffractometer (XRD), an optical contact angle meter, a digital Vickers micro-hardness (Hv) tester, and electronic universal testing. The results show that, after the liquid plasma and electrochemical machining, micro/nano-scale binary structures composed of micro-scale pits and nano-scale elongated boss structures were present on the sample surfaces. As a result, the anti-adhesion surfaces fabricated by the above coupling method have good anti-adhesion properties, better wear resistance and lower roughness.

Preparation of anti-adhesion surfaces on aluminium substrates of rubber plastic moulds using a coupling method of liquid plasma and electrochemical machining

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

Meng, Jianbing, E-mail: jianbingmeng@126.com; Dong, Xiaojuan; Wei, Xiuting

Hard anti-adhesion surfaces, with low roughness and wear resistance, on aluminium substrates of rubber plastic moulds were fabricated via a new coupling method of liquid plasma and electrochemical machining. With the aid of liquid plasma thermal polishing and electrochemical anodic dissolution, micro/nano-scale binary structures were prepared as the base of the anti-adhesion surfaces. The anti-adhesion behaviours of the resulting aluminium surfaces were analysed by a surface roughness measuring instrument, a scanning electron microscope (SEM), a Fourier-transform infrared spectrophotometer (FTIR), an X-ray diffractometer (XRD), an optical contact angle meter, a digital Vickers micro-hardness (Hv) tester, and electronic universal testing. The resultsmore » show that, after the liquid plasma and electrochemical machining, micro/nano-scale binary structures composed of micro-scale pits and nano-scale elongated boss structures were present on the sample surfaces. As a result, the anti-adhesion surfaces fabricated by the above coupling method have good anti-adhesion properties, better wear resistance and lower roughness.« less

Multi-layer seal for electrochemical devices

DOEpatents

Chou, Yeong-Shyung [Richland, WA; Meinhardt, Kerry D [Kennewick, WA; Stevenson, Jeffry W [Richland, WA

2010-11-16

Multi-layer seals are provided that find advantageous use for reducing leakage of gases between adjacent components of electrochemical devices. Multi-layer seals of the invention include a gasket body defining first and second opposing surfaces and a compliant interlayer positioned adjacent each of the first and second surfaces. Also provided are methods for making and using the multi-layer seals, and electrochemical devices including said seals.

Multi-layer seal for electrochemical devices

DOEpatents

Chou, Yeong-Shyung [Richland, WA; Meinhardt, Kerry D [Kennewick, WA; Stevenson, Jeffry W [Richland, WA

2010-09-14

Multi-layer seals are provided that find advantageous use for reducing leakage of gases between adjacent components of electrochemical devices. Multi-layer seals of the invention include a gasket body defining first and second opposing surfaces and a compliant interlayer positioned adjacent each of the first and second surfaces. Also provided are methods for making and using the multi-layer seals, and electrochemical devices including said seals.

Electrochemical characteristics of calcium-phosphatized AZ31 magnesium alloy in 0.9 % NaCl solution.

PubMed

Hadzima, Branislav; Mhaede, Mansour; Pastorek, Filip

2014-05-01

Magnesium alloys suffer from their high reactivity in common environments. Protective layers are widely created on the surface of magnesium alloys to improve their corrosion resistance. This article evaluates the influence of a calcium-phosphate layer on the electrochemical characteristics of AZ31 magnesium alloy in 0.9 % NaCl solution. The calcium phosphate (CaP) layer was electrochemically deposited in a solution containing 0.1 M Ca(NO3)2, 0.06 M NH4H2PO4 and 10 ml l(-1) of H2O2. The formed surface layer was composed mainly of brushite [(dicalcium phosphate dihidrate (DCPD)] as proved by energy-dispersive X-ray analysis. The surface morphology was observed by scanning electron microscopy. Immersion test was performed in order to observe degradation of the calcium phosphatized surfaces. The influence of the phosphate layer on the electrochemical characteristics of AZ31, in 0.9 % NaCl solution, was evaluated by potentiodynamic measurements and electrochemical impedance spectroscopy. The obtained results were analysed by the Tafel-extrapolation method and equivalent circuits method. The results showed that the polarization resistance of the DCPD-coated surface is about 25 times higher than that of non-coated surface. The CaP electro-deposition process increased the activation energy of corrosion process.

Molecular Machine Powered Surface Programmatic Chain Reaction for Highly Sensitive Electrochemical Detection of Protein.

PubMed

Zhu, Jing; Gan, Haiying; Wu, Jie; Ju, Huangxian

2018-04-17

A bipedal molecular machine powered surface programmatic chain reaction was designed for electrochemical signal amplification and highly sensitive electrochemical detection of protein. The bipedal molecular machine was built through aptamer-target specific recognition for the binding of one target protein with two DNA probes, which hybridized with surface-tethered hairpin DNA 1 (H1) via proximity effect to expose the prelocked toehold domain of H1 for the hybridization of ferrocene-labeled hairpin DNA 2 (H2-Fc). The toehold-mediated strand displacement reaction brought the electrochemical signal molecule Fc close to the electrode and meanwhile released the bipedal molecular machine to traverse the sensing surface by the surface programmatic chain reaction. Eventually, a large number of duplex structures of H1-H2 with ferrocene groups facing to the electrode were formed on the sensor surface to generate an amplified electrochemical signal. Using thrombin as a model target, this method showed a linear detection range from 2 pM to 20 nM with a detection limit of 0.76 pM. The proposed detection strategy was enzyme-free and allowed highly sensitive and selective detection of a variety of protein targets by using corresponding DNA-based affinity probes, showing potential application in bioanalysis.

Electrochemical label-free and sensitive nanobiosensing of DNA hybridization by graphene oxide modified pencil graphite electrode.

PubMed

Ahour, F; Shamsi, A

2017-09-01

Based on the strong interaction between single-stranded DNA (ss-DNA) and graphene material, we have constructed a novel label-free electrochemical biosensor for rapid and facile detection of short sequences ss-DNA molecules related to hepatitis C virus 1a using graphene oxide modified pencil graphite electrode. The sensing mechanism is based on the superior adsorption of single-stranded DNA to GO over double stranded DNA (ds-DNA). The intrinsic guanine oxidation signal measured by differential pulse voltammetry (DPV) has been used for duplex DNA formation detection. The probe ss-DNA adsorbs onto the surface of GO via the π- π* stacking interactions leading to a strong background guanine oxidation signal. In the presence of complementary target, formation of helix which has weak binding ability to GO induced ds-DNA to release from the electrode surface and significant variation in differential pulse voltammetric response of guanine bases. The results indicated that the oxidation peak current was proportional to the concentration of complementary strand in the range of 0.1 nM-0.5 μM with a detection limit of 4.3 × 10 -11  M. The simple fabricated electrochemical biosensor has high sensitivity, good selectivity, and could be applied as a new platform for a range of target molecules in future. Copyright © 2017 Elsevier Inc. All rights reserved.

Electrochemical vs X-ray Spectroscopic Measurements of NiFe(CN)6 Crystals

NASA Astrophysics Data System (ADS)

Peecher, Benjamin; Hampton, Jennifer

Pseudocapacitive materials like hexacyanoferrate have greater energy storage capabilities than standard capacitors while maintaining an ability to charge and discharge quickly. We modify the surface of an electrodeposited Ni thin film with a layer of hexacyanoferrate. Charging and discharging these modified films using cyclic voltammetry (CV) allows us to measure the electrochemically active Fe in the film. To determine how closely this resembles the full amount of Fe in the film, we measure the films' composition using particle-induced x-ray emission (PIXE). We also vary the amount of Ni deposited, both to compare the electrolysis value of charge deposited to the PIXE measurement of Ni in the film, and also to measure how varying the thickness of the Ni surface affects the presence of Fe in the film. Comparisons of the CV and PIXE measurements show agreement in Ni levels but disagreement in Fe levels. PIXE measurements of Fe in the film have positive correlation with Ni in the film. This correlation between PIXE measurements of Ni and Fe suggests that PIXE provides a reliable measure of Fe in the film. This implies that a variable proportion of total Fe in a given film is electrochemically active. This research was made possible by the Hope College Department of Physics Frissel Research Fund and the National Science Foundation under Grants RUI-DMR-1104725, MRI-CHE-0959282, and MRI/RUI-PHY-0319523.

Sensitive electrochemical immunoassay for 2,4,6-trinitrotoluene based on functionalized silica nanoparticle labels

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

Wang, Jun; Liu, Guodong; Wu, Hong

2008-03-03

We present a poly(guanine)-functionalized silica nanoparticle (NP) label-based electrochemical immunoassay for sensitively detecting 2,4,6-trinitrotoluene (TNT). This immunoassay takes advantage of magnetic bead–based platform for competitive displacement immunoreactions and separation, and use electroactive nanoparticles as labels for signal amplification. For this assay, anti-TNT-coated magnetic beads interacted with TNT analog-conjugated poly(guanine)-silica NPs and formed analog-anti-TNT immunocomplexes on magnetic beads. The immunocomplexes coated magnetic beads were exposed to TNT samples, which resulted in displacing the analog conjugated poly(guanine) silica NPs into solution by TNT. In contrast, there are no guanine residues releasing into the solution in the absence of TNT. The reaction solutionmore » was then separated from the magnetic beads and transferred to the electrode surface for electrochemical measurements of guanine oxidation with Ru(bpy)32+ as mediator. The sensitivity of this TNT assay was greatly enhanced through dual signal amplifications: 1) a large amount of guanine residues on silica nanoparticles is introduced into the test solution by displacement immunoreactions and 2) a Ru(bpy)32+-induced guanine catalytic oxidation further enhances the electrochemical signal. Some experimental parameters for the nanoparticle label-based electrochemical immunoassay were studied and the performance of this assay was evaluated. The method is found to be very sensitive and the detection limit of this assay is ~ 0.1 ng mL-1 TNT. The electrochemical immunoassay based on the poly[guanine]-functionalized silica NP label offers a new approach for sensitive detection of explosives.« less

Single- and multi-frequency detection of surface displacements via scanning probe microscopy.

PubMed

Romanyuk, Konstantin; Luchkin, Sergey Yu; Ivanov, Maxim; Kalinin, Arseny; Kholkin, Andrei L

2015-02-01

Piezoresponse force microscopy (PFM) provides a novel opportunity to detect picometer-level displacements induced by an electric field applied through a conducting tip of an atomic force microscope (AFM). Recently, it was discovered that superb vertical sensitivity provided by PFM is high enough to monitor electric-field-induced ionic displacements in solids, the technique being referred to as electrochemical strain microscopy (ESM). ESM has been implemented only in multi-frequency detection modes such as dual AC resonance tracking (DART) and band excitation, where the response is recorded within a finite frequency range, typically around the first contact resonance. In this paper, we analyze and compare signal-to-noise ratios of the conventional single-frequency method with multi-frequency regimes of measuring surface displacements. Single-frequency detection ESM is demonstrated using a commercial AFM.

Biocompatibility of Mg Ion Doped Hydroxyapatite Films on Ti-6Al-4V Surface by Electrochemical Deposition.

PubMed

Lee, Kang; Choe, Han-Cheol

2016-02-01

In this study, we prepared magnesium (Mg) doped nano-phase hydroxyapatite (HAp) films on the TiO2 nano-network surface using electrochemical deposition method. Ti-6Al-4V ELI surface was anodized in 5 M NaOH solution at 0.3 A for 10 min. Nano-network TiO2 surface were formed by these anodization steps which acted as templates and anchorage for growth of the Mg doped HAp during subsequent pulsed electrochemical deposition process at 85 degrees C. The phase and morphologies of HAp deposits were influenced by the Mg ion concentration.

Colonization of Bacteria on the Surfaces of Cold-Sprayed Copper Coatings Alters Their Electrochemical Behaviors

NASA Astrophysics Data System (ADS)

Suo, Xinkun; Abdoli, Leila; Liu, Yi; Xia, Peng; Yang, Guanjun; Li, Hua

2017-04-01

Copper coatings were fabricated on stainless steel plates by cold spraying. Attachment and colonization of Bacillus sp. on their surfaces in artificial seawater were characterized, and their effects on anticorrosion performances of the coatings were examined. Attached bacteria were observed using field emission scanning electron microscopy. Electrochemical behaviors including potentiodynamic polarization and electrochemical impedance spectroscopy with/without bacterial attachment were evaluated using commercial electrochemical analysis station Modulab. Results show that Bacillus sp. opt to settle on low-lying spots of the coating surfaces in early stage, followed by recruitment and attachment of extracellular polymeric substances (EPS) secreted through metabolism of Bacillus sp. The bacteria survive with the protection of EPS. An attachment model is proposed to illustrate the bacterial behaviors on the surfaces of the coatings. Electrochemical data show that current density under Bacillus sp. environment decreases compared to that without the bacteria. Charge-transfer resistance increases markedly in bacteria-containing seawater, suggesting that corrosion resistance increases and corrosion rate decreases. The influencing mechanism of bacteria settlement on corrosion resistance of the cold-sprayed copper coatings was discussed and elucidated.

Effect of black clay soil moisture on the electrochemical behavior of API X70 pipeline steel

NASA Astrophysics Data System (ADS)

Hendi, R.; Saifi, H.; Belmokre, K.; Ouadah, M.; Smili, B.; Talhi, B.

2018-03-01

The effect of moisture content variation (20–100 wt.%) on the electrochemical behavior of API X70 pipeline steel buried in the soil of Skikda (East of Algeria) was studied using electrochemical techniques, scanning electron microscopy (SEM), X ray diffraction analysis (XRD) and weight loss measurement. The electrochemical measurements showed that the corrosion current Icorr is directly proportional to the moisture content up to 50 wt.%, beyond this content, this value becomes almost constant. The result were confirmed by electrochemical impedance spectroscopy; the capacitance of the double layer formed on the surface is the highest at 50 wt.%. A single time constant was detected by plotting the Bode diagrams. The steel surface degradation has been appreciated using the scanning electron microscopy observations. A few pitting corrosion at 20 wt.% moisture, followed by more degradation at 50 wt.% have been revealed. However, when the moisture amount exceeded 50 wt.%, the surface became entirely covered by a corrosion product. XRD analysis revealed the dominance of FeOOH and Fe3O4 phases on steel surface for a moisture content of 50 wt.%.

Concentration and density changes at an electrode surface and the principle of unchanging total concentration

DOE PAGES

Stephen W. Feldberg; Lewis, Ernie R.

2016-02-17

In this study, the principle of unchanging total concentration as described by Oldham and Feldberg [J. Phys. Chem. B, 103, 1699 (1999)] is invoked to analyze systems comprising a redox pair (X z1 1 and X z2 2) plus one or more non-electroactive species (X z3 3,X z4 4...X zjmax jmax) where X zj j is the j th species with charge z j and concentration; c j. The principle states that if the diffusion coefficients for all species are identical and mass transport is governed by the Nernst-Planck expression, the total concentration does not change during any electrochemical perturbation,more » i.e.: Σ jmax j=1[X zj j]=Σ jmax j=1 c j = S P With this principle we deduce the electrochemically induced difference between the surface and bulk concentrations for each species. Those concentration differences are translated into density differences which are a function of the density of the solvent and of the concentration differences, molecular masses and the standard partial molar volumes of all species. Those density differences in turn can induce convection that will ultimately modify the observed current. However, we did not attempt to quantify details of the natural convection and current modification produced by those density differences.« less

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

Wu, Chun-Lan; Yuan, Hongtao; Li, Yanbin

Electric-double-layer (EDL) gating with liquid electrolyte has been a powerful tool widely used to explore emerging interfacial electronic phenomena. Due to the large EDL capacitance, a high carrier density up to 10 14 cm –2 can be induced, directly leading to the realization of field-induced insulator to metal (or superconductor) transition. However, the liquid nature of the electrolyte has created technical issues including possible side electrochemical reactions or intercalation, and the potential for huge strain at the interface during cooling. In addition, the liquid coverage of active devices also makes many surface characterizations and in situ measurements challenging. Here, wemore » demonstrate an all solid-state EDL device based on a solid superionic conductor LaF 3, which can be used as both a substrate and a fluorine ionic gate dielectric to achieve a wide tunability of carrier density without the issues of strain or electrochemical reactions and can expose the active device surface for external access. Based on LaF 3 EDL transistors (EDLTs), we observe the metal–insulator transition in MoS 2. Interestingly, the well-defined crystal lattice provides a more uniform potential distribution in the substrate, resulting in less interface electron scattering and therefore a higher mobility in MoS 2 transistors. Finally, this result shows the powerful gating capability of LaF 3 solid electrolyte for new possibilities of novel interfacial electronic phenomena.« less

Temperature Dependence of Electric Transport in Few-layer Graphene under Large Charge Doping Induced by Electrochemical Gating

PubMed Central

Gonnelli, R. S.; Paolucci, F.; Piatti, E.; Sharda, Kanudha; Sola, A.; Tortello, M.; Nair, Jijeesh R.; Gerbaldi, C.; Bruna, M.; Borini, S.

2015-01-01

The temperature dependence of electric transport properties of single-layer and few-layer graphene at large charge doping is of great interest both for the study of the scattering processes dominating the conductivity at different temperatures and in view of the theoretically predicted possibility to reach the superconducting state in such extreme conditions. Here we present the results obtained in 3-, 4- and 5-layer graphene devices down to 3.5 K, where a large surface charge density up to about 6.8·1014 cm−2 has been reached by employing a novel polymer electrolyte solution for the electrochemical gating. In contrast with recent results obtained in single-layer graphene, the temperature dependence of the sheet resistance between 20 K and 280 K shows a low-temperature dominance of a T2 component – that can be associated with electron-electron scattering – and, at about 100 K, a crossover to the classic electron-phonon regime. Unexpectedly, this crossover does not show any dependence on the induced charge density, i.e. on the large tuning of the Fermi energy. PMID:25906088

[The effect of epigallocatechin gallate (EGCG) on the surface properties of nickel-chromium dental casting alloys after electrochemical corrosion].

PubMed

Qiao, Guang-yan; Zhang, Li-xia; Wang, Jue; Shen, Qing-ping; Su, Jian-sheng

2014-08-01

To investigate the effect of epigallocatechin gallate (EGCG) on the surface properties of nickel-chromium dental alloys after electrochemical corrosion. The surface morphology and surface structure of nickel-chromium dental alloys were examined by stereomicroscope and scanning electron microscopy before and after electrochemical tests in 0 g/L and 1.0 g/L EGCG artificial saliva. The surface element component and chemical states of nickel-chromium dental alloys were analyzed by X-ray photoelectron spectrograph after electrochemical tests in 0 g/L and 1.0 g/L EGCG artificial saliva. More serious corrosion happened on the surface of nickel-chromium alloy in 1.0 g/L EGCG artificial saliva than in 0 g/L EGCG. The diameters of corrosion pits were smaller, and the dendrite structure of the alloy surface was not affected in 0 g/L EGCG. While the diameters of corrosion pits were larger, the dendritic interval of the alloy surface began to merge, and the dendrite structure was fuzzy in 1.0 g/L EGCG. In addition, the O, Ni, Cr, Be, C and Mo elements were detected on the surface of nickel-chromium alloys after sputtered for 120 s in 0 g/L EGCG and 1.0 g/L EGCG artificial saliva after electrochemical corrosion, and the surface oxides were mainly NiO and Cr(2)O(3). Compared with 0 g/L EGCG artificial saliva, the content of O, NiO and Cr(2)O(3) were lower in 1.0 g/L EGCG. The results of surface morphology and the corrosion products both show that the corrosion resistance of nickel-chromium alloys become worse and the oxide content of corrosion products on the surface reduce in 1.0 g/L EGCG artificial saliva.

Electrochemically Initiated Tagging of Thiols Using an Electrospray Ionization-Based Liquid Microjunction Surface Sampling Probe Two-Electrode Cell

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

Van Berkel, Gary J; Kertesz, Vilmos

2009-01-01

This paper reports on the conversion of a liquid microjunction surface sampling probe (LMJ-SSP) into a two electrode electrochemical cell using a conductive sample surface and the probe as the two electrodes with an appropriate battery powered circuit. With this LMJ-SSP, two-electrode cell arrangement, tagging of analyte thiol functionalities (in this case peptide cysteine residues) with hydroquinone tags was initiated electrochemically using a hydroquinone doped solution when the analyte either was initially in solution or was sampled from a surface. Efficient tagging (~90%), at flow rates of 5-10 L/min, could be achieved for up to at least two cysteines onmore » a peptide. The high tagging efficiency observed was explained with a simple kinetic model. In general, the incorporation of a two-electrode electrochemical cell, or other multiple electrode arrangement, into the LMJ-SSP is expected to add to the versatility of this approach for surface sampling and ionization coupled with mass spectrometric detection.« less

Methods for making a multi-layer seal for electrochemical devices

DOEpatents

Chou, Yeong-Shyung [Richland, WA; Meinhardt, Kerry D [Kennewick, WA; Stevenson, Jeffry W [Richland, WA

2007-05-29

Multi-layer seals are provided that find advantageous use for reducing leakage of gases between adjacent components of electrochemical devices. Multi-layer seals of the invention include a gasket body defining first and second opposing surfaces and a compliant interlayer positioned adjacent each of the first and second surfaces. Also provided are methods for making and using the multi-layer seals, and electrochemical devices including said seals.

An ultra-sensitive Au nanoparticles functionalized DNA biosensor for electrochemical sensing of mercury ions.

PubMed

Zhang, Yanyan; Zhang, Cong; Ma, Rui; Du, Xin; Dong, Wenhao; Chen, Yuan; Chen, Qiang

2017-06-01

The present work describes an effective strategy to fabricate a highly sensitive and selective DNA-biosensor for the determination of mercury ions (Hg 2+ ). The DNA 1 was modified onto the surface of Au electrode by the interaction between sulfydryl group and Au electrode. DNA probe is complementary with DNA 1. In the presence of Hg 2+ , the electrochemical signal increases owing to that Hg 2+ -mediated thymine bases induce the conformation of DNA probe to change from line to hairpin and less DNA probes adsorb into DNA 1. Taking advantage of its reduction property, methylene blue is considered as the signal indicating molecule. For improving the sensitivity of the biosensor, Au nanoparticles (Au NPs) modified reporter DNA 3 is used to adsorb DNA 1. Electrochemical behaviors of the biosensor were evaluated by electrochemical impedance spectroscopy and cyclic voltammetry. Several important parameters which could affect the property of the biosensor were studied and optimized. Under the optimal conditions, the biosensor exhibits wide linear range, high sensitivity and low detection limit. Besides, it displays superior selectivity and excellent stability. The biosensor was also applied for water sample detection with satisfactory result. The novel strategy of fabricating biosensor provides a potential platform for fabricating a variety of metal ions biosensors. Copyright © 2017 Elsevier B.V. All rights reserved.

Self-healing of cracks formed in Silicon-Aluminum anodes electrochemically cycled at high lithiation rates

NASA Astrophysics Data System (ADS)

Bhattacharya, Sandeep; Alpas, Ahmet T.

2016-10-01

Lithiation-induced volume changes in Si result in fracture and fragmentation of Si anodes in Li-ion batteries. This paper reports the self-healing behaviour of cracks observed in micron-sized Si particles dispersed in a ductile Al matrix of a Si-Al electrode electrochemically cycled vs. Li/Li+ using a high lithiation rate of 15.6 C. Cross-sectional high-resolution transmission electron microscopy and Raman spectroscopy revealed that an amorphous layer with a depth up to ∼100 nm was formed at the surface of Si particles. In-situ optical microscopy performed during electrochemical experiments revealed development of cracks in Si particles as the voltage decreased to 0.02 V during lithiation. Self-healing of cracks in Si particles occurred in two steps: i) arresting of the crack growth at the Si/Al interface as the surrounding Al matrix had a higher fracture toughness and thus acted as a barrier to crack propagation, and ii) closure of cracks due to compressive stresses applied to the crack faces by the amorphous zones formed on each side of the crack paths.

Oxidation-Mediated Fingering in Liquid Metals

NASA Astrophysics Data System (ADS)

Eaker, Collin B.; Hight, David C.; O'Regan, John D.; Dickey, Michael D.; Daniels, Karen E.

2017-10-01

We identify and characterize a new class of fingering instabilities in liquid metals; these instabilities are unexpected due to the large interfacial tension of metals. Electrochemical oxidation lowers the effective interfacial tension of a gallium-based liquid metal alloy to values approaching zero, thereby inducing drastic shape changes, including the formation of fractals. The measured fractal dimension (D =1.3 ±0.05 ) places the instability in a different universality class than other fingering instabilities. By characterizing changes in morphology and dynamics as a function of droplet volume and applied electric potential, we identify the three main forces involved in this process: interfacial tension, gravity, and oxidative stress. Importantly, we find that electrochemical oxidation can generate compressive interfacial forces that oppose the tensile forces at a liquid interface. The surface oxide layer ultimately provides a physical and electrochemical barrier that halts the instabilities at larger positive potentials. Controlling the competition between interfacial tension and oxidative (compressive) stresses at the interface is important for the development of reconfigurable electronic, electromagnetic, and optical devices that take advantage of the metallic properties of liquid metals.

Growth kinetics of white graphene (h-BN) on a planarised Ni foil surface

PubMed Central

Cho, Hyunjin; Park, Sungchan; Won, Dong-Il; Kang, Sang Ook; Pyo, Seong-Soo; Kim, Dong-Ik; Kim, Soo Min; Kim, Hwan Chul; Kim, Myung Jong

2015-01-01

The morphology of the surface and the grain orientation of metal catalysts have been considered to be two important factors for the growth of white graphene (h-BN) by chemical vapour deposition (CVD). We report a correlation between the growth rate of h-BN and the orientation of the nickel grains. The surface of the nickel (Ni) foil was first polished by electrochemical polishing (ECP) and subsequently annealed in hydrogen at atmospheric pressure to suppress the effect of the surface morphology. Atmospheric annealing with hydrogen reduced the nucleation sites of h-BN, which induced a large crystal size mainly grown from the grain boundary with few other nucleation sites in the Ni foil. A higher growth rate was observed from the Ni grains that had the {110} or {100} orientation due to their higher surface energy. PMID:26156068

Fabricating porous silicon carbide

NASA Technical Reports Server (NTRS)

Shor, Joseph S. (Inventor); Kurtz, Anthony D. (Inventor)

1994-01-01

The formation of porous SiC occurs under electrochemical anodization. A sample of SiC is contacted electrically with nickel and placed into an electrochemical cell which cell includes a counter electrode and a reference electrode. The sample is encapsulated so that only a bare semiconductor surface is exposed. The electrochemical cell is filled with an HF electrolyte which dissolves the SiC electrochemically. A potential is applied to the semiconductor and UV light illuminates the surface of the semiconductor. By controlling the light intensity, the potential and the doping level, a porous layer is formed in the semiconductor and thus one produces porous SiC.

Method for removing strongly adsorbed surfactants and capping agents from metal to facilitate their catalytic applications

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

Adzic, Radoslav R.; Gong, Kuanping; Cai, Yun

A method of synthesizing activated electrocatalyst, preferably having a morphology of a nanostructure, is disclosed. The method includes safely and efficiently removing surfactants and capping agents from the surface of the metal structures. With regard to metal nanoparticles, the method includes synthesis of nanoparticle(s) in polar or non-polar solution with surfactants or capping agents and subsequent activation by CO-adsorption-induced surfactant/capping agent desorption and electrochemical oxidation. The method produces activated macroparticle or nanoparticle electrocatalysts without damaging the surface of the electrocatalyst that includes breaking, increasing particle thickness or increasing the number of low coordination sites.

Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation

PubMed Central

Zhu, Gaohua; Liu, Jun; Zheng, Qiye; Zhang, Ruigang; Li, Dongyao; Banerjee, Debasish; Cahill, David G.

2016-01-01

Thermal conductivity of two-dimensional (2D) materials is of interest for energy storage, nanoelectronics and optoelectronics. Here, we report that the thermal conductivity of molybdenum disulfide can be modified by electrochemical intercalation. We observe distinct behaviour for thin films with vertically aligned basal planes and natural bulk crystals with basal planes aligned parallel to the surface. The thermal conductivity is measured as a function of the degree of lithiation, using time-domain thermoreflectance. The change of thermal conductivity correlates with the lithiation-induced structural and compositional disorder. We further show that the ratio of the in-plane to through-plane thermal conductivity of bulk crystal is enhanced by the disorder. These results suggest that stacking disorder and mixture of phases is an effective mechanism to modify the anisotropic thermal conductivity of 2D materials. PMID:27767030

Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas

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

Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.

Determining the surface areas of electrocatalysts is critical for separating the key properties of area-specific activity and electrochemical surface area from mass activity. Hydrogen underpotential deposition and carbon monoxide oxidation are typically used to evaluate iridium (Ir) surface areas, but are ineffective on oxides and can be sensitive to surface oxides formed on Ir metals. Mercury underpotential deposition is presented in this study as an alternative, able to produce reasonable surface areas on Ir and Ir oxide nanoparticles, and able to produce similar surface areas prior to and following characterization in oxygen evolution. Reliable electrochemical surface areas allow for comparativemore » studies of different catalyst types and the characterization of advanced oxygen evolution catalysts. Lastly, they also enable the study of catalyst degradation in durability testing, both areas of increasing importance within electrolysis and electrocatalysis.« less

Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas

DOE PAGES

Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.; ...

2016-06-02

Determining the surface areas of electrocatalysts is critical for separating the key properties of area-specific activity and electrochemical surface area from mass activity. Hydrogen underpotential deposition and carbon monoxide oxidation are typically used to evaluate iridium (Ir) surface areas, but are ineffective on oxides and can be sensitive to surface oxides formed on Ir metals. Mercury underpotential deposition is presented in this study as an alternative, able to produce reasonable surface areas on Ir and Ir oxide nanoparticles, and able to produce similar surface areas prior to and following characterization in oxygen evolution. Reliable electrochemical surface areas allow for comparativemore » studies of different catalyst types and the characterization of advanced oxygen evolution catalysts. Lastly, they also enable the study of catalyst degradation in durability testing, both areas of increasing importance within electrolysis and electrocatalysis.« less

Nano-Electrochemistry and Nano-Electrografting with an Original Combined AFM-SECM

PubMed Central

Ghorbal, Achraf; Grisotto, Federico; Charlier, Julienne; Palacin, Serge; Goyer, Cédric; Demaille, Christophe; Ben Brahim, Ammar

2013-01-01

This study demonstrates the advantages of the combination between atomic force microscopy and scanning electrochemical microscopy. The combined technique can perform nano-electrochemical measurements onto agarose surface and nano-electrografting of non-conducting polymers onto conducting surfaces. This work was achieved by manufacturing an original Atomic Force Microscopy-Scanning ElectroChemical Microscopy (AFM-SECM) electrode. The capabilities of the AFM-SECM-electrode were tested with the nano-electrografting of vinylic monomers initiated by aryl diazonium salts. Nano-electrochemical and technical processes were thoroughly described, so as to allow experiments reproducing. A plausible explanation of chemical and electrochemical mechanisms, leading to the nano-grafting process, was reported. This combined technique represents the first step towards improved nano-processes for the nano-electrografting. PMID:28348337

High Power Electrochemical Capacitors

DTIC Science & Technology

2012-03-23

electrochemical properties of vanadium oxide aerogels prepared by a freeze-drying process. Journal of the Electrochemical Society, 2004. 151(5): p...Electrochemical Society, 2002. 149(1): p. A26-A30. 12. Rolison, D.R. and B. Dunn, Electrically conductive oxide aerogels : new materials in...surface area vanadium oxide aerogels . Electrochemical and Solid-State Letters, 2000. 3(10): p. 457-459. 14. Shembel, E., et al., Synthesis, investigation

Superhydrophobic surfaces by electrochemical processes.

PubMed

Darmanin, Thierry; Taffin de Givenchy, Elisabeth; Amigoni, Sonia; Guittard, Frederic

2013-03-13

This review is an exhaustive representation of the electrochemical processes reported in the literature to produce superhydrophobic surfaces. Due to the intensive demand in the elaboration of superhydrophobic materials using low-cost, reproducible and fast methods, the use of strategies based on electrochemical processes have exponentially grown these last five years. These strategies are separated in two parts: the oxidation processes, such as oxidation of metals in solution, the anodization of metals or the electrodeposition of conducting polymers, and the reduction processed such as the electrodeposition of metals or the galvanic deposition. One of the main advantages of the electrochemical processes is the relative easiness to produce various surface morphologies and a precise control of the structures at a micro- or a nanoscale. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Voltage-dependent cluster expansion for electrified solid-liquid interfaces: Application to the electrochemical deposition of transition metals

NASA Astrophysics Data System (ADS)

Weitzner, Stephen E.; Dabo, Ismaila

2017-11-01

The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface electrification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parametrize a cluster expansion of the electrified interface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.

Effect of surface nanostructuring on corrosion behavior of Ti–6Al–4V alloy

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

Kumar, Sanjeev, E-mail: sanjeevphy85@gmail.com; Ch

Surface nanostructure was induced in Ti–6Al–4V alloy by ultrasonic shot peening (USSP) for different durations, from 15 s to 30 min, and the modified surface was characterized by optical, scanning, atomic force and transmission electron microscopy. Nano size grains were observed to form on surface of the USSPed samples and surface roughness was increased with duration of USSP. Polarization study was carried out in Ringer's solution to examine the effect of surface nanostructuring on corrosion resistance of this alloy. Electrochemical corrosion was carried out for all the USSPed specimens as well as the non-USSPed sample in Ringer's solution. Surface morphologymore » of the corroded samples was examined by SEM. In general, corrosion resistance was improved by USSP up to the duration of 15 min and there was maximum improvement in the specimen USSPed for 1 min. However, corrosion resistance was drastically reduced due to USSP for long duration of 30 min. - Highlights: •Nanostructure was induced by USSP on alloy Ti–6Al–4V of about 28 nm. •Grain refinement was confirmed by XRD and TEM. •USSP is an effective technique for the improvement in corrosion resistance. •Nanostructured surface promotes formation of protective surface layer of TiO{sub 2}.« less

A post-labeling strategy based on dye-induced peeling of the aptamer off single-walled carbon nanotubes for electrochemical aptasensing.

PubMed

Fu, Yingchun; Wang, Ting; Bu, Lijuan; Xie, Qingji; Li, Penghao; Chen, Jinhua; Yao, Shouzhuo

2011-03-07

A simple and efficient post-labeling strategy based on dye-induced peeling of the aptamer molecules off single-walled carbon nanotubes was developed for electrochemical aptasensing of thrombin with a detection limit down to 3 pM.

Electrochemical Deposition of Si-Ca/P on Nanotube Formed Beta Ti Alloy by Cyclic Voltammetry Method.

PubMed

Jeong, Yong-Hoon; Choe, Han-Cheol

2015-08-01

The purpose of this study was to investigate electrochemical deposition of Si-Ca/P on nanotube formed Ti-35Nb-10Zr alloy by cyclic voltammetry method. Electrochemical deposition of Si substituted Ca/P was performed by pulsing the applied potential on nanotube formed surface. The surface characteristics were observed by field-emission scanning electron microscopy, X-ray diffractometer, and potentiodynamic polarization test. The phase structure and surface morphologies of Si-Ca/P deposition were affected by deposition cycles. From the anodic polarization test, nanotube formed surface at 20 V showed the high corrosion resistance with lower value of Icorr, I300, and Ipass.

Surface-Electrochemical Sensor for the Measurement of Anti-Cholinesterase Activity

NASA Astrophysics Data System (ADS)

Matsuura, Hiroaki; Sato, Yukari; Yabuki, Soichi; Sawaguchi, Takahiro; Mizutani, Fumio

An organophosphorus pesticide, ethylthiometon (0.01-0.2 ppm) was determined by using a surface-electrochemical sensor system: the monolayer formation (chemisorption)-reductive desorption of thiocholine was applied to monitor the activity change of cholinesterase caused by the pesticide.

Influence of electrochemical potential on the displacement of aqueous electrolyte from a copper surface by oil

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

Kendig, M.W.; Fadner, T.A.

1985-02-01

The forces responsible for the meniscus formed during the dynamic displacement of a 0.1 M H/sub 3/BO/sub 3/ + 0.5 M NaClO/sub 4/ solution by oil from a copper surface depend on the electrochemical potential of the copper and on an active component in the oil. For a nonpolar mineral oil containing oleic acid, a negative potential applied to copper produces hydrophilic behavior of the copper surface in the aqueous phase. This result is attribute largely to electrochemical destabilization of metallic soaps and possibly to electroosmotic transport.

Corrosion of NiTi Wires with Cracked Oxide Layer

NASA Astrophysics Data System (ADS)

Racek, Jan; Šittner, Petr; Heller, Luděk; Pilch, Jan; Petrenec, Martin; Sedlák, Petr

2014-07-01

Corrosion behavior of superelastic NiTi shape memory alloy wires with cracked TiO2 surface oxide layers was investigated by electrochemical corrosion tests (Electrochemical Impedance Spectroscopy, Open Circuit Potential, and Potentiodynamic Polarization) on wires bent into U-shapes of various bending radii. Cracks within the oxide on the surface of the bent wires were observed by FIB-SEM and TEM methods. The density and width of the surface oxide cracks dramatically increase with decreasing bending radius. The results of electrochemical experiments consistently show that corrosion properties of NiTi wires with cracked oxide layers (static load keeps the cracks opened) are inferior compared to the corrosion properties of the straight NiTi wires covered by virgin uncracked oxides. Out of the three methods employed, the Electrochemical Impedance Spectroscopy seems to be the most appropriate test for the electrochemical characterization of the cracked oxide layers, since the impedance curves (Nyquist plot) of differently bent NiTi wires can be associated with increasing state of the surface cracking and since the NiTi wires are exposed to similar conditions as the surfaces of NiTi implants in human body. On the other hand, the potentiodynamic polarization test accelerates the corrosion processes and provides clear evidence that the corrosion resistance of bent superelastic NiTi wires degrades with oxide cracking.

A Twice Electrochemical-Etching Method to Fabricate Superhydrophobic-Superhydrophilic Patterns for Biomimetic Fog Harvest.

PubMed

Yang, Xiaolong; Song, Jinlong; Liu, Junkai; Liu, Xin; Jin, Zhuji

2017-08-18

Superhydrophobic-superhydrophilic patterned surfaces have attracted more and more attention due to their great potential applications in the fog harvest process. In this work, we developed a simple and universal electrochemical-etching method to fabricate the superhydrophobic-superhydrophilic patterned surface on metal superhydrophobic substrates. The anti-electrochemical corrosion property of superhydrophobic substrates and the dependence of electrochemical etching potential on the wettability of the fabricated dimples were investigated on Al samples. Results showed that high etching potential was beneficial for efficiently producing a uniform superhydrophilic dimple. Fabrication of long-term superhydrophilic dimples on the Al superhydrophobic substrate was achieved by combining the masked electrochemical etching and boiling-water immersion methods. A long-term wedge-shaped superhydrophilic dimple array was fabricated on a superhydrophobic surface. The fog harvest test showed that the surface with a wedge-shaped pattern array had high water collection efficiency. Condensing water on the pattern was easy to converge and depart due to the internal Laplace pressure gradient of the liquid and the contact angle hysteresis contrast on the surface. The Furmidge equation was applied to explain the droplet departing mechanism and to control the departing volume. The fabrication technique and research of the fog harvest process may guide the design of new water collection devices.

Coupled diffusion and mechanics in battery electrodes

NASA Astrophysics Data System (ADS)

Eshghinejad, Ahmadreza

We are living in a world with continuous production and consumption of energy. The energy production in the past decades has started to move away from petrochemical sources toward sustainable sources such as solar, wind and geothermal. Also, the energy consumption is further adapting to the sustainable sources. For instance, in recent years electric vehicles are growing fast that can consume sustainable electric energy stored in their batteries. In this direction, in order to further move toward sustainable energy, materials are becoming increasingly important for storing electric energy. Although, currently the technologies such as Li-ion batteries and solid-oxide fuel cells are commercially available for energy applications, improvements are crucial for the next generation of many other technologies producing or consuming sustainable energies. A critical aspect of the electrochemical activities involved in energy storage technologies such as Li-ion batteries and solid-oxide fuel cells is the diffusion of ions into the electrode materials. This process ultimately governs various functional properties of the batteries such as capacity and charging/discharging rates. The first goal of this dissertation is to develop mathematical tools to analyze the ionic diffusion and investigate its coupling with mechanics in electrodes. For this purpose, a thermodynamics-based modeling framework is developed and numerically solved using two numerical methods to analyze ionic diffusion in heterogeneous and structured electrodes. The next goal of this dissertation is to develop and analyze characterization techniques to probe the electrochemical processes at the nano-scale. To this end, the mathematical models are first employed to model a previously developed Atomic Force Microscopy based technique to probe local electrochemical activities called Electrochemical Strain Microscopy (ESM). This method probes the activities by inducing AC electric field to perturb ionic activities and measuring the surface vibrations. Different aspects of this technique are analyzed and the limitations are discussed. Such limitations moves the dissertation toward development of a new technique for probing the electrochemical activities, to overcome the previous limitations, called Scanning Thermo-ionic Microscopy (STIM). In this method, the local activities are probed by inducing AC temperature oscillations to perturb ionic activities and measuring the surface vibrations. The principle mathematical analysis of the coupled governing equations and the method of probing electrochemical activities are discussed in detail. Also, the method is implemented into the AFM hardware/software and the STIM response is confirmed using experiments on LiFePO4 and Sm-doped Ceria as well-known battery and fuel cell electrodes. The STIM method provides a clean method for analyzing energy storage materials and designing novel nano-structured materials for improved performance. Finally, conclusion of the presented work is discussed in the last chapter and the future works to continue the development of the modeling and experiments are listed.

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.

Electrochemical Properties of Graphene Oxide/Resol Composites as Electrode Materials for Supercapacitor Applications.

PubMed

Park, Geon Woo; Jeon, Sang Kwon; Yang, Jin Yong; Choi, Sung Dae; Kim, Geon Joong

2016-05-01

RGO/Resol carbon composites were prepared from a mixture of reduced GO and a low-molecular-weight phenolic resin (Resol) solution. The effects of the calcination temperature, amount of Resol added and KOH treatment on the electrochemical performance of the RGO/Resol composites were investigated. The physical and electrochemical properties of the composite materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer, Emmett and Teller (BET) surface areas measurements, and cyclic voltammetry (CV). The relationships between their physical properties and their electrochemical performance were examined for use as super-capacitors (SCs). The RGO/Resol composite calcined at 400 degrees C after the KOH loading showed dramatically improved electrochemical properties, showing a high BET surface and capacitance of 2190 m2/g and 220 F/g, respectively. The RGO/Resol composites calcined after the KOH treatment showed much better capacitor performance than those treated only thermally at the same temperature without KOH impregnation. The fabrication of high surface electrodes was essential for improving the SCs properties.

Electrochemical annealing of nanoporous gold by application of cyclic potential sweeps

PubMed Central

Sharma, Abeera; Bhattarai, Jay K.; Alla, Allan J.; Demchenko, Alexei V.; Stine, Keith J.

2015-01-01

An electrochemical method for annealing the pore sizes of nanoporous gold is reported. The pore sizes of nanoporous gold can be increased by electrochemical cycling with the upper potential limit being just at the onset of gold oxide formation. This study has been performed in electrolyte solutions including potassium chloride, sodium nitrate and sodium perchlorate. Scanning electron microscopy images have been used for ligament and pore size analysis. We examine the modifications of nanoporous gold due to annealing using electrochemical impedance spectroscopy, and cyclic voltammetry and offer a comparison of the surface coverage using the gold oxide stripping method as well as the method in which electrochemically accessible surface area is determined by using a diffusing redox probe. The effect of additives adsorbed on the nanoporous gold surface when subjected to annealing in different electrolytes as well as the subsequent structural changes in nanoporous gold are also reported. The effect of the annealing process on the application of nanoporous gold as a substrate for glucose electro-oxidation is briefly examined. PMID:25649027

Contact electrification induced interfacial reactions and direct electrochemical nanoimprint lithography in n-type gallium arsenate wafer.

PubMed

Zhang, Jie; Zhang, Lin; Wang, Wei; Han, Lianhuan; Jia, Jing-Chun; Tian, Zhao-Wu; Tian, Zhong-Qun; Zhan, Dongping

2017-03-01

Although metal assisted chemical etching (MacEtch) has emerged as a versatile micro-nanofabrication method for semiconductors, the chemical mechanism remains ambiguous in terms of both thermodynamics and kinetics. Here we demonstrate an innovative phenomenon, i.e. , the contact electrification between platinum (Pt) and an n-type gallium arsenide (100) wafer (n-GaAs) can induce interfacial redox reactions. Because of their different work functions, when the Pt electrode comes into contact with n-GaAs, electrons will move from n-GaAs to Pt and form a contact electric field at the Pt/n-GaAs junction until their electron Fermi levels ( E F ) become equal. In the presence of an electrolyte, the potential of the Pt/electrolyte interface will shift due to the contact electricity and induce the spontaneous reduction of MnO 4 - anions on the Pt surface. Because the equilibrium of contact electrification is disturbed, electrons will transfer from n-GaAs to Pt through the tunneling effect. Thus, the accumulated positive holes at the n-GaAs/electrolyte interface make n-GaAs dissolve anodically along the Pt/n-GaAs/electrolyte 3-phase interface. Based on this principle, we developed a direct electrochemical nanoimprint lithography method applicable to crystalline semiconductors.

Fast-pulverization enabled simultaneous enhancement on cycling stability and rate capability of C@NiFe2O4 hierarchical fibrous bundle

NASA Astrophysics Data System (ADS)

Chen, Zerui; Zhang, Yu; Wang, Xiaoling; Sun, Wenping; Dou, Shixue; Huang, Xin; Shi, Bi

2017-09-01

Electrochemical-grinding induced pulverization is the origin of capacity fading in NiFe2O4. Increasing current density normally accelerates the pulverization that deteriorates lithium storage properties of NiFe2O4. Here we show that the high current induced fast-pulverization can serve as an efficient activation strategy for quick and simultaneous enhancement on cycling stability and rate capability of NiFe2O4 nanoparticles (NPs) that are densely packed on the hierarchically structured carbon nanofiber strand. At a high current density, the pulverization of NiFe2O4 NPs can be accomplished in a few cycles exposing more active surface. During the fast-pulverization, the hierarchically structured carbon nanofiber strand maintains conductive contact for the densely packed NiFe2O4 NPs regardless of charge or discharge, which also effectively suppresses the repetitive breaks and growths of solid-electrolyte-interphase (SEI) via multiple-level structural adaption that favourites the quick formation of a thin and dense SEI, thus providing strong interparticle connectivity with enhancement on cycling stability and rate capability (e.g. doubled capacity). Our findings demonstrate the potential importance of high current induced fast-pulverization as an efficient activation strategy for achieving durable electrode materials suffering from electrochemical-grinding effects.

Reclamation of niobium compounds from ionic liquid electrochemical polishing of superconducting radio frequency cavities

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

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-06-01

Recent research has shown that choline chloride (vitamin B4)-based solutions can be used as a greener alternative to acid-based electrochemical polishing solutions. This study demonstrated a successful method for electrochemical deposition of niobium compounds onto the surface of copper substrates using a novel choline chloride-based ionic liquid. Niobium ions present in the ionic liquid solution were dissolved into the solution prior to deposition via electrochemical polishing of solid niobium. A black coating was clearly visible on the surface of the Cu following deposition. This coating was analyzed using scanning electron microscopy (SEM), electron dispersive X-ray spectroscopy (EDX), atomic force microscopymore » (AFM), and X-ray fluorescence spectroscopy (XRF). This ionic liquid-based electrochemical deposition method effectively recycles previously dissolved niobium from electrochemical polishing of superconducting radio frequency (SRF) cavities.« less

Application of a Nanostructured Enzymatic Biosensor Based on Fullerene and Gold Nanoparticles to Polyphenol Detection.

PubMed

Tortolini, Cristina; Sanzò, Gabriella; Antiochia, Riccarda; Mazzei, Franco; Favero, Gabriele

2017-01-01

Electrochemical biosensors provide an attractive means of analyzing the content of a biological sample due to the direct conversion of a biological event to an electronic signal. The signal transduction and the general performance of electrochemical biosensors are often determined by the surface architectures that connect the sensing element to the biological sample at the nanometer scale. The most common surface modification techniques, the various electrochemical transduction mechanisms, and the choice of the recognition receptor molecules all influence the ultimate sensitivity of the sensor. We show herein a novel electrochemical biosensing platform based on the coupling of two different nanostructured materials (gold nanoparticles and fullerenols) displaying interesting electrochemical features. The use of these nanomaterials improved the electrochemical performance of the proposed biosensor.An application of the nanostructured enzyme-based biosensor has been developed for evaluating the detection of polyphenols either in buffer solution or in real wine samples.

Role of Defects and Adsorbed Water Film in Influencing the Electrical, Optical and Catalytic Properties of Transition Metal Oxides

NASA Astrophysics Data System (ADS)

Wang, Qi

Transition metal oxides (TMOs) constitute a large group of materials that exhibit a wide range of optical, electrical, electrochemical, dielectric and catalytic properties, and thus making them highly regarded as promising materials for a variety of applications in next generation electronic, optoelectronic, catalytic, photonic, energy storage and energy conversion devices. Some of the unique properties of TMOs are their strong electron-electron correlations that exists between the valence electrons of narrow d- or f-shells and their ability to exist in variety of oxidation states. This gives TMOs an enormous range of fascinating electronic and other physical properties. Many of these remarkable properties of TMOs arises from the complex surface charge transfer processes at the oxide surface/electrochemical redox species interface and non-stoichiometry due to the presence of lattice vacancies that may cause significant perturbation to the electronic structure of the material. Stoichiometry, oxidation state of the metal center and lattice vacancy defects all play important roles in affecting the physical properties, electronic structures, device behavior and other functional properties of TMOs. However, the underlying relationships between them is not clearly known. For instance, the exchange of electrons between adsorbates and defects can lead to the passivation of existing defect states or formation of new defects, both of which affect defect equilibria, and consequently, functional properties. In depth understanding of the role of lattice defects on the electrical, catalytic and optical properties of TMOs is central to further expansion of the technological applications of TMO based devices. The focus of this work is to elucidate the interactions of vacancy defects with various electrochemical adsorbates in TMOs. The ability to directly probe the interactions of vacancy defects with gas and liquid phase species under in-operando conditions is highly desirable to obtain a mechanistic understanding of the charge transfer process. We have developed a spectroscopic technique for studying vacancy defects in TMOs using near-infrared photoluminescence (NIR-PL) spectroscopy and showed that this technique is uniquely suited for studying defect-adsorbate interactions. In this work, a series of studies were carried out to elucidate the underlying structure-defect-property correlations of TMOs and their role in catalyzing electrical and electrochemical properties. In the first study, we report a new type of electrical phase transition in p-type, non-stoichiometric nickel oxide involving a semiconductor-to-insulator-to-metal transition along with the complete change of conductivity from p- to n-type at room temperature induced by electrochemical Li+ intercalation. Direct observation of vacancy-ion interactions using in-situ NIR-PL show that the transition is a result of passivation of native nickel (cationic) vacancy defects and subsequent formation of oxygen (anionic) vacancy defects driven by Li+ insertion into the lattice. X-ray photoemission spectroscopy studies performed to examine the changes in the oxidation states of nickel due to defect interactions support the above conclusions. In the second study, main effects of oxygen vacancy defects on the electronic and optical properties of V2O5 nanowires were studied using in-situ Raman, photoluminescence, absorption, and photoemission spectroscopy. We show that both thermal reduction and electrochemical reduction via Li+ insertion results in the creation of oxygen vacancy defects in the crystal that leads to band filling and an increase in the optical band gap of V2O5 from 1.95 eV to 2.45 eV, an effect known as the Burstein-Moss effect. In the third study, we report a new type of semiconductor-adsorbed water interaction in metal oxides known as "electrochemical surface transfer doping," a phenomenon that has been previously been observed on hydrogen-terminated diamond, carbon nanotube, gallium nitride and zinc oxide. Most TMOs at room temperature are known to be strongly hydrated. We show that an adsorbed water film present on the surface of TMOs facilitates the dissolution of gaseous species and promotes charge transfers at the adsorbed-water/oxide interfaces. Further, we show the role of vacancy defects in enhancing catalytic processes by directly monitoring the charge transfer process between gaseous species and vacancy defects in non-stoichiometric p-type nickel oxide and n-type tungsten oxide using in-situ NIR-PL, electrical resistance, and X-ray photoelectron spectroscopy. We find the importance of adsorbed water and vacancy defects in affecting catalytic, electronic, electrical, and optical changes such as insulator-to-metal transitions and radiative emissions during electrochemical reactions. In addition, we demonstrate that electrochemical surface transfer doping exists in another system, specifically, in gallium nitride, and the presence of this adsorbed water film present on the surface of GaN induces electron transfer from GaN that leads to the formation of an electron depletion region on the surface.

Rational Design of Bi Nanoparticles for Efficient Electrochemical CO 2 Reduction: The Elucidation of Size and Surface Condition Effects

DOE PAGES

Zhang, Zhiyong; Chi, Miaofang; Veith, Gabriel M.; ...

2016-08-08

Here we report an efficient electrochemical conversion of CO 2 to CO on surface-activated bismuth nanoparticles (NPs) in acetonitrile (MeCN) under ambient conditions, with the assistance of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]). Through the comparison between electrodeposited Bi films (Bi-ED) and different types of Bi NPs, we, for the first time, demonstrate the effects of catalyst’s size and surface condition on organic phase electrochemical CO 2 reduction. Our study reveals that the surface inhibiting layer (hydrophobic surfactants and Bi 3+ species) formed during the synthesis and purification process hinders the CO 2 reduction, leading to a 20% drop in Faradaic efficiency formore » CO evolution (FE CO). Bi particle size showed a significant effect on FE CO when the surface of Bi was air-oxidized, but this effect of size on FE CO became negligible on surface-activated Bi NPs. After the surface activation (hydrazine treatment) that effectively removed the native inhibiting layer, activated 36-nm Bi NPs exhibited an almost-quantitative conversion of CO 2 to CO (96.1% FE CO), and a mass activity for CO evolution (MA CO) of 15.6 mA mg –1, which is three-fold higher than the conventional Bi-ED, at ₋2.0 V (vs Ag/AgCl). Ultimately, this work elucidates the importance of the surface activation for an efficient electrochemical CO 2 conversion on metal NPs and paves the way for understanding the CO 2 electrochemical reduction mechanism in nonaqueous media.« less

Influence of biocompatible metal ions (Ag, Fe, Y) on the surface chemistry, corrosion behavior and cytocompatibility of Mg-1Ca alloy treated with MEVVA.

PubMed

Liu, Yang; Bian, Dong; Wu, Yuanhao; Li, Nan; Qiu, Kejin; Zheng, Yufeng; Han, Yong

2015-09-01

Mg-1Ca samples were implanted with biocompatible alloy ions Ag, Fe and Y respectively with a dose of 2×10(17)ionscm(-2) by metal vapor vacuum arc technique (MEVVA). The surface morphologies and surface chemistry were investigated by SEM, AES and XPS. Surface changes were observed after all three kinds of elemental ion implantation. The results revealed that the modified layer was composed of two sublayers, including an outer oxidized layer with mixture of oxides and an inner implanted layer, after Ag and Fe ion implantation. Y ion implantation induced an Mg/Ca-deficient outer oxidized layer and the distribution of Y along with depth was more homogeneous. Both electrochemical test and immersion test revealed accelerated corrosion rate of Ag-implanted Mg-1Ca and Fe-implanted Mg-1Ca, whereas Y ion implantation showed a short period of protection since enhanced corrosion resistance was obtained by electrochemical test, but accelerated corrosion rate was found by long period immersion test. Indirect cytotoxicity assay indicated good cytocompatibility of Y-implanted Mg-1Ca. Moreover, the corresponding corrosion mechanisms involving implanting ions into magnesium alloys were proposed, which might provide guidance for further application of plasma ion implantation to biodegradable Mg alloys. Copyright © 2015 Elsevier B.V. All rights reserved.

Reciprocal interaction between dental alloy biocorrosion and Streptococcus mutans virulent gene expression.

PubMed

Zhang, Songmei; Qiu, Jing; Ren, Yanfang; Yu, Weiqiang; Zhang, Fuqiang; Liu, Xiuxin

2016-04-01

Corrosion of dental alloys is a major concern in dental restorations. Streptococcus mutans reduces the pH in oral cavity and induces demineralization of the enamel as well as corrosion of restorative dental materials. The rough surfaces of dental alloys induced by corrosion enhance the subsequent accumulation of plaque. In this study, the corrosion process of nickel-chromium (Ni-Cr) and cobalt-chromium (Co-Cr) alloys in a nutrient-rich medium containing S. mutans was studied using inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray photoelectron spectroscopy (XPS) and electrochemical corrosion test. Our results showed that the release of Ni and Co ions increased, particularly after incubation for 3 days. The electrochemical corrosion results showed a significant decrease in the corrosion resistance (Rp) value after the alloys were immersed in the media containing S. mutans for 3 days. Correspondingly, XPS revealed a reduction in the relative dominance of Ni, Co, and Cr in the surface oxides after the alloys were immersed in the S. mutans culture. After removal of the biofilm, the pre-corroded alloys were re-incubated in S. mutans medium, and the expressions of genes associated with the adhesion and acidogenesis of S. mutans, including gtfBCD, gbpB, fif and ldh, were evaluated by detecting the mRNA levels using real-time reverse transcription polymerase chain reaction (RT-PCR). We found that the gtfBCD, gbpB, ftf and Idh expression of S. mutans were noticeably increased after incubation with pre-corroded alloys for 24 h. This study demonstrated that S. mutans enhanced the corrosion behavior of the dental alloys, on the other hand, the presence of corroded alloy surfaces up-regulated the virulent gene expression in S. mutans. Compared with smooth surfaces, the rough corroded surfaces of dental alloys accelerated the bacteria-adhesion and corrosion process by changing the virulence gene expression of S. mutans.

Preparation of superhydrophobic copper surface by a novel silk-screen printing aided electrochemical machining method

NASA Astrophysics Data System (ADS)

Yan, X. Y.; Chen, G. X.; Liu, J. W.

2018-03-01

A kind of superhydrophobic copper surface with micro-nanocomposite structure has been successfully fabricated by employing a silk-screen printing aided electrochemical machining method. At first silk-screen printing technology has been used to form a column point array mask, and then the microcolumn array would be fabricated by electrochemical machining (ECM) effect. In this study, the drop contact angles have been studied and scanning electron microscopy (SEM) has been used to study the surface characteristic of the workpiece. The experiment results show that the micro-nanocomposite structure with cylindrical array can be successfully fabricated on the metal surface. And the maximum contact angle is 151° when the fluoroalkylsilane ethanol solution was used to modify the machined surface in this study.

Electrode for electrochemical cell

DOEpatents

Kaun, T.D.; Nelson, P.A.; Miller, W.E.

1980-05-09

An electrode structure for a secondary electrochemical cell includes an outer enclosure defining a compartment containing electrochemical active material. The enclosure includes a rigid electrically conductive metal sheet with perforated openings over major side surfaces. The enclosure can be assembled as first and second trays each with a rigid sheet of perforated electrically conductive metal at major side surfaces and normally extending flanges at parametric margins. The trays can be pressed together with moldable active material between the two to form an expandable electrode. A plurality of positive and negative electrodes thus formed are arranged in an alternating array with porous frangible interelectrode separators within the housing of the secondary electrochemical cell.

Electrode for electrochemical cell

DOEpatents

Kaun, Thomas D.; Nelson, Paul A.; Miller, William E.

1981-01-01

An electrode structure for a secondary electrochemical cell includes an outer enclosure defining a compartment containing electrochemical active material. The enclosure includes a rigid electrically conductive metal sheet with perforated openings over major side surfaces. The enclosure can be assembled as first and second trays each with a rigid sheet of perforated electrically conductive metal at major side surfaces and normally extending flanges at parametric margins. The trays can be pressed together with moldable active material between the two to form an expandable electrode. A plurality of positive and negative electrodes thus formed are arranged in an alternating array with porous frangible interelectrode separators within the housing of the secondary electrochemical cell.

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.

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.

Self-Assembled Three-Dimensional Graphene Macrostructures: Synthesis and Applications in Supercapacitors.

PubMed

Xu, Yuxi; Shi, Gaoquan; Duan, Xiangfeng

2015-06-16

Graphene and its derivatives are versatile building blocks for bottom-up assembly of advanced functional materials. In particular, with exceptionally large specific surface area, excellent electrical conductivity, and superior chemical/electrochemical stability, graphene represents the ideal material for various electrochemical energy storage devices including supercapacitors. However, due to the strong π-π interaction between graphene sheets, the graphene flakes tend to restack to form graphite-like powders when they are processed into practical electrode materials, which can greatly reduce the specific surface area and lead to inefficient utilization of the graphene layers for electrochemical energy storage. The self-assembly of two-dimensional graphene sheets into three-dimensional (3D) framework structures can largely retain the unique properties of individual graphene sheets and has recently garnered intense interest for fundamental investigations and potential applications in diverse technologies. In this Account, we review the recent advances in preparing 3D graphene macrostructures and exploring them as a unique platform for supercapacitor applications. We first describe the synthetic strategies, in which reduction of a graphene oxide dispersion above a certain critical concentration can induce the reduced graphene oxide sheets to cross-link with each other via partial π-π stacking interactions to form a 3D interconnected porous macrostructure. Multiple reduction strategies, including hydrothermal/solvothermal reduction, chemical reduction, and electrochemical reduction, have been developed for the preparation of 3D graphene macrostructures. The versatile synthetic strategies allow for easy incorporation of heteroatoms, carbon nanomaterials, functional polymers, and inorganic nanostructures into the macrostructures to yield diverse composites with tailored structures and properties. We then summarize the applications of the 3D graphene macrostructures for high-performance supercapacitors. With a unique framework structure in which the graphene sheets are interlocked in 3D space to prevent their restacking, the graphene macrostructures feature very high specific surface areas, rapid electron and ion transport, and superior mechanical strength. They can thus be directly used as supercapacitor electrodes with excellent specific capacitances, rate capabilities, and cycling stabilities. We finally discuss the current challenges and future opportunities in this research field. By regarding the graphene as both a single-atom-thick carbon sheet and a conjugated macromolecule, our work opens a new avenue to bottom-up self-assembly of graphene macromolecule sheets into functional 3D graphene macrostructures with remarkable electrochemical performances. We hope that this Account will promote further efforts toward fundamental investigation of graphene self-assembly and the development of advanced 3D graphene materials for their real-world applications in electrochemical energy storage devices and beyond.

Electrochemical and thermal grafting of alkyl grignard reagents onto (100) silicon surfaces.

PubMed

Vegunta, Sri Sai S; Ngunjiri, Johnpeter N; Flake, John C

2009-11-03

Passivation of (100) silicon surfaces using alkyl Grignard reagents is explored via electrochemical and thermal grafting methods. The electrochemical behavior of silicon in methyl or ethyl Grignard reagents in tetrahydrofuran is investigated using cyclic voltammetry. Surface morphology and chemistry are investigated using atomic force microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that electrochemical pathways provide an efficient and more uniform passivation method relative to thermal methods, and XPS results demonstrate that electrografted terminations are effective at limiting native oxide formation for more than 55 days in ambient conditions. A two-electron per silicon mechanism is proposed for electrografting a single (1:1) alkyl group per (100) silicon atom. The mechanism includes oxidation of two Grignard species and subsequent hydrogen abstraction and alkylation reaction resulting in a covalent attachment of alkyl groups with silicon.

Electrochemical micro/nano-machining: principles and practices.

PubMed

Zhan, Dongping; Han, Lianhuan; Zhang, Jie; He, Quanfeng; Tian, Zhao-Wu; Tian, Zhong-Qun

2017-03-06

Micro/nano-machining (MNM) is becoming the cutting-edge of high-tech manufacturing because of the increasing industrial demand for supersmooth surfaces and functional three-dimensional micro/nano-structures (3D-MNS) in ultra-large scale integrated circuits, microelectromechanical systems, miniaturized total analysis systems, precision optics, and so on. Taking advantage of no tool wear, no surface stress, environmental friendliness, simple operation, and low cost, electrochemical micro/nano-machining (EC-MNM) has an irreplaceable role in MNM. This comprehensive review presents the state-of-art of EC-MNM techniques for direct writing, surface planarization and polishing, and 3D-MNS fabrications. The key point of EC-MNM is to confine electrochemical reactions at the micro/nano-meter scale. This review will bring together various solutions to "confined reaction" ranging from electrochemical principles through technical characteristics to relevant applications.

Electrochemical nitridation of metal surfaces

DOEpatents

Wang, Heli; Turner, John A.

2015-06-30

Electrochemical nitridation of metals and the produced metals are disclosed. An exemplary method of electrochemical nitridation of metals comprises providing an electrochemical solution at low temperature. The method also comprises providing a three-electrode potentiostat system. The method also comprises stabilizing the three-electrode potentiostat system at open circuit potential. The method also comprises applying a cathodic potential to a metal.

Isolating the effect of pore size distribution on electrochemical double-layer capacitance using activated fluid coke

NASA Astrophysics Data System (ADS)

Zuliani, Jocelyn E.; Tong, Shitang; Kirk, Donald W.; Jia, Charles Q.

2015-12-01

Electrochemical double-layer capacitors (EDLCs) use physical ion adsorption in the capacitive electrical double layer of high specific surface area (SSA) materials to store electrical energy. Previous work shows that the SSA-normalized capacitance increases when pore diameters are less than 1 nm. However, there still remains uncertainty about the charge storage mechanism since the enhanced SSA-normalized capacitance is not observed in all microporous materials. In previous studies, the total specific surface area and the chemical composition of the electrode materials were not controlled. The current work is the first reported study that systematically compares the performance of activated carbon prepared from the same raw material, with similar chemical composition and specific surface area, but different pore size distributions. Preparing samples with similar SSAs, but different pores sizes is not straightforward since increasing pore diameters results in decreasing the SSA. This study observes that the microporous activated carbon has a higher SSA-normalized capacitance, 14.1 μF cm-2, compared to the mesoporous material, 12.4 μF cm-2. However, this enhanced SSA-normalized capacitance is only observed above a threshold operating voltage. Therefore, it can be concluded that a minimum applied voltage is required to induce ion adsorption in these sub-nanometer micropores, which increases the capacitance.

Electric Arc and Electrochemical Surface Texturing Technologies

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Rutledge, Sharon K.; Snyder, Scott A.

1997-01-01

Surface texturing of conductive materials can readily be accomplished by means of a moving electric arc which produces a plasma from the environmental gases as well as from the vaporized substrate and arc electrode materials. As the arc is forced to move across the substrate surface, a condensate from the plasma re-deposits an extremely rough surface which is intimately mixed and attached to the substrate material. The arc textured surfaces produce greatly enhanced thermal emittance and hold potential for use as high temperature radiator surfaces in space, as well as in systems which use radiative heat dissipation such as computer assisted tomography (CAT) scan systems. Electrochemical texturing of titanium alloys can be accomplished by using sodium chloride solutions along with ultrasonic agitation to produce a random distribution of craters on the surface. The crater size and density can be controlled to produce surface craters appropriately sized for direct bone in-growth of orthopaedic implants. Electric arc texturing and electrochemical texturing techniques, surface properties and potential applications will be presented.

Nanotubular surface modification of metallic implants via electrochemical anodization technique.

PubMed

Wang, Lu-Ning; Jin, Ming; Zheng, Yudong; Guan, Yueping; Lu, Xin; Luo, Jing-Li

2014-01-01

Due to increased awareness and interest in the biomedical implant field as a result of an aging population, research in the field of implantable devices has grown rapidly in the last few decades. Among the biomedical implants, metallic implant materials have been widely used to replace disordered bony tissues in orthopedic and orthodontic surgeries. The clinical success of implants is closely related to their early osseointegration (ie, the direct structural and functional connection between living bone and the surface of a load-bearing artificial implant), which relies heavily on the surface condition of the implant. Electrochemical techniques for modifying biomedical implants are relatively simple, cost-effective, and appropriate for implants with complex shapes. Recently, metal oxide nanotubular arrays via electrochemical anodization have become an attractive technique to build up on metallic implants to enhance the biocompatibility and bioactivity. This article will thoroughly review the relevance of electrochemical anodization techniques for the modification of metallic implant surfaces in nanoscale, and cover the electrochemical anodization techniques used in the development of the types of nanotubular/nanoporous modification achievable via electrochemical approaches, which hold tremendous potential for bio-implant applications. In vitro and in vivo studies using metallic oxide nanotubes are also presented, revealing the potential of nanotubes in biomedical applications. Finally, an outlook of future growth of research in metallic oxide nanotubular arrays is provided. This article will therefore provide researchers with an in-depth understanding of electrochemical anodization modification and provide guidance regarding the design and tuning of new materials to achieve a desired performance and reliable biocompatibility.

Nanotubular surface modification of metallic implants via electrochemical anodization technique

PubMed Central

Wang, Lu-Ning; Jin, Ming; Zheng, Yudong; Guan, Yueping; Lu, Xin; Luo, Jing-Li

2014-01-01

Due to increased awareness and interest in the biomedical implant field as a result of an aging population, research in the field of implantable devices has grown rapidly in the last few decades. Among the biomedical implants, metallic implant materials have been widely used to replace disordered bony tissues in orthopedic and orthodontic surgeries. The clinical success of implants is closely related to their early osseointegration (ie, the direct structural and functional connection between living bone and the surface of a load-bearing artificial implant), which relies heavily on the surface condition of the implant. Electrochemical techniques for modifying biomedical implants are relatively simple, cost-effective, and appropriate for implants with complex shapes. Recently, metal oxide nanotubular arrays via electrochemical anodization have become an attractive technique to build up on metallic implants to enhance the biocompatibility and bioactivity. This article will thoroughly review the relevance of electrochemical anodization techniques for the modification of metallic implant surfaces in nanoscale, and cover the electrochemical anodization techniques used in the development of the types of nanotubular/nanoporous modification achievable via electrochemical approaches, which hold tremendous potential for bio-implant applications. In vitro and in vivo studies using metallic oxide nanotubes are also presented, revealing the potential of nanotubes in biomedical applications. Finally, an outlook of future growth of research in metallic oxide nanotubular arrays is provided. This article will therefore provide researchers with an in-depth understanding of electrochemical anodization modification and provide guidance regarding the design and tuning of new materials to achieve a desired performance and reliable biocompatibility. PMID:25258532

Electrochemical analysis of gold-coated magnetic nanoparticles for detecting immunological interaction

NASA Astrophysics Data System (ADS)

Pham, Thao Thi-Hien; Sim, Sang Jun

2010-01-01

An electrochemical impedance immunosensor was developed for detecting the immunological interaction between human immunoglobulin (IgG) and protein A from Staphylococcus aureus based on the immobilization of human IgG on the surface of modified gold-coated magnetic nanoparticles. The nanoparticles with an Au shell and Fe oxide cores were functionalized by a self-assembled monolayer of 11-mercaptoundecanoic acid. The electrochemical analysis was conducted on the modified magnetic carbon paste electrodes with the nanoparticles. The magnetic nanoparticles were attached to the surface of the magnetic carbon paste electrodes via magnetic force. The cyclic voltammetry technique and electrochemical impedance spectroscopy measurements of the magnetic carbon paste electrodes coated with magnetic nanoparticles-human IgG complex showed changes in its alternating current (AC) response both after the modification of the surface of the electrode and the addition of protein A. The immunological interaction between human IgG on the surface of the modified magnetic carbon paste electrodes and protein A in the solution could be successfully monitored.

Surface Modifications of Materials by Electrochemical Methods to Improve the Properties for Industrial and Medical Applications

NASA Astrophysics Data System (ADS)

Benea, Lidia

2018-06-01

There are two applied electrochemical methods in our group in order to obtain advanced functional surfaces on materials: (i) direct electrochemical synthesis by electro-codeposition process and (ii) anodization of materials to form nanoporous oxide layers followed by electrodeposition of hydroxyapatite or other bioactive molecules and compounds into porous film. Electrodeposition is a process of low energy consumption, and therefore very convenient for the surface modification of various types of materials. Electrodeposition is a powerful method compared with other methods, which led her to be adopted and spread rapidly in nanotechnology to obtain nanostructured layers and films. Nanoporous thin oxide layers on titanum alloys as support for hydroxyapatite or other biomolecules electrodeposition in view of biomedical applications could be obtained by electrochemical methods. For surface modification of titanium or titanium alloys to improve the biocompatibility or osseointegration, the two steps must be fulfilled; the first is controlled growth of oxide layer followed by second being biomolecule electrodeposition into nanoporous formed titanium oxide layer.

Electrochemically Driven Deactivation and Recovery in PrBaCo2 O5+δ Oxygen Electrodes for Reversible Solid Oxide Fuel Cells.

PubMed

Zhu, Lin; Wei, Bo; Wang, Zhihong; Chen, Kongfa; Zhang, Haiwu; Zhang, Yaohui; Huang, Xiqiang; Lü, Zhe

2016-09-08

The understanding of surface chemistry changes on oxygen electrodes is critical for the development of reversible solid oxide fuel cell (RSOFC). Here, we report for the first time that the electrochemical potentials can drastically affect the surface composition and hence the electrochemical activity and stability of PrBaCo2 O5+δ (PBCO) electrodes. Anodic polarization degrades the activity of the PBCO electrode, whereas the cathodic bias could recover its performance. Alternating anodic/cathodic polarization for 180 h confirms this behavior. Microstructure and chemical analysis clearly show that anodic bias leads to the accumulation and segregation of insulating nanosized BaO on the electrode surface, whereas cathodic polarization depletes the surface species. Therefore, a mechanism based on the segregation and incorporation of BaO species under electrochemical potentials is considered to be responsible for the observed deactivation and recovery process, respectively. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface treatment influences electrochemical stability of cpTi exposed to mouthwashes.

PubMed

Beline, Thamara; Garcia, Camila S; Ogawa, Erika S; Marques, Isabella S V; Matos, Adaias O; Sukotjo, Cortino; Mathew, Mathew T; Mesquita, Marcelo F; Consani, Rafael X; Barão, Valentim A R

2016-02-01

The role of surface treatment on the electrochemical behavior of commercially pure titanium (cpTi) exposed to mouthwashes was tested. Seventy-five disks were divided into 15 groups according to surface treatment (machined, sand blasted with Al2O3, and acid etched) and electrolyte solution (artificial saliva — control, 0.12% chlorhexidine digluconate, 0.05% cetylpyridinium chloride, 0.2% sodium fluoride, and 1.5% hydrogen peroxide) (n = 5). Open-circuit-potential and electrochemical impedance spectroscopy were conducted at baseline and after 7 and 14 days of immersion in each solution. Potentiodynamic test and total weight loss of disks were performed after 14 days of immersion. Scanning electron microscopy, energy dispersive spectroscopy, white light interferometry and profilometry were conducted for surface characterization before and after the electrochemical tests. Sandblasting promoted the lowest polarization resistance (Rp) (P b .0001) and the highest capacitance (CPE) (P b .006), corrosion current density (Icorr) and corrosion rate (P b .0001). In contrast, acid etching increased Rp and reduced CPE, independent to the mouthwash; while hydrogen peroxide reduced Rp (P b .008) and increased Icorr and corrosion rate (P b .0001). The highest CPE values were found for hydrogen peroxide and 0.2% sodium fluoride. Immersion for longer period improved the electrochemical stability of cpTi (P b .05). In conclusion, acid etching enhanced the electrochemical stability of cpTi. Hydrogen peroxide and sodium fluoride reduced the resistance to corrosion of cpTi, independent to the surface treatment. Chlorhexidine gluconate and cetylpyridinium chloride did not alter the corrosive behavior of cpTi.

Rechargeable Batteries with High Energy Storage Activated by In-situ Induced Fluorination of Carbon Nanotube Cathode

PubMed Central

Cui, Xinwei; Chen, Jian; Wang, Tianfei; Chen, Weixing

2014-01-01

High performance rechargeable batteries are urgently demanded for future energy storage systems. Here, we adopted a lithium-carbon battery configuration. Instead of using carbon materials as the surface provider for lithium-ion adsorption and desorption, we realized induced fluorination of carbon nanotube array (CNTA) paper cathodes, with the source of fluoride ions from electrolytes, by an in-situ electrochemical induction process. The induced fluorination of CNTA papers activated the reversible fluorination/defluorination reactions and lithium-ion storage/release at the CNTA paper cathodes, resulting in a dual-storage mechanism. The rechargeable battery with this dual-storage mechanism demonstrated a maximum discharging capacity of 2174 mAh gcarbon−1 and a specific energy of 4113 Wh kgcarbon−1 with good cycling performance. PMID:24931036

The aqueous electrochemistry of carbon-based surfaces-investigation by scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Mühl, T.; Myhra, S.

2007-04-01

Electro-oxidation of carbon-based materials will lead to conversion of the solid to CO2/CO at the anode, with H2 being produced at the cathode. Recent voltammetric investigations of carbon nano-tubes and single crystal graphite have shown that only edge sites and other defect sites are electrochemically active. Local oxidation of diamond-like carbon films (DLC) by an STM tip in moist air followed by imaging allows correlation of topographical change with electro-chemical conditions and surface reactivity. The results may have implications for lithographic processing of carbon surfaces, and may have relevance for electrochemical H2 production.

Electrochemical synthesis of gold nanoparticles on the surface of multi-walled carbon nanotubes with glassy carbon electrode and their application

NASA Astrophysics Data System (ADS)

Song, Y. Z.; Li, X.; Song, Y.; Cheng, Z. P.; Zhong, H.; Xu, J. M.; Lu, J. S.; Wei, C. G.; Zhu, A. F.; Wu, F. Y.; Xu, J.

2013-01-01

Gold nanoparticles on the surface of multi-walled carbon nanotubes with glassy carbon electrode were prepared using electrochemical synthesis method. The thin films of gold Nanoparticles/multi-walled carbon nanotubes were characterized by scanning electron microscopy, powder X-ray diffraction, and cyclic voltammetry. Electrochemical behavior of adrenaline hydrochloride at gold nanoparticles/multi-walled carbon nanotube modified glassy carbon electrode was investigated. A simple, sensitive, and inexpensive method for determination of adrenaline hydrochloride was proposed.

Tribolayer Formation in a Metal-on-Metal (MoM) Hip Joint: An Electrochemical Investigation

PubMed Central

Mathew, MT; Nagelli, C; Pourzal, R; Fischer, A; Laurent, MP; Jacobs, JJ; Wimmer, MA

2013-01-01

The demand for total hip replacement (THR) surgery is increasing in the younger population due to faster rehabilitation and more complete restoration of function. Up to 2009, metal-on-metal (MoM) hip joint bearings were a popular choice due to their design flexibility, post-operative stability and relatively low wear rates. The main wear mechanisms that occur along the bearing surface of MoM joints are tribochemical reactions that deposit a mixture of wear debris, metal ions and organic matrix of decomposed proteins known as a tribolayer. No in-depth electrochemical studies have been reported on the structure and characteristics of this tribolayer or about the parameters involved in its formation. In this study, we conducted an electrochemical investigation of different surfaces (bulk-like: control, nano-crystalline: new implant and tribolayer surface: retrieved implant) made out of two commonly used hip CoCrMo alloys (high-carbon and low-carbon). As per ASTM standard, cyclic polarization tests and electrochemical impedance spectroscopy tests were conducted. The results obtained from electrochemical parameters for different surfaces clearly indicated a reduction in corrosion for the tribolayer surface (Icorr: 0.76 μA/cm2). Further, polarization resistance (Rp:2.39±0.60MΩ/cm2) and capacitance (Cdl:15.20±0.75 μF/cm2) indicated variation in corrosion kinetics for the tribolayer surface, that attributed to its structure and stability in a simulated body environment. PMID:24099949

STM, SECPM, AFM and Electrochemistry on Single Crystalline Surfaces

PubMed Central

Wolfschmidt, Holger; Baier, Claudia; Gsell, Stefan; Fischer, Martin; Schreck, Matthias; Stimming, Ulrich

2010-01-01

Scanning probe microscopy (SPM) techniques have had a great impact on research fields of surface science and nanotechnology during the last decades. They are used to investigate surfaces with scanning ranges between several 100 μm down to atomic resolution. Depending on experimental conditions, and the interaction forces between probe and sample, different SPM techniques allow mapping of different surface properties. In this work, scanning tunneling microscopy (STM) in air and under electrochemical conditions (EC-STM), atomic force microscopy (AFM) in air and scanning electrochemical potential microscopy (SECPM) under electrochemical conditions, were used to study different single crystalline surfaces in electrochemistry. Especially SECPM offers potentially new insights into the solid-liquid interface by providing the possibility to image the potential distribution of the surface, with a resolution that is comparable to STM. In electrocatalysis, nanostructured catalysts supported on different electrode materials often show behavior different from their bulk electrodes. This was experimentally and theoretically shown for several combinations and recently on Pt on Au(111) towards fuel cell relevant reactions. For these investigations single crystals often provide accurate and well defined reference and support systems. We will show heteroepitaxially grown Ru, Ir and Rh single crystalline surface films and bulk Au single crystals with different orientations under electrochemical conditions. Image studies from all three different SPM methods will be presented and compared to electrochemical data obtained by cyclic voltammetry in acidic media. The quality of the single crystalline supports will be verified by the SPM images and the cyclic voltammograms. Furthermore, an outlook will be presented on how such supports can be used in electrocatalytic studies. PMID:28883327

Economically synthesized NiCo2S4/reduced graphene oxide composite as efficient counter electrode in dye-sensitized solar cell

NASA Astrophysics Data System (ADS)

Nan, Hui; Han, Jianhua; Luo, Qiang; Yin, Xuewen; Zhou, Yu; Yao, Zhibo; Zhao, Xiaochong; Li, Xin; Lin, Hong

2018-04-01

Exploiting efficient Pt-free counter-electrode materials with low cost and highly catalytic property is a hot topic in the field of Dye-sensitized solar cells (DSCs). Here, NiCo2S4/reduced graphene oxide (RGO) was prepared via an economical synthesis route, and the as-prepared composite exhibited comparable electrocatalytic property with the conventional Pt electrode as the counter-electrode. Notably, the introduction of RGO into the NiCo2S4 counter-electrode induces a significantly promoted electrocatalytic rate towards the triiodide reduction than that of pristine NiCo2S4 by increasing surface area in the composite electrode, as revealed by electrochemical impedance spectroscopic measurement and Tafel polarization measurement. The easy synthesis, low cost and excellent electrochemical performance of the NiCo2S4/RGO composites enable themselves to serve as promising counter-electrode candidates for efficient DSCs.

Fabrication of solid oxide fuel cell by electrochemical vapor deposition

DOEpatents

Brian, Riley; Szreders, Bernard E.

1989-01-01

In a high temperature solid oxide fuel cell (SOFC), the deposition of an impervious high density thin layer of electrically conductive interconnector material, such as magnesium doped lanthanum chromite, and of an electrolyte material, such as yttria stabilized zirconia, onto a porous support/air electrode substrate surface is carried out at high temperatures (approximately 1100.degree.-1300.degree. C.) by a process of electrochemical vapor deposition. In this process, the mixed chlorides of the specific metals involved react in the gaseous state with water vapor resulting in the deposit of an impervious thin oxide layer on the support tube/air electrode substrate of between 20-50 microns in thickness. An internal heater, such as a heat pipe, is placed within the support tube/air electrode substrate and induces a uniform temperature profile therein so as to afford precise and uniform oxide deposition kinetics in an arrangement which is particularly adapted for large scale, commercial fabrication of SOFCs.

Electrochemical surface modification of titanium in dentistry.

PubMed

Kim, Kyo-Han; Ramaswamy, Narayanan

2009-01-01

Titanium and its alloys have good biocompatibility with body cells and tissues and are widely used for implant applications. However, clinical procedures place more stringent and tough requirements on the titanium surface necessitating artificial surface treatments. Among the many methods of titanium surface modification, electrochemical techniques are simple and cheap. Anodic oxidation is the anodic electrochemical technique while electrophoretic and cathodic depositions are the cathodic electrochemical techniques. By anodic oxidation it is possible to obtain desired roughness, porosity and chemical composition of the oxide. Anodic oxidation at high voltages can improve the crystallinity of the oxide. The chief advantage of this technique is doping of the coating of the bath constituents and incorporation of these elements improves the properties of the oxide. Electrophoretic deposition uses hydroxyapatite (HA) powders dispersed in a suitable solvent at a particular pH. Under these operating conditions these particles acquire positive charge and coatings are obtained on the cathodic titanium by applying an external electric field. These coatings require a post-sintering treatment to improve the coating properties. Cathodic deposition is another type of electrochemical method where HA is formed in situ from an electrolyte containing calcium and phosphate ions. It is also possible to alter structure and/or chemistry of the obtained deposit. Nano-grained HA has higher surface energy and greater biological activity and therefore emphasis is being laid to produce these coatings by cathodic deposition.

Electrochemical monitoring of biointeraction by graphene-based material modified pencil graphite electrode.

PubMed

Eksin, Ece; Zor, Erhan; Erdem, Arzum; Bingol, Haluk

2017-06-15

Recently, the low-cost effective biosensing systems based on advanced nanomaterials have received a key attention for development of novel assays for rapid and sequence-specific nucleic acid detection. The electrochemical biosensor based on reduced graphene oxide (rGO) modified disposable pencil graphite electrodes (PGEs) were developed herein for electrochemical monitoring of DNA, and also for monitoring of biointeraction occurred between anticancer drug, Daunorubicin (DNR), and DNA. First, rGO was synthesized chemically and characterized by using UV-Vis, TGA, FT-IR, Raman Spectroscopy and SEM techniques. Then, the quantity of rGO assembling onto the surface of PGE by passive adsorption was optimized. The electrochemical behavior of rGO-PGEs was examined by cyclic voltammetry (CV). rGO-PGEs were then utilized for electrochemical monitoring of surface-confined interaction between DNR and DNA using differential pulse voltammetry (DPV) technique. Additionally, voltammetric results were complemented with electrochemical impedance spectroscopy (EIS) technique. Electrochemical monitoring of DNR and DNA was resulted with satisfying detection limits 0.55µM and 2.71µg/mL, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

High-Temperature Carbon Deposition on Oxide Surfaces by CO Disproportionation

PubMed Central

2016-01-01

Carbon deposition due to the inverse Boudouard reaction (2CO → CO2 + C) has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 in comparison to CH4 by a variety of different chemical, structural, and spectroscopic characterization techniques, including electrochemical impedance spectroscopy (EIS), Fourier-transform infrared (FT-IR) spectroscopy and imaging, Raman spectroscopy, and electron microscopy. Consentaneously, all experimental methods prove the formation of a more or less conducting carbon layer (depending on the used oxide) of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in flowing CO at temperatures above ∼1023 K. All measurements show that during carbon deposition, a more or less substantial surface reduction of the oxides takes place. These results, therefore, reveal that the studied pure oxides can act as efficient nonmetallic substrates for CO-induced growth of highly distorted graphitic carbon with possible important technological implications especially with respect to treatment in pure CO or CO-rich syngas mixtures. Compared to CH4, more carbon is generally deposited in CO under otherwise similar experimental conditions. Although Raman and electron microscopy measurements do not show substantial differences in the structure of the deposited carbon layers, in particular, electrochemical impedance measurements reveal major differences in the dynamic growth process of the carbon layer, eventually leading to less percolated islands and suppressed metallic conductivity in comparison to CH4-induced graphite. PMID:26877828

Folding- and Dynamics-Based Electrochemical DNA Sensors.

PubMed

Lai, Rebecca Y

2017-01-01

A number of electrochemical DNA sensors based on the target-induced change in the conformation and/or flexibility of surface-bound oligonucleotides have been developed in recent years. These sensors, which are often termed E-DNA sensors, are comprised of an oligonucleotide probe modified with a redox label (e.g., methylene blue) at one terminus and attached to a gold electrode via a thiol-gold bond at the other. Binding of the target to the DNA probe changes its structure and dynamics, which, in turn, influences the efficiency of electron transfer to the interrogating electrode. Since electrochemically active contaminants are less common, these sensors are resistant to false-positive signals arising from the nonspecific adsorption of contaminants and perform well even when employed directly in serum, whole blood, and other realistically complex sample matrices. Moreover, because all of the sensor components are chemisorbed to the electrode, the E-DNA sensors are essentially label-free and readily reusable. To date, these sensors have achieved state-of-the-art sensitivity, while offering the unprecedented selectivity, reusability, and the operational convenience of direct electrochemical detection. This chapter reviews the recent advances in the development of both "signal-off" and "signal-on" E-DNA sensors. Critical aspects that dictate the stability and performance of these sensors are also addressed so as to provide a realistic overview of this oligonucleotide detection platform. © 2017 Elsevier Inc. All rights reserved.

Fabrication of Compositionally and Topographically Complex Robust Tissue Forms by 3D-Electrochemical Compaction of Collagen

PubMed Central

Younesi, Mousa; Islam, Anowarul; Kishore, Vipuil; Panit, Stefi; Akkus, Ozan

2015-01-01

Collagen solutions are phase-transformed to mechanically robust shell structures with curviplanar topographies using electrochemically induced pH gradients. The process enables rapid layer-by-layer deposition of collagen-rich mixtures over the entire field simultaneously to obtain compositionally diverse multilayered structures. In-plane tensile strength and modulus of the electrocompacted collagen sheet samples were 5200 -fold and 2300 -fold greater than that of uncompacted collagen samples. Out of plane compression tests showed 27 -fold and fold increase in compressive stress and 46 -fold increase in compressive modulus compared to uncompacted collagen sheets. Cells proliferated 4.9 times faster, and cellular area spread was 2.7 times greater on compacted collagen sheets. Electrocompaction also resulted in 2.9 times greater focal adhesion area than on regular collagen hydrogel. The reported improvements in the cell-matrix interactions with electrocompaction would serve to expedite the population of electrocompacted collagen scaffolds by cells. The capacity of the method to fabricate nonlinear curved topographies with compositional heterogeneous layers is demonstrated by sequential deposition of collagenhydroxyapatite layer over a collagen layer. The complex curved topography of the nasal structure is replicated by the electrochemical compaction method. The presented electrochemical compaction process is an enabling modality which holds significant promise for reconstruction of a wide spectrum of topographically complex systems such as joint surfaces, craniofacial defects, ears, nose or urogenital forms. PMID:26069162

Ultrafast electrochemical preparation of graphene/CoS nanosheet counter electrodes for efficient dye-sensitized solar cells

DOE PAGES

Zhu, Chongyang; Zhu, Yimei; Min, Huihua; ...

2015-10-05

Utilizing inexpensive, high-efficiency counter electrodes (CEs) to replace the traditional platinum counterparts in dye-sensitized solar cells (DSSCs) is worthwhile. In this paper, we detail how we synchronously prepared composite CEs of CoS nanosheet arrays and reduced graphene oxide (rGO) layers for the first time via a low temperature, ultrafast one-step electrochemical strategy. With this approach, the whole fabrication process of the composite CEs was only a small percentage of the average time (~15 hours) using other methods. The DSSC assembled with the rGO–CoS composite CE achieved an enhanced power conversion efficiency (PCE) of 8.34%, which is dramatically higher than 6.27%more » of pure CoS CE-based DSSC and even exceeds 7.50% of Pt CE-based DSSC. The outstanding PCE breakthrough is undoubtedly attributed to the enhancement in electrocatalytic ability of the rGO–CoS composite CE due to the incorporation of highly conducting rGO layers and the GO layers-induced growth of CoS nanosheet arrays with higher density and larger surface area. Therefore, lower charge-transfer resistance and higher exchange current density can be achieved as corroborated by the electrochemical impedance spectra (EIS) and Tafel polarization curves (TPCs). As a result, further experiments also proved that the electrochemical strategy exhibited its universality of fabricating other graphene-enhanced chalcogenide functional composite films.« less

Au nanoparticles/hollow molybdenum disulfide microcubes based biosensor for microRNA-21 detection coupled with duplex-specific nuclease and enzyme signal amplification.

PubMed

Shuai, Hong-Lei; Huang, Ke-Jing; Chen, Ying-Xu; Fang, Lin-Xia; Jia, Meng-Pei

2017-03-15

An ultrasensitive electrochemical biosensor for detecting microRNAs is fabricated based on hollow molybdenum disulfide (MoS 2 ) microcubes. Duplex-specific nuclease, enzyme and electrochemical-chemical-chemical redox cycling are used for signal amplification. Hollow MoS 2 microcubes constructed by ultrathin nanosheets are synthesized by a facile template-assisted strategy and used as supporting substrate. For biosensor assembling, biotinylated ssDNA capture probes are first immobilized on Au nanoparticles (AuNPs)/MoS 2 modified electrode in order to combine with streptavidin-conjugated alkaline phosphatase (SA-ALP). When capture probes hybridize with miRNAs, duplex-specific nuclease cleaves the formative duplexes. At the moment, the biotin group strips from the electrode surface and SA-ALP is incapacitated to attach onto electrode. Then, ascorbic acids induce the electrochemical-chemical-chemical redox cycling to produce electrochemical response in the presence of ferrocene methanol and tris (2-carboxyethyl) phosphine. Under optimum conditions, the proposed biosensor shows a good linear relationship between the current variation and logarithm of the microRNAs concentration ranging from 0.1fM to 0.1pM with a detection limit of 0.086fM (S/N=3). Furthermore, the biosensor is successfully applied to detect target miRNA-21 in human serum samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO 2

DOE PAGES

Hod, Idan; Sampson, Matthew D.; Deria, Pravas; ...

2015-09-18

Realization of heterogeneous electrochemical CO 2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal–organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO 2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (~10 15 sites/cm 2). The chemical products of the reduction, obtained withmore » ~100% Faradaic efficiency, are mixtures of CO and H 2. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.« less

Electrochemical characterization of gelatinized starch dispersions: voltammetry and electrochemical impedance spectroscopy on platinum surface.

PubMed

Hernandez-Jaimes, C; Lobato-Calleros, C; Sosa, E; Bello-Pérez, L A; Vernon-Carter, E J; Alvarez-Ramirez, J

2015-06-25

The electrochemical properties of gelatinized starch dispersions (GSD; 5% w/w) from different botanical sources were studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests over a platinum surface. The phenomenological modelling of EIS data using equivalent circuits indicated that after gelatinization the electrical resistance was determined mainly by the resistance of insoluble material (i.e., ghosts). Sonication of the GSD disrupted the ghost microstructure, and produced an increase in electrical conductivity by reducing the resistance of the insoluble material. The CV data showed three oxidation peaks at potentials where glucose solutions displayed oxidation waves. It is postulated that hydrolysis at the bulk and electrocatalyzed oxidation on the Pt-surface are reactions involved in the starch transformation. Starches peak intensity increased with the amylose content, suggesting that the amylose-rich matrix played an important role in the charge transfer in the electrolytic system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Self-heating–induced healing of lithium dendrites

NASA Astrophysics Data System (ADS)

Li, Lu; Basu, Swastik; Wang, Yiping; Chen, Zhizhong; Hundekar, Prateek; Wang, Baiwei; Shi, Jian; Shi, Yunfeng; Narayanan, Shankar; Koratkar, Nikhil

2018-03-01

Lithium (Li) metal electrodes are not deployable in rechargeable batteries because electrochemical plating and stripping invariably leads to growth of dendrites that reduce coulombic efficiency and eventually short the battery. It is generally accepted that the dendrite problem is exacerbated at high current densities. Here, we report a regime for dendrite evolution in which the reverse is true. In our experiments, we found that when the plating and stripping current density is raised above ~9 milliamperes per square centimeter, there is substantial self-heating of the dendrites, which triggers extensive surface migration of Li. This surface diffusion heals the dendrites and smoothens the Li metal surface. We show that repeated doses of high-current-density healing treatment enables the safe cycling of Li-sulfur batteries with high coulombic efficiency.

Salt-induced square prism Pd microtubes and their ethanol electrocatalysis properties

NASA Astrophysics Data System (ADS)

Jiang, Kunpeng; Ma, Shenghua; Wang, Yinan; Zhang, Ying; Han, Xiaojun

2017-05-01

The synthesis of square prism tubes are always challenging due to their thermo and dynamical instability. We demonstrated a simple method using Pd2+ doped PoPD oligomers as building blocks to assemble into 1D square prism metal-organic microtubes, which consists of cataphracted nanosheets on the surfaces. After high temperature treatment, the microtubes became square prism Pd tubes with a cross section size of 3 μm. The pure Pd microtubes showed excellent catalyzing activity towards the electro oxidation of ethanol. Their electrochemically active surface area is 48.2 m2 g-1, which indicates the square prism Pd tubes have great potential in the field of fuel cell.

Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy

PubMed Central

Huang, Yi-Fan; Kooyman, Patricia J.; Koper, Marc T. M.

2016-01-01

Understanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts. PMID:27514695

Oxide modified air electrode surface for high temperature electrochemical cells

DOEpatents

Singh, Prabhakar; Ruka, Roswell J.

1992-01-01

An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

Electrochemical synthesis of Sm2O3 nanoparticles: Application in conductive polymer composite films for supercapacitors.

PubMed

Mohammad Shiri, Hamid; Ehsani, Ali; Jalali Khales, Mina

2017-11-01

A novel electrosynthetic method was introduced to synthesize of Sm 2 O 3 nanoparticles and furthermore, for improving the electrochemical performance of conductive polymer, hybrid POAP/Sm 2 O 3 films have then been fabricated by POAP electropolymerization in the presence of Sm 2 O 3 nanoparticles as active electrodes for electrochemical supercapacitors. The structure, morphology, chemical composition of Sm 2 O 3 nanoparticles was examined. Surface and electrochemical analyses have been used for characterization of Sm 2 O 3 and POAP/Sm 2 O 3 composite films. Different electrochemical methods including galvanostatic charge discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy have been applied to study the system performance. The supercapacity behavior of the composite film was attributed to the (i) high active surface area of the composite, (ii) charge transfer along the polymer chain due to the conjugation form of the polymer and finally (iii) synergism effect between conductive polymer and Sm 2 O 3 nanoparticles. Copyright © 2017 Elsevier Inc. All rights reserved.

Preparation, Modification, Characterization, and Biosensing Application of Nanoporous Gold Using Electrochemical Techniques

PubMed Central

Neupane, Dharmendra; Nepal, Bishal; Mikhaylov, Vasilii; Stine, Keith J.

2018-01-01

Nanoporous gold (np-Au), because of its high surface area-to-volume ratio, excellent conductivity, chemical inertness, physical stability, biocompatibility, easily tunable pores, and plasmonic properties, has attracted much interested in the field of nanotechnology. It has promising applications in the fields of catalysis, bio/chemical sensing, drug delivery, biomolecules separation and purification, fuel cell development, surface-chemistry-driven actuation, and supercapacitor design. Many chemical and electrochemical procedures are known for the preparation of np-Au. Recently, researchers are focusing on easier and controlled ways to tune the pores and ligaments size of np-Au for its use in different applications. Electrochemical methods have good control over fine-tuning pore and ligament sizes. The np-Au electrodes that are prepared using electrochemical techniques are robust and are easier to handle for their use in electrochemical biosensing. Here, we review different electrochemical strategies for the preparation, post-modification, and characterization of np-Au along with the synergistic use of both electrochemistry and np-Au for applications in biosensing. PMID:29547580

Preparation, Modification, Characterization, and Biosensing Application of Nanoporous Gold Using Electrochemical Techniques.

PubMed

Bhattarai, Jay K; Neupane, Dharmendra; Nepal, Bishal; Mikhaylov, Vasilii; Demchenko, Alexei V; Stine, Keith J

2018-03-16

Nanoporous gold (np-Au), because of its high surface area-to-volume ratio, excellent conductivity, chemical inertness, physical stability, biocompatibility, easily tunable pores, and plasmonic properties, has attracted much interested in the field of nanotechnology. It has promising applications in the fields of catalysis, bio/chemical sensing, drug delivery, biomolecules separation and purification, fuel cell development, surface-chemistry-driven actuation, and supercapacitor design. Many chemical and electrochemical procedures are known for the preparation of np-Au. Recently, researchers are focusing on easier and controlled ways to tune the pores and ligaments size of np-Au for its use in different applications. Electrochemical methods have good control over fine-tuning pore and ligament sizes. The np-Au electrodes that are prepared using electrochemical techniques are robust and are easier to handle for their use in electrochemical biosensing. Here, we review different electrochemical strategies for the preparation, post-modification, and characterization of np-Au along with the synergistic use of both electrochemistry and np-Au for applications in biosensing.

A single-electrode electrochemical system for multiplex electrochemiluminescence analysis based on a resistance induced potential difference.

PubMed

Gao, Wenyue; Muzyka, Kateryna; Ma, Xiangui; Lou, Baohua; Xu, Guobao

2018-04-28

Developing low-cost and simple electrochemical systems is becoming increasingly important but still challenged for multiplex experiments. Here we report a single-electrode electrochemical system (SEES) using only one electrode not only for a single experiment but also for multiplex experiments based on a resistance induced potential difference. SEESs for a single experiment and multiplex experiments are fabricated by attaching a self-adhesive label with a hole and multiple holes onto an ITO electrode, respectively. This enables multiplex electrochemiluminescence analysis with high sensitivity at a very low safe voltage using a smartphone as a detector. For the multiplex analysis, the SEES using a single electrode is much simpler, cheaper and more user-friendly than conventional electrochemical systems and bipolar electrochemical systems using electrode arrays. Moreover, SEESs are free from the electrochemiluminescent background problem from driving electrodes in bipolar electrochemical systems. Since numerous electrodes and cover materials can be used to fabricate SEESs readily and electrochemistry is being extensively used, SEESs are very promising for broad applications, such as drug screening and high throughput analysis.

Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

DOE PAGES

Park, Joong Sun; An, Jihwan; Lee, Min Hwan; ...

2015-11-01

In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created withmore » yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.« less

Label-free signal-on aptasensor for sensitive electrochemical detection of arsenite.

PubMed

Cui, Lin; Wu, Jie; Ju, Huangxian

2016-05-15

A signal-on aptasensor was fabricated for highly sensitive and selective electrochemical detection of arsenite with a label-free Ars-3 aptamer self-assembled on a screen-printed carbon electrode (SPCE) via Au-S bond. The Ars-3 aptamer could adsorb cationic polydiallyldimethylammonium (PDDA) via electrostatic interaction to repel other cationic species. In the presence of arsenite, the change of Ars-3 conformation due to the formation of Ars-3/arsenite complex led to less adsorption of PDDA, and the complex could adsorb more positively charged [Ru(NH3)6](3+) as an electrochemically active indicator on the aptasensor surface, which produced a sensitive "turn-on" response. The target-induced structure switching could be used for sensitive detection of arsenite with a linear range from 0.2 nM to 100 nM and a detection limit down to 0.15 nM. Benefiting from Ars-3 aptamer, the proposed system exhibited excellent specificity against other heavy metal ions. The SPCE-based aptasensor exhibited the advantages of low cost and simple fabrication, providing potential application of arsenite detection in environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of Molecular Crowding on the Response of an Electrochemical DNA Sensor

PubMed Central

Ricci, Francesco; Lai, Rebecca Y.; Heeger, Alan J.; Plaxco, Kevin W.; Sumner, James J.

2009-01-01

E-DNA sensors, the electrochemical equivalent of molecular beacons, appear to be a promising means of detecting oligonucleotides. E-DNA sensors are comprised of a redox-modified (here, methylene blue or ferrocene) DNA stem-loop covalently attached to an interrogating electrode. Because E-DNA signaling arises due to binding-induced changes in the conformation of the stem-loop probe, it is likely sensitive to the nature of the molecular packing on the electrode surface. Here we detail the effects of probe density, target length, and other aspects of molecular crowding on the signaling properties, specificity, and response time of a model E-DNA sensor. We find that the highest signal suppression is obtained at the highest probe densities investigated, and that greater suppression is observed with longer and bulkier targets. In contrast, sensor equilibration time slows monotonically with increasing probe density, and the specificity of hybridization is not significantly affected. In addition to providing insight into the optimization of electrochemical DNA sensors, these results suggest that E-DNA signaling arises due to hybridization-linked changes in the rate, and thus efficiency, with which the redox moiety collides with the electrode and transfers electrons. PMID:17488132

Electrochemical Biosensors - Sensor Principles and Architectures

PubMed Central

Grieshaber, Dorothee; MacKenzie, Robert; Vörös, Janos; Reimhult, Erik

2008-01-01

Quantification of biological or biochemical processes are of utmost importance for medical, biological and biotechnological applications. However, converting the biological information to an easily processed electronic signal is challenging due to the complexity of connecting an electronic device directly to a biological environment. Electrochemical biosensors provide an attractive means to analyze the content of a biological sample due to the direct conversion of a biological event to an electronic signal. Over the past decades several sensing concepts and related devices have been developed. In this review, the most common traditional techniques, such as cyclic voltammetry, chronoamperometry, chronopotentiometry, impedance spectroscopy, and various field-effect transistor based methods are presented along with selected promising novel approaches, such as nanowire or magnetic nanoparticle-based biosensing. Additional measurement techniques, which have been shown useful in combination with electrochemical detection, are also summarized, such as the electrochemical versions of surface plasmon resonance, optical waveguide lightmode spectroscopy, ellipsometry, quartz crystal microbalance, and scanning probe microscopy. The signal transduction and the general performance of electrochemical sensors are often determined by the surface architectures that connect the sensing element to the biological sample at the nanometer scale. The most common surface modification techniques, the various electrochemical transduction mechanisms, and the choice of the recognition receptor molecules all influence the ultimate sensitivity of the sensor. New nanotechnology-based approaches, such as the use of engineered ion-channels in lipid bilayers, the encapsulation of enzymes into vesicles, polymersomes, or polyelectrolyte capsules provide additional possibilities for signal amplification. In particular, this review highlights the importance of the precise control over the delicate interplay between surface nano-architectures, surface functionalization and the chosen sensor transducer principle, as well as the usefulness of complementary characterization tools to interpret and to optimize the sensor response. PMID:27879772

Imaging of biological macromolecules on mica in humid air by scanning electrochemical microscopy

PubMed Central

Fan, Fu-Ren F.; Bard, Allen J.

1999-01-01

Imaging of DNA, keyhole limpet hemocyanin, mouse monoclonal IgG, and glucose oxidase on a mica substrate has been accomplished by scanning electrochemical microscopy with a tungsten tip. The technique requires the use of a high relative humidity to form a thin film of water on the mica surface that allows electrochemical reactions to take place at the tip and produce a faradaic current (≈1 pA) that can be used to control tip position. The effect of relative humidity and surface pretreatment with buffer solutions on the ionic conductivity of a mica surface was investigated to find appropriate conditions for imaging. Resolution of the order of 1 nm was obtained. PMID:10588687

Investigation of the electrochemically active surface area and lithium diffusion in graphite anodes by a novel OsO4 staining method

NASA Astrophysics Data System (ADS)

Pfaffmann, Lukas; Birkenmaier, Claudia; Müller, Marcus; Bauer, Werner; Mitsch, Tim; Feinauer, Julian; Krämer, Yvonne; Scheiba, Frieder; Hintennach, Andreas; Schleid, Thomas; Schmidt, Volker; Ehrenberg, Helmut

2016-03-01

Negative electrodes of lithium-ion batteries generally consist of graphite-based active materials. In order to realize batteries with a high current density and therefore accelerated charging processes, the intercalation of lithium and the diffusion processes of these carbonaceous materials must be understood. In this paper, we visualized the electrochemical active surface area for three different anode materials using a novel OsO4 staining method in combination with scanning electron microscopy techniques. The diffusion behavior of these three anode materials is investigated by potentiostatic intermittent titration technique measurements. From those we determine the diffusion coefficient with and without consideration of the electrochemical active surface area.

Enhanced lithium storage performance of hierarchical CuO nanomaterials with surface fractal characteristics

NASA Astrophysics Data System (ADS)

Li, Ang; He, Renyue; Bian, Zhuo; Song, Huaihe; Chen, Xiaohong; Zhou, Jisheng

2018-06-01

Self-assembled hierarchical CuO nanostructures with fractal structures were prepared by a mild method and exhibited excellent lithium storage properties, certain of which even demonstrated a high reversible capacity of 827 mAh g-1 at a rate of 0.1 C. An interesting phenomenon was observed that the electrochemical performance varies along with the structure complexity, and the products with higher surface factal dimensions exhibited larger capability and better cyclability. Structural and electrochemical analysis methods were used to explore the lithiation kinetics of the samples and the reasons for the outstanding electrochemical performances related to the complexities of hierarchical nanostructures and the irregularities of surface and mass distribution.

The effects of printing orientation on the electrochemical behaviour of 3D printed acrylonitrile butadiene styrene (ABS)/carbon black electrodes.

PubMed

Bin Hamzah, Hairul Hisham; Keattch, Oliver; Covill, Derek; Patel, Bhavik Anil

2018-06-14

Additive manufacturing also known as 3D printing is being utilised in electrochemistry to reproducibly develop complex geometries with conductive properties. In this study, we explored if the electrochemical behavior of 3D printed acrylonitrile butadiene styrene (ABS)/carbon black electrodes was influenced by printing direction. The electrodes were printed in both horizontal and vertical directions. The horizsontal direction resulted in a smooth surface (HPSS electrode) and a comparatively rougher surface (HPRS electrode) surface. Electrodes were characterized using cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry. For various redox couples, the vertical printed (VP) electrode showed enhanced current response when compared the two electrode surfaces generated by horizontal print direction. No differences in the capacitive response was observed, indicating that the conductive surface area of all types of electrodes were identical. The VP electrode had reduced charge transfer resistance and uncompensated solution resistance when compared to the HPSS and HPRS electrodes. Overall, electrodes printed in a vertical direction provide enhanced electrochemical performance and our study indicates that print orientation is a key factor that can be used to enhance sensor performance.

Corrosion of Mg alloy AZ91D in the presence of living cells.

PubMed

Seuss, F; Seuss, S; Turhan, M C; Fabry, B; Virtanen, S

2011-11-01

Mg and Mg alloys are of interest for biodegradable implants as they readily corrode in biological fluids, and dissolved Mg ions are nontoxic. Even though it is well known that Mg dissolution leads to pH increase in the surroundings, the effect of the corrosion-induced alkalization on the biological environment has not been studied in detail. We therefore explored the interactions between corrosion-induced pH increase and cell growth on Mg alloy AZ91D surface. Cell adhesion and spreading on the alloy surface is unimpeded initially. However, with time a large fraction of cells de-adhere. We attribute this to the observed increase of the pH in the cell culture medium in the process of alloy dissolution. Cytotoxicity tests with HeLa cells grown on glass surfaces confirm that cell death increases with increasing alkalinity of the cell culture medium. We also show that a the cells that adhere on the Mg alloy surface act as a corrosion-blocking surface layer. In consequence, a slower pH increase in the medium takes place when the alloy surface is covered with cells. Electrochemical impedance spectroscopy measurements (EIS) verify that a cell layer slows down the corrosion process. 2011 Wiley Periodicals, Inc.

Cold pressure welding of aluminium-steel blanks: Manufacturing process and electrochemical surface preparation

NASA Astrophysics Data System (ADS)

Schmidt, Hans Christian; Homberg, Werner; Orive, Alejandro Gonzalez; Grundmeier, Guido; Hordych, Illia; Maier, Hans Jürgen

2018-05-01

In this study the manufacture of aluminium-steel blanks by cold pressure welding and their preparation for a welding process through electrochemical surface treatment are investigated and discussed. The cold pressure welding process was done with an incremental rolling tool that allows for the partial pressure welding of two blanks along a prepared path. The influence of the surface preparation by electrochemical deposition of bond promoting organosilane-based agents and roughening on a nano-scale is investigated and compared to conventional surface treatments. Coating the surfaces with a thin organosilane-based film incorporating specific functional groups should promote additional bonding between the mating oxide layers; its influence on the total weld strength is studied. Pressure welding requires suitable process strategies, and the current advances in the proposed incremental rolling process for the combination of mild steel and aluminium are presented.

Guided evolution of bulk metallic glass nanostructures: A platform for designing three-dimensional electrocatalytic surfaces

DOE PAGES

Doubek, Gustavo; Sekol, Ryan C.; Li, Jinyang; ...

2015-12-22

Precise control over catalyst surface composition and structure is necessary to improve the function of electrochemical systems. To that end, bulk metallic glass (BMG) alloys with atomically dispersed elements provide a highly processable, nanoscale platform for electrocatalysis and surface modification. Here we report on nanostructures of Pt-based BMGs that are modified with various subtractive and additive processes to improve their electrochemical performance.

Surface Modification of the LiFePO4 Cathode for the Aqueous Rechargeable Lithium Ion Battery.

PubMed

Tron, Artur; Jo, Yong Nam; Oh, Si Hyoung; Park, Yeong Don; Mun, Junyoung

2017-04-12

The LiFePO 4 surface is coated with AlF 3 via a simple chemical precipitation for aqueous rechargeable lithium ion batteries (ARLBs). During electrochemical cycling, the unfavorable side reactions between LiFePO 4 and the aqueous electrolyte (1 M Li 2 SO 4 in water) leave a highly resistant passivation film, which causes a deterioration in the electrochemical performance. The coated LiFePO 4 by 1 wt % AlF 3 has a high discharge capacity of 132 mAh g -1 and a highly improved cycle life, which shows 93% capacity retention even after 100 cycles, whereas the pristine LiFePO 4 has a specific capacity of 123 mAh g -1 and a poor capacity retention of 82%. The surface analysis results, which include X-ray photoelectron spectroscopy and transmission electron microscopy results, show that the AlF 3 coating material is highly effective for reducing the detrimental surface passivation by relieving the electrochemical side reactions of the fragile aqueous electrolyte. The AlF 3 coating material has good compatibility with the LiFePO 4 cathode material, which mitigates the surface diffusion obstacles, reduces the charge-transfer resistances and improves the electrochemical performance and surface stability of the LiFePO 4 material in aqueous electrolyte solutions.

Effect of Initial State of Lithium on the Propensity for Dendrite Formation: A Theoretical Study

DOE PAGES

Barai, Pallab; Higa, Kenneth; Srinivasan, Venkat

2016-12-17

Mechanical constraints have been widely used experimentally to prevent the growth of dendrites within lithium metal. The only article known to the authors that tries to theoretically understand how mechanical forces prevent dendrite growth was published by Monroe and Newman [J. Electrochem. Soc., 150 (10) A1377 (2005)]. Based on the assumption that surface tension prevents the growth of interfacial roughness, Monroe and Newman considered pre-stressed conditions of the lithium electrodes. This scenario indicates that prevention of dendrite growth by mechanical means is only possible by using electrolytes with shear modulus at least two times larger than that of lithium metal.more » Here, a different scenario of relaxed lithium metal (without any pre-existing surface stresses) has been considered in the present analysis. Deposition of lithium due to electrochemical reaction at the lithium/electrolyte interface induces compressive stress at the electrode, the electrolyte, and the newly deposited lithium metal. Present simulations indicate that during operation at low current densities, the scenario of relaxed lithium leads to no dendrites. Rather, the present study points to the importance of including the effect of current distribution to accurately capture the mechanical forces needed to prevent dendrite growth.« less

Effect of Initial State of Lithium on the Propensity for Dendrite Formation: A Theoretical Study

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

Barai, Pallab; Higa, Kenneth; Srinivasan, Venkat

Mechanical constraints have been widely used experimentally to prevent the growth of dendrites within lithium metal. The only article known to the authors that tries to theoretically understand how mechanical forces prevent dendrite growth was published by Monroe and Newman [J. Electrochem. Soc., 150 (10) A1377 (2005)]. Based on the assumption that surface tension prevents the growth of interfacial roughness, Monroe and Newman considered pre-stressed conditions of the lithium electrodes. This scenario indicates that prevention of dendrite growth by mechanical means is only possible by using electrolytes with shear modulus at least two times larger than that of lithium metal.more » Here, a different scenario of relaxed lithium metal (without any pre-existing surface stresses) has been considered in the present analysis. Deposition of lithium due to electrochemical reaction at the lithium/electrolyte interface induces compressive stress at the electrode, the electrolyte, and the newly deposited lithium metal. Present simulations indicate that during operation at low current densities, the scenario of relaxed lithium leads to no dendrites. Rather, the present study points to the importance of including the effect of current distribution to accurately capture the mechanical forces needed to prevent dendrite growth.« less

Porous carbon-coated silica macroparticles as anode materials for lithium ion batteries: Effect of boric acid

NASA Astrophysics Data System (ADS)

Kim, Young-Kuk; Moon, Jong-Woo; Lee, Jung-Goo; Baek, Youn-Kyung; Hong, Seong-Hyun

2014-12-01

We report carbon-coated porous silica macroparticles (SiO2@C) prepared using polymeric templates and subsequent carbonization with sucrose for improved electrochemical energy storage in lithium-ion batteries (LIBs). In addition, boron is introduced to improve the stability of electrochemical cells by pyrolyzing mixtures of sucrose and boric acid (SiO2@C + B) under inert atmosphere. The initially large surface area of porous SiO2 (SBET ∼ 658 m2 g-1) is reduced to 102 m2 g-1 after carbonization and introduction of boric acid. Surface of both SiO2@C and SiO2@C + B are covered with amorphous carbon. In particular, SiO2@C + B particles containing borosilicate (Si-O-B) phase and B-O bondings and Si-C-O bondings are also detected from the X-ray photoelectron spectra. The SiO2@C + B macroparticles shows high reversible charge capacity up to 503 mAh g-1 after 103 cycles of Li intercalation/de-intercalation although initial capacity was 200 mAh g-1. The improved charge capacity of SiO2@C + B is attributed to formation of advantageous microstructures induced from boric acid.

Hydrothermally Driven Transformation of Oxygen Functional Groups at Multiwall Carbon Nanotubes for Improved Electrocatalytic Applications.

PubMed

Suryanto, Bryan H R; Chen, Sheng; Duan, Jingjing; Zhao, Chuan

2016-12-28

The role of carbon nanotubes in the advancement of energy conversion and storage technologies is undeniable. In particular, carbon nanotubes have attracted significant applications for electrocatalysis. However, one central issue related to the use of carbon nanotubes is the required oxidative pretreatment that often leads to significant damage of graphitic structures which deteriorates their electrochemical properties. Traditionally, the oxidized carbon nanomaterials are treated at high temperature under an inert atmosphere to repair the oxidation-induced defect sites, which simultaneously removes a significant number of oxygen functional groups. Nevertheless, recent studies have shown that oxygen functional groups on the surface of MWCNT are the essential active centers for a number of important electrocatalytic reactions such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). Herein we first show that hydrothermal treatment as a mild method to improve the electrochemical properties and activities of surface-oxidized MWCNT for OER, HER, and ORR without significantly altering the oxygen content. The results indicate that hydrothermal treatment could potentially repair the defects without significantly reducing the pre-existing oxygen content, which has never been achieved before with conventional high-temperature annealing treatment.

Effects of Nanowire Length and Surface Roughness on the Electrochemical Sensor Properties of Nafion-Free, Vertically Aligned Pt Nanowire Array Electrodes

PubMed Central

Li, Zhiyang; Leung, Calvin; Gao, Fan; Gu, Zhiyong

2015-01-01

In this paper, vertically aligned Pt nanowire arrays (PtNWA) with different lengths and surface roughnesses were fabricated and their electrochemical performance toward hydrogen peroxide (H2O2) detection was studied. The nanowire arrays were synthesized by electroplating Pt in nanopores of anodic aluminum oxide (AAO) template. Different parameters, such as current density and deposition time, were precisely controlled to synthesize nanowires with different surface roughnesses and various lengths from 3 μm to 12 μm. The PtNWA electrodes showed better performance than the conventional electrodes modified by Pt nanowires randomly dispersed on the electrode surface. The results indicate that both the length and surface roughness can affect the sensing performance of vertically aligned Pt nanowire array electrodes. Generally, longer nanowires with rougher surfaces showed better electrochemical sensing performance. The 12 μm rough surface PtNWA presented the largest sensitivity (654 μA·mM−1·cm−2) among all the nanowires studied, and showed a limit of detection of 2.4 μM. The 12 μm rough surface PtNWA electrode also showed good anti-interference property from chemicals that are typically present in the biological samples such as ascorbic, uric acid, citric acid, and glucose. The sensing performance in real samples (river water) was tested and good recovery was observed. These Nafion-free, vertically aligned Pt nanowires with surface roughness control show great promise as versatile electrochemical sensors and biosensors. PMID:26404303

Synthesis and characterization of transition metal oxide/sulfide nanostructures for electrochemical applications

NASA Astrophysics Data System (ADS)

Yilmaz, Gamze

This thesis is essentially oriented to develop low-cost nanostructured transition metal (nickel and vanadium) oxides and sulfides with high energy density, power density and electrochemical stability via strategies of structural design, hybridization, functionalization and surface engineering. Metal oxide and metal oxide/sulfide hybrid nanostructures in several designs, including hierarchical porous nanostructures, hollow polyhedrons, nanocubes, nanoframes, octopod nanoframes, and nanocages, were synthesized to study the contribution of structural design, compositional engineering, functionalization and surface engineering to the electrochemical properties of the materials. Modulated compositional and structural features disclosed the opportunities of large accessible active sites, facile ion transport, robustness and enhanced electrical conductivity. The best electrochemical performance with merits of highest energy density (38.9 Wh kg-1), power density (7.4 kW kg-1) and electrochemical stability (90.9% after 10000 cycles) was obtained for nickel cobalt layered double hydroxide/cobalt sulfide (NiCo-LDH/Co9S8) hybrid hollow polyhedron structure.

Electrochemical Performance Estimation of Anodized AZ31B Magnesium Alloy as Function of Change in the Current Density

NASA Astrophysics Data System (ADS)

Girón, L.; Aperador, W.; Tirado, L.; Franco, F.; Caicedo, J. C.

2017-08-01

The anodized AZ31B magnesium alloys were synthesized via electrodeposition processes. The aim of this work was to determine the electrochemical behavior of magnesium alloys by using anodized alloys as a protective coating. The anodized alloys were characterized by x-ray diffraction, exhibiting the crystallography orientation for Mg and MgO phases. The x-ray photoelectron spectroscopy was used to determine the chemical composition of anodized magnesium alloys. By using electrochemical impedance spectroscopy and Tafel curves, it was possible to estimate the electrochemical behavior of anodized AZ31B magnesium alloys in Hank's balanced salt solution (HBSS). Scanning electron microscopy was performed to analyze chemical changes and morphological surface changes on anodized Mg alloys due to the reaction in HBSS/anodized magnesium surface interface. Electrochemical behavior in HBSS indicates that the coatings may be a promising material for biomedical industry.

Directing Stem Cell Differentiation via Electrochemical Reversible Switching between Nanotubes and Nanotips of Polypyrrole Array.

PubMed

Wei, Yan; Mo, Xiaoju; Zhang, Pengchao; Li, Yingying; Liao, Jingwen; Li, Yongjun; Zhang, Jinxing; Ning, Chengyun; Wang, Shutao; Deng, Xuliang; Jiang, Lei

2017-06-27

Control of stem cell behaviors at solid biointerfaces is critical for stem-cell-based regeneration and generally achieved by engineering chemical composition, topography, and stiffness. However, the influence of dynamic stimuli at the nanoscale from solid biointerfaces on stem cell fate remains unclear. Herein, we show that electrochemical switching of a polypyrrole (Ppy) array between nanotubes and nanotips can alter surface adhesion, which can strongly influence mechanotransduction activation and guide differentiation of mesenchymal stem cells (MSCs). The Ppy array, prepared via template-free electrochemical polymerization, can be reversibly switched between highly adhesive hydrophobic nanotubes and poorly adhesive hydrophilic nanotips through an electrochemical oxidation/reduction process, resulting in dynamic attachment and detachment to MSCs at the nanoscale. Multicyclic attachment/detachment of the Ppy array to MSCs can activate intracellular mechanotransduction and osteogenic differentiation independent of surface stiffness and chemical induction. This smart surface, permitting transduction of nanoscaled dynamic physical inputs into biological outputs, provides an alternative to classical cell culture substrates for regulating stem cell fate commitment. This study represents a general strategy to explore nanoscaled interactions between stem cells and stimuli-responsive surfaces.

Outstanding resistance and passivation behaviour of new Fe-Co metal-metal glassy alloys in alkaline media

PubMed Central

Al-Harbi, Albandaree K.

2018-01-01

The electrochemical behavior of the oxide layers on two metal-metal glassy alloys, Fe78Co9Cr10Mo2Al1 (VX9)and Fe49Co49V2 (VX50) (at.%), were studied using electrochemical techniques including electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) measurements. The morphology and composition of the alloy surfaces were investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion rate and surface roughness of both alloys increased as the concentration of NaOH in aqueous solution was raised. The presence of some protective elements in the composition of the alloys led to the formation of a spontaneous passive layer on the alloy surface. The higher resistance values of both alloys were associated with the magnitude of the dielectric properties of the passive films formed on their surfaces. Both alloys are classified as having outstanding resistance to corrosion, which results from the formation of a passive film that acts as an efficient barrier to corrosion in alkaline solution. PMID:29337992

Outstanding resistance and passivation behaviour of new Fe-Co metal-metal glassy alloys in alkaline media.

PubMed

Emran, Khadijah M; Al-Harbi, Albandaree K

2018-01-01

The electrochemical behavior of the oxide layers on two metal-metal glassy alloys, Fe78Co9Cr10Mo2Al1 (VX9)and Fe49Co49V2 (VX50) (at.%), were studied using electrochemical techniques including electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) measurements. The morphology and composition of the alloy surfaces were investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion rate and surface roughness of both alloys increased as the concentration of NaOH in aqueous solution was raised. The presence of some protective elements in the composition of the alloys led to the formation of a spontaneous passive layer on the alloy surface. The higher resistance values of both alloys were associated with the magnitude of the dielectric properties of the passive films formed on their surfaces. Both alloys are classified as having outstanding resistance to corrosion, which results from the formation of a passive film that acts as an efficient barrier to corrosion in alkaline solution.

Electrochemical oxidation of ampicillin antibiotic at boron-doped diamond electrodes and process optimization using response surface methodology.

PubMed

Körbahti, Bahadır K; Taşyürek, Selin

2015-03-01

Electrochemical oxidation and process optimization of ampicillin antibiotic at boron-doped diamond electrodes (BDD) were investigated in a batch electrochemical reactor. The influence of operating parameters, such as ampicillin concentration, electrolyte concentration, current density, and reaction temperature, on ampicillin removal, COD removal, and energy consumption was analyzed in order to optimize the electrochemical oxidation process under specified cost-driven constraints using response surface methodology. Quadratic models for the responses satisfied the assumptions of the analysis of variance well according to normal probability, studentized residuals, and outlier t residual plots. Residual plots followed a normal distribution, and outlier t values indicated that the approximations of the fitted models to the quadratic response surfaces were very good. Optimum operating conditions were determined at 618 mg/L ampicillin concentration, 3.6 g/L electrolyte concentration, 13.4 mA/cm(2) current density, and 36 °C reaction temperature. Under response surface optimized conditions, ampicillin removal, COD removal, and energy consumption were obtained as 97.1 %, 92.5 %, and 71.7 kWh/kg CODr, respectively.

Nanoparticle shape evolution and proximity effects during tip-induced electrochemical processes

DOE PAGES

Yang, Sangmo; Paranthaman, Mariappan Parans; Noh, Tae Won; ...

2016-01-08

The voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When themore » grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag +/Ag redox reaction to Ag +-ion diffusion with the increase in the applied voltage and pulse duration. Our study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.« less

Reversible superconductor-insulator transition in LiTi2O4 induced by Li-ion electrochemical reaction

PubMed Central

Yoshimatsu, K.; Niwa, M.; Mashiko, H.; Oshima, T.; Ohtomo, A.

2015-01-01

Transition metal oxides display various electronic and magnetic phases such as high-temperature superconductivity. Controlling such exotic properties by applying an external field is one of the biggest continuous challenges in condensed matter physics. Here, we demonstrate clear superconductor-insulator transition of LiTi2O4 films induced by Li-ion electrochemical reaction. A compact electrochemical cell of pseudo-Li-ion battery structure is formed with a superconducting LiTi2O4 film as an anode. Li content in the film is controlled by applying a constant redox voltage. An insulating state is achieved by Li-ion intercalation to the superconducting film by applying reduction potential. In contrast, the superconducting state is reproduced by applying oxidation potential to the Li-ion intercalated film. Moreover, superconducting transition temperature is also recovered after a number of cycles of Li-ion electrochemical reactions. This complete reversible transition originates in difference in potentials required for deintercalation of initially contained and electrochemically intercalated Li+ ions. PMID:26541508

Reversible superconductor-insulator transition in LiTi2O4 induced by Li-ion electrochemical reaction.

PubMed

Yoshimatsu, K; Niwa, M; Mashiko, H; Oshima, T; Ohtomo, A

2015-11-06

Transition metal oxides display various electronic and magnetic phases such as high-temperature superconductivity. Controlling such exotic properties by applying an external field is one of the biggest continuous challenges in condensed matter physics. Here, we demonstrate clear superconductor-insulator transition of LiTi2O4 films induced by Li-ion electrochemical reaction. A compact electrochemical cell of pseudo-Li-ion battery structure is formed with a superconducting LiTi2O4 film as an anode. Li content in the film is controlled by applying a constant redox voltage. An insulating state is achieved by Li-ion intercalation to the superconducting film by applying reduction potential. In contrast, the superconducting state is reproduced by applying oxidation potential to the Li-ion intercalated film. Moreover, superconducting transition temperature is also recovered after a number of cycles of Li-ion electrochemical reactions. This complete reversible transition originates in difference in potentials required for deintercalation of initially contained and electrochemically intercalated Li(+) ions.

Electrochemical Characterization of InP and GaAs Based Structures for Space Solar Cell Applications.

NASA Technical Reports Server (NTRS)

Faur, Maria; Faur, Mircea; Jenkins, Philip P.; Goradia, Manju; Wilt, David M.

1994-01-01

In this paper the emphasis is on accurate majority carrier concentration EC-V profiling of structures based on Indium Phosphide and Gallium Arsenide, using a newly developed electrolyte based on Hydrogen Flouride, Acetic Acid, Phosphoric Acid, 1-phenyl-2-propanamine and Ammonia Diflouride. Some preliminary data on the use of this electrolyte for determining the energy distribution of surface and deep states of these structures, applicable to fabrication process optimization and radiation induced defects studies of solar cells, are also provided.

A novel electrochemical aptasensor based on single-walled carbon nanotubes, gold electrode and complimentary strand of aptamer for ultrasensitive detection of cocaine.

PubMed

Taghdisi, Seyed Mohammad; Danesh, Noor Mohammad; Emrani, Ahmad Sarreshtehdar; Ramezani, Mohammad; Abnous, Khalil

2015-11-15

Cocaine is a strong central nervous system stimulant and one of the most commonly abused drugs. In this study, an electrochemical aptasensor was designed for sensitive and selective detection of cocaine, based on single-walled carbon nanotubes (SWNTs), gold electrode and complimentary strand of aptamer (CS). This electrochemical aptasensor inherits properties of SWNTs and gold such as large surface area and high electrochemical conductivity, as well as high affinity and selectivity of aptamer toward its target and the stronger interaction of SWNTs with single-stranded DNA (ssDNA) than double-stranded DNA (dsDNA). In the absence of cocaine, a little amount of SWNTs bind to Aptamer-CS-modified electrode, so that the electrochemical signal is weak. In the presence of cocaine, aptamer binds to cocaine, leaves the surface of electrode. So that, a large amount of SWNTs bind to CS-modified electrode, generating to a strong electrochemical signal. The designed electrochemical aptasensor showed good selectivity toward cocaine with a limit of detection (LOD) as low as 105 pM. Moreover, the fabricated electrochemical aptasensor was successfully applied to detect cocaine in serum with a LOD as low as 136 pM. Copyright © 2015 Elsevier B.V. All rights reserved.

Degradation of oxygen reduction reaction kinetics in porous La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes due to aging-induced changes in surface chemistry

NASA Astrophysics Data System (ADS)

Baqué, Laura C.; Soldati, Analía L.; Teixeira-Neto, Erico; Troiani, Horacio E.; Schreiber, Anja; Serquis, Adriana C.

2017-01-01

The modification of surface composition after long-term operation is one of the most reported degradation mechanisms of (La,Sr)(Co,Fe)O3-δ (LSCFO) cathodes for Solid Oxide Fuel Cells (SOFCs). Nevertheless, its effect on the oxygen reduction reaction kinetics of porous LSCFO cathodes has not been yet reliably established. In this work, La- and Sr-enrichment at the LSCFO surface of porous cathodes has been induced after 50 h aging at 800 °C under air. Such cation redistribution can extend up to ∼400 nm depth under the LSCFO surface as detected by high resolution Scanning Transmission Electron Microscopy-Energy Dispersive Spectroscopy maps acquired inside the cathode pores. The observed surface chemical changes hamper the oxygen surface exchange reaction at the LSCFO/gas interface. Accordingly, a suitable Electrochemical Impedance Spectroscopy analysis revealed that the oxygen ion conductivity remains practically unaltered during the aging treatment while the oxygen surface exchange resistance increases up to 1.8 times. As a result, the cathode impedance response deteriorates within the 10-0.1 Hz frequency range during the aging treatment, resulting in a total cathode area specific resistance increase of 150%. The methodology adopted has demonstrated to be very valuable for studying the degradation of SOFC cathodes produced by the modification of surface composition.

Effect of La3+ substitution with Gd3+ on the resistive switching properties of La0.7Sr0.3MnO3 thin films

NASA Astrophysics Data System (ADS)

Lee, Hong-Sub; Park, Chang-Sun; Park, Hyung-Ho

2014-05-01

This study demonstrated that the resistive switching voltage of perovskite manganite material could be controlled by A-site cation substitution in "A" MnO3 perovskite manganite structure. A partial substitution of La3+ in La0.7Sr0.3MnO3 with smaller cation Gd3+ induced A-site vacancy of the largest Sr2+ cation with surface segregation of SrOy due to ionic size mismatch, and the induced vacancies reduced migration energy barrier. The operating voltage decreased from 3.5 V to 2.5 V due to a favorable condition for electrochemical migration and redox of oxygen ions. Moreover, surface-segregated SrOy was enhanced with Gd-substitution and the SrOy reduced Schottky-like barrier height and resistive switching ratio from the potential drop and screening effect. The relationship between A-site vacancy generation resulting in surface segregation of SrOy and resistive switching behavior was also investigated by energy resolved x-ray photoelectron spectroscopy, O 1s near edge x-ray absorption spectroscopy, and current voltage measurement.

Passive film growth on titanium alloys: physicochemical and biologic considerations.

PubMed

Eliades, T

1997-01-01

The role of reactive oxygen derivatives (hydroxy peroxide, hydroxyl radical, and singlet oxygen) on the precipitation of inorganic and organic complexes onto the surface of titanium implant alloys is discussed in this review. In addition, the effect of possible implication of several biologic entities surrounding the implant on the implant-tissue interface constituents is described. Evidence from relevant studies suggests that local microenvironmental byproducts and factors associated with the inflammatory response resulting from the implant-induced tissue insult may enhance the expressivity of the inherent, clinically important property of titanium to form oxides. Growth of titanium oxide may be explained through several processes derived from biologic, thermodynamic, and electrochemical approaches. The models proposed to interpret this phenomenon are often contradictory, demonstrating inward or outward from the bulk material passive film growth, with increasing or self-limiting levels of oxide formation as a function of time. However, in vivo observations are consistent with aging-induced thickening of the complexes precipitated on the implant material surface. This review attempts to clarify several critical issues pertaining to passive film formation and kinetics on titanium-alloy surfaces.

Electrodeposition of gold nanoparticles on aryl diazonium monolayer functionalized HOPG surfaces.

PubMed

González, M C R; Orive, A G; Salvarezza, R C; Creus, A H

2016-01-21

Gold nanoparticle electrodeposition on a modified HOPG surface with a monolayer organic film based on aryl diazonium chemistry has been studied. This organic monolayer is electrochemically grown with the use of 2,2-diphenyl-1-picrylhydrazyl (DPPH), a radical scavenger. The electrodeposition of gold on this modified surface is highly favored resulting in an AuNP surface density comparable to that found on glassy carbon. AuNPs grow only in the areas covered by the organic monolayer leaving free clean HOPG zones. A progressive mechanism for the nucleation and growth is followed giving hemispherical AuNPs, homogeneously distributed on the surface and their sizes can be well controlled by the applied electrodeposition potential. By using AFM, C-AFM and electrochemical measurements with the aid of two redox probes, namely Fe(CN)6(4-)/Fe(CN)6(3-) and dopamine, relevant results about the electrochemical modified surface as well as the gold nanoparticles electrodeposited on them are obtained.

Drag reduction using metallic engineered surfaces with highly ordered hierarchical topographies: nanostructures on micro-riblets

NASA Astrophysics Data System (ADS)

Kim, Taekyung; Shin, Ryung; Jung, Myungki; Lee, Jinhyung; Park, Changsu; Kang, Shinill

2016-03-01

Durable drag-reduction surfaces have recently received much attention, due to energy-saving and power-consumption issues associated with harsh environment applications, such as those experienced by piping infrastructure, ships, aviation, underwater vehicles, and high-speed ground vehicles. In this study, a durable, metallic surface with highly ordered hierarchical structures was used to enhance drag-reduction properties, by combining two passive drag-reduction strategies: an air-layer effect induced by nanostructures and secondary vortex generation by micro-riblet structures. The nanostructures and micro-riblet structures were designed to increase slip length. The top-down fabrication method used to form the metallic hierarchical structures combined laser interference lithography, photolithography, thermal reflow, nanoimprinting, and pulse-reverse-current electrochemical deposition. The surfaces were formed from nickel, which has high hardness and corrosion resistance, making it suitable for use in harsh environments. The drag-reduction properties of various metal surfaces were investigated based on the surface structure: a bare surface, a nanostructured surface, a micro-riblet surface, and a hierarchically structured surface of nanostructures on micro-riblets.

Energy efficient synthesis of boranes

DOEpatents

Thorn, David L [Los Alamos, NM; Tumas, William [Los Alamos, NM; Schwarz, Daniel E [Los Alamos, NM; Burrell, Anthony K [Los Alamos, NM

2012-01-24

The reaction of halo-boron compounds (B--X compounds, compounds having one or more boron-halogen bonds) with silanes provides boranes (B--H compounds, compounds having one or more B--H bonds) and halosilanes. Inorganic hydrides, such as surface-bound silane hydrides (Si--H) react with B--X compounds to form B--H compounds and surface-bound halosilanes. The surface bound halosilanes are converted back to surface-bound silanes electrochemically. Halo-boron compounds react with stannanes (tin compounds having a Sn--H bond) to form boranes and halostannanes (tin compounds having a Sn--X bond). The halostannanes are converted back to stannanes electrochemically or by the thermolysis of Sn-formate compounds. When the halo-boron compound is BCl.sub.3, the B--H compound is B.sub.2H.sub.6, and where the reducing potential is provided electrochemically or by the thermolysis of formate.

Energy efficient synthesis of boranes

DOEpatents

Thorn, David L.; Tumas, William; Schwarz, Daniel E.; Burrell, Anthony K.

2010-11-23

The reaction of halo-boron compounds (B--X compounds, compounds having one or more boron-halogen bonds) with silanes provides boranes (B--H compounds, compounds having one or more B--H bonds) and halosilanes. Inorganic hydrides, such as surface-bound silane hydrides (Si--H) react with B--X compounds to form B--H compounds and surface-bound halosilanes. The surface bound halosilanes are converted back to surface-bound silanes electrochemically. Halo-boron compounds react with stannanes (tin compounds having a Sn--H bond) to form boranes and halostannanes (tin compounds having a Sn--X bond). The halostannanes are converted back to stannanes electrochemically or by the thermolysis of Sn-formate compounds. When the halo-boron compound is BCl.sub.3, the B--H compound is B.sub.2H.sub.6, and where the reducing potential is provided electrochemically or by the thermolysis of formate.

Preparation of RuO2-TiO2/Nano-graphite composite anode for electrochemical degradation of ceftriaxone sodium.

PubMed

Li, Dong; Guo, Xiaolei; Song, Haoran; Sun, Tianyi; Wan, Jiafeng

2018-06-05

Graphite-like material is widely used for preparing various electrodes for wastewater treatment. To enhance the electrochemical degradation efficiency of Nano-graphite (Nano-G) anode, RuO 2 -TiO 2 /Nano-G composite anode was prepared through the sol-gel method and hot-press technology. RuO 2 -TiO 2 /Nano-G composite was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and N 2 adsorption-desorption. Results showed that RuO 2 , TiO 2 and Nano-G were composited successfully, and RuO 2 and TiO 2 nanoparticles were distributed uniformly on the surface of Nano-G sheet. Specific surface area of RuO 2 -TiO 2 /Nano-G composite was higher than that of TiO 2 /Nano-G composite and Nano-G. Electrochemical performances of RuO 2 -TiO 2 /Nano-G anode were investigated by cyclic voltammetry, electrochemical impedance spectroscopy. RuO 2 -TiO 2 /Nano-G anode was applied to electrochemical degradation of ceftriaxone. The generation of hydroxyl radical (OH) was measured. Results demonstrated that RuO 2 -TiO 2 /Nano-G anode displayed enhanced electrochemical degradation efficiency towards ceftriaxone and yield of OH, which is derived from the synergetic effect between RuO 2 , TiO 2 and Nano-G, which enhance the specific surface area, improve the electrochemical oxidation activity and lower the charge transfer resistance. Besides, the possible degradation intermediates and pathways of ceftriaxone sodium were identified. This study may provide a viable and promising prospect for RuO 2 -TiO 2 /Nano-G anode towards effective electrochemical degradation of antibiotics from wastewater. Copyright © 2018 Elsevier B.V. All rights reserved.

Degradation of all-vanadium redox flow batteries (VRFB) investigated by electrochemical impedance and X-ray photoelectron spectroscopy: Part 2 electrochemical degradation

NASA Astrophysics Data System (ADS)

Derr, Igor; Bruns, Michael; Langner, Joachim; Fetyan, Abdulmonem; Melke, Julia; Roth, Christina

2016-09-01

Electrochemical degradation (ED) of carbon felt electrodes was investigated by cycling of a flow through all-vanadium redox flow battery (VRFB) and conducting half-cell measurements with two reference electrodes inside the test bench. ED was detected using half-cell and full-cell electrochemical impedance spectroscopy (EIS) at different states of charge (SOC). Reversing the polarity of the battery to recover cell performance was performed with little success. Renewing the electrolyte after a certain amount of cycles restored the capacity of the battery. X-ray photoelectron spectroscopy (XPS) reveals that the amount of surface functional increases by more than a factor of 3 for the negative side as well as for the positive side. Scanning electron microscope (SEM) images show a peeling of the fiber surface after cycling the felts, which leads to a loss of electrochemically active surface area (ECSA). Long term cycling shows that ED has a stronger impact on the negative half-cell [V(II)/V(III)] than the positive half-cell [V(IV)/V(V)] and that the negative half-cell is the rate-determining half-cell for the VRFB.

Porous TiO2-ZrO2 thin film formed by electrochemical technique to improve the biocompatibility of titanium alloy in physiological environment

NASA Astrophysics Data System (ADS)

Benea, L.; Dănăilă, E.; Ponthiaux, P.

2017-02-01

Porous Ti and Ti alloys have received increasing research interest for bone tissue engineering, especially for dental and orthopaedic implants because they provide cell ingrowths and vascularization, improving of adhesion and osseointegration. The tribocorrosion process is encountered in orthopaedic and dentistry applications, since it is known that the implants are often exposed to simultaneous chemical/electrochemical and mechanical stresses. The purpose of this study was to carry out a systematic investigation of the tribo-electrochemical performance of porous TiO2-ZrO2 thin film formed by anodization of Ti-10Zr alloy surface in an artificial saliva solution and to compare the resulted performance with that of the untreated Ti-10Zr alloy surface in order to be applied for biomedical use. The in situ electrochemical technique used for investigation of tribo-electrochemical degradation was the open circuit potential (OCP) measurement performed before, during and after sliding tests. The results presented herein show that controlled anodic oxidation method can significantly improve the tribocorrosion and friction performances of Ti-10Zr alloy surface intended for biomedical applications.

Development of graphene oxide/poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) thin film-based electrochemical surface plasmon resonance immunosensor for detection of human immunoglobulin G

NASA Astrophysics Data System (ADS)

Pothipor, Chammari; Lertvachirapaiboon, Chutiparn; Shinbo, Kazunari; Kato, Keizo; Kaneko, Futao; Ounnunkad, Kontad; Baba, Akira

2018-02-01

An electrochemically synthesized graphene oxide (GO)/poly(3,4-ethylenedioxythiophene) (PEDOT)/poly(styrene sulfonate) (PSS) thin film-based electrochemical surface plasmon resonance (EC-SPR) sensor chip was developed and employed for the detection of human immunoglobulin G (IgG). GO introduced the carboxylic group on the film surface, which also allowed electrochemical control, for the immobilization of the anti-IgG antibody via covalent bonding through amide coupling reaction. The SPR sensitivity of the detection was improved under the control by applying an electrochemical potential, by which the sensitivity was increased by the increment in applied potential. Among the open-circuit and different applied potentials in the range of -1.0 to 0.50 V, the EC-SPR immunosensor at an applied potential of 0.50 V exhibited the highest sensitivity of 6.08 × 10-3 mL µg-1 cm-2 and linearity in the human IgG concentration range of 1.0 to 10 µg mL-1 with a relatively low detection limit of 0.35 µg mL-1. The proposed sensor chip is promising for immunosensing at the physiological level.

Local probing of ionic diffusion by electrochemical strain microscopy: Spatial resolution and signal formation mechanisms

NASA Astrophysics Data System (ADS)

Morozovska, A. N.; Eliseev, E. A.; Balke, N.; Kalinin, S. V.

2010-09-01

Electrochemical insertion-deintercalation reactions are typically associated with significant change in molar volume of the host compound. This strong coupling between ionic currents and strains underpins image formation mechanisms in electrochemical strain microscopy (ESM), and allows exploring the tip-induced electrochemical processes locally. Here we analyze the signal formation mechanism in ESM, and develop the analytical description of operation in frequency and time domains. The ESM spectroscopic modes are compared to classical electrochemical methods including potentiostatic and galvanostatic intermittent titration, and electrochemical impedance spectroscopy. This analysis illustrates the feasibility of spatially resolved studies of Li-ion dynamics on the sub-10-nm level using electromechanical detection.

Influence of artificial biological fluid composition on the biocorrosion of potential orthopedic Mg-Ca, AZ31, AZ91 alloys.

PubMed

Gu, X N; Zheng, Y F; Chen, L J

2009-12-01

The electrochemical behavior of potential orthopedic Mg-Ca, AZ31 and AZ91 alloys was studied in Hank's solution, Dulbecco's Modified Eagle's Medium (DMEM) and serum-containing medium (DMEM adding 10% fetal bovine serum (DMEM+FBS)) over a 7 day immersion period. The biocorrosion of the above three alloys for various immersion time intervals was investigated by linear polarization and electrochemical impedance spectroscopy (EIS). After 7 day immersion, potentiodynamic polarization tests were carried out and the surface morphologies of experimental samples were examined by scanning electron microscopy (SEM) observation complemented by energy-disperse spectrometer (EDS) analysis. It was shown that the corrosion of magnesium alloys was influenced by the composition of the solution. The results indicated that chloride ion could reduce the corrosion resistance and the hydrocarbonate ions could induce rapid surface passivation. The adsorbed amino acid on the experimental magnesium alloys' surface increased their polarization resistance and reduced current densities. The influence of the serum protein on corrosion was found to be associated with the magnesium alloy compositions. A Mg-Ca alloy exhibited an increased corrosion rate in the presence of serum protein. An AZ31 alloy showed an increased corrosion rate in DMEM+FBS in the initial 3 day immersion and the corrosion rate decreased thereafter. An AZ91 alloy, with high Al content, showed a reduced corrosion rate with the addition of FBS into DMEM.

Electrochemical investigations of advanced materials for microelectronic and energy storage devices

NASA Astrophysics Data System (ADS)

Goonetilleke, Pubudu Chaminda

A broad range of electrochemical techniques are employed in this work to study a selected set of advanced materials for applications in microelectronics and energy storage devices. The primary motivation of this study has been to explore the capabilities of certain modern electrochemical techniques in a number of emerging areas of material processing and characterization. The work includes both aqueous and non-aqueous systems, with applications in two rather general areas of technology, namely microelectronics and energy storage. The sub-systems selected for investigation are: (i) Electrochemical mechanical and chemical mechanical planarization (ECMP and CMP, respectively), (ii) Carbon nanotubes in combination with room temperature ionic liquids (ILs), and (iii) Cathode materials for high-performance Li ion batteries. The first group of systems represents an important building block in the fabrication of microelectronic devices. The second and third groups of systems are relevant for new energy storage technologies, and have generated immense interests in recent years. A common feature of these different systems is that they all are associated with complex surface reactions that dictate the performance of the devices based on them. Fundamental understanding of these reactions is crucial to further development and expansion of their associated technologies. It is the complex mechanistic details of these surface reactions that we address using a judicious combination of a number of state of the art electrochemical techniques. The main electrochemical techniques used in this work include: (i) Cyclic voltammetry (CV) and slow scan cyclic voltammetry (SSCV, a special case of CV); (ii) Galvanostatic (or current-controlled) measurements; (iii) Electrochemical impedance spectroscopy (EIS), based on two different methodologies, namely, Fourier transform EIS (FT-EIS, capable of studying fast reaction kinetics in a time-resolved mode), and EIS using frequency response analysis (employed to study slow reactions such as solid state diffusion of Li). The designs of both the experimental equipment and the control variables change for studying the different aqueous and non-aqueous systems. The protocols for data analysis also change depending on the systems. In addition, it often becomes necessary to combine different aspects of the different experimental methods to obtain the necessary information about the system(s) under study. The experimental strategies and the associated theoretical considerations for developing these strategies are discussed in appropriate contexts of this work. CNT electrodes in combination with IL electrolytes are potentially important for electrochemical super-capacitors. We have carried out electrochemical investigation of such a system involving a paper-electrode of multiwall CNT in the IL of 1-Ethyl-3-methyl imidazolium ethylsulfate (EMIM-EtSO4). Our study concentrated on the analytical aspects of cyclic voltammetry (CV) to probe the double layer capacitance of these relatively unconventional systems. (that involve rather large charge-discharge time constants). Both theoretical and experimental aspects of CV for such systems have been discussed, focusing in particular, on the effects of faradaic side-reactions, electrolyte resistance and voltage scan speeds. The results have been analyzed using an electrode equivalent circuit model, demonstrating a method to account for the typical artifacts expected in CV of CNT-IL interfaces. Chemical-mechanical planarization (CMP) of copper has now become an integral part of modern semiconductor fabrication technology. Recently, electrochemical-mechanical planarization (ECMP) has emerged as a possible extension of CMP, where through voltage-activated removal of Cu surface layers, one can substantially minimize the down-force necessary for mechanical polishing However, the detailed electrochemical factors that are central to designing efficient abrasive-free electrolytes for ECMP are not clearly understood at the present time. The present work has addressed this issue by studying the relative electrochemical effects of selected different chemical additives. Controlling the surface reactions (that is controlling the voltage-induced material removal) in ECMP requires a carefully designed combination of a number of electrochemical input variables (voltage activation program and electrolyte composition). We have studied the main experimental factors for designing these parameters, using triangular and rectangular-voltage-pulse modulated dissolution of Cu in electrolytes of different chemical compositions. Applications of rechargeable Li ion batteries have considerably expanded in recent years. As a result, research activities involving material-fabrication and characterization for these batteries also have expanded during this period. The importance of studying these specific materials lies in the fact that the cathode plays a major role in its contribution to the battery performance LiMn2O4 cathodes are being considered for next generation of Li ion batteries. The current work focuses on a specific problem commonly associated with Li cathode systems, namely surface film formation on the cathodes. LiMn2O4 cathodes tend to develop native surface films in carbonate electrolytes. By combining D.C. SSCV with A.C. EIS, we have studied how these films would react with an electrolyte of LiBF4 in ethylene and diethyl carbonates. We have demonstrated that such reactions could affect the measurement of the characteristic electrochemical parameters of the cathode, namely the intercalation capacitance, initial capacity-loss, coulometric titration profiles, and the solid state diffusion coefficient of Li+. A generalized framework for data analysis, based on the considerations of electrode equivalent circuits, has been used to combine the results of the D.C. and A.C. measurements.

Protein electrochemistry using graphene-based nano-assembly: an ultrasensitive electrochemical detection of protein molecules via nanoparticle-electrode collisions.

PubMed

Li, Da; Liu, Jingquan; Barrow, Colin J; Yang, Wenrong

2014-08-04

We describe a new electrochemical detection approach towards single protein molecules (microperoxidase-11, MP-11), which are attached to the surface of graphene nanosheets. The non-covalently functionalized graphene nanosheets exhibit enhanced electroactive surface area, where amplified redox current is produced when graphene nanosheets collide with the electrode.

Effect of electrochemical corrosion on the subsurface microstructure evolution of a CoCrMo alloy in albumin containing environment

NASA Astrophysics Data System (ADS)

Wang, Zhongwei; Yan, Yu; Su, Yanjing; Qiao, Lijie

2017-06-01

The subsurface microstructures of metallic implants play a key role in bio-tribocorrosion. Due to wear or change of local environment, the implant surface can have inhomogeneous electrochemical corrosion properties. In this work, the effect of electrochemical corrosion conditions on the subsurface microstructure evolution of CoCrMo alloys for artificial joints was investigated. Transmission electron microscope (TEM) was employed to observe the subsurface microstructures of worn areas at different applied potentials in a simulated physiological solution. The results showed that applied potentials could affect the severity of the subsurface deformation not only by changing the surface passivation but also affecting the adsorption of protein on the alloy surface.

Electrochemical Oxidation of Resorcinol in Aqueous Medium Using Boron-Doped Diamond Anode: Reaction Kinetics and Process Optimization with Response Surface Methodology

PubMed Central

Körbahti, Bahadır K.; Demirbüken, Pelin

2017-01-01

Electrochemical oxidation of resorcinol in aqueous medium using boron-doped diamond anode (BDD) was investigated in a batch electrochemical reactor in the presence of Na2SO4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100–500 g/L), current density (2–10 mA/cm2), Na2SO4 concentration (0–20 g/L), and reaction temperature (25–45°C) was analyzed on electrochemical oxidation using response surface methodology (RSM). The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm2 current density, 12 g/L Na2SO4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction. PMID:29082225

Sol-gel Technology and Advanced Electrochemical Energy Storage Materials

NASA Technical Reports Server (NTRS)

Chu, Chung-tse; Zheng, Haixing

1996-01-01

Advanced materials play an important role in the development of electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. The sol-gel process is a versatile solution for use in the fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. This processing technique is particularly useful in producing porous materials with high surface area and low density, two of the most desirable characteristics for electrode materials. In addition,the porous surface of gels can be modified chemically to create tailored surface properties, and inorganic/organic micro-composites can be prepared for improved material performance device fabrication. Applications of several sol-gel derived electrode materials in different energy storage devices are illustrated in this paper. V2O5 gels are shown to be a promising cathode material for solid state lithium batteries. Carbon aerogels, amorphous RuO2 gels and sol-gel derived hafnium compounds have been studied as electrode materials for high energy density and high power density electrochemical capacitors.

Fabrication of hollow boron-doped diamond nanostructure via electrochemical corrosion of a tungsten oxide template.

PubMed

Lim, Young-Kyun; Lee, Eung-Seok; Lee, Choong-Hyun; Lim, Dae-Soon

2018-08-10

In the study, a hollow boron-doped diamond (BDD) nanostructure electrode is fabricated to increase the reactive surface area for electrochemical applications. Tungsten oxide nanorods are deposited on the silicon substrate as a template by the hot filament chemical vapor deposition (HFCVD) method. The template is coated with a 100 nm BDD layer deposited by HFCVD to form a core-shell nanostructure. The WO x core is finally electrochemically dissolved to form hollow BDD nanostructure. The fabricated hollow BDD nanostructure electrode is investigated via scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The specific surface areas of the electrodes were analyzed and compared by using Brunauer-Emmett-Teller method. Furthermore, cyclic voltammetry and chronocoulometry are used to investigate the electrochemical characteristics and the reactive surface area of the as-prepared hollow BDD nanostructure electrode. A hollow BDD nanostructure electrode exhibits a reactive area that is 15 times that of a planar BDD thin electrode.

Redox competition mode of scanning electrochemical microscopy (RC-SECM) for visualisation of local catalytic activity.

PubMed

Eckhard, Kathrin; Chen, Xingxing; Turcu, Florin; Schuhmann, Wolfgang

2006-12-07

In order to locally analyse catalytic activity on modified surfaces a transient redox competition mode of scanning electrochemical microscopy (SECM) has been developed. In a bi-potentiostatic experiment the SECM tip competes with the sample for the very same analyte. This leads to a current decrease at the SECM tip, if it is positioned in close proximity to an active catalyst site on the surface. Specifically, local catalytic activity of a Pt-catalyst modified sample with respect to the catalytic reduction of molecular oxygen was investigated. At higher local catalytic activity the local 02 partial pressure within the gap between accurately positioned SECM tip and sample is depleted, leading to a noticeable tip current decrease over active sites. A flexible software module has been implemented into the SECM to adapt the competition conditions by proper definition of tip and sample potentials. A potential pulse profile enables the localised electrochemically induced generation of molecular oxygen prior to the competition detection. The current decay curves are recorded over the entire duration of the applied reduction pulse. Hence, a time resolved processing of the acquired current values provides movies of the local oxygen concentration against x,y-position. The SECM redox competition mode was verified with a macroscopic Pt-disk electrode as a test sample to demonstrate the feasibility of the approach. Moreover, highly dispersed electro-deposited spots of gold and platinum on glassy carbon were visualised using the redox competition mode of SECM. Catalyst spots of different nature as well as activity inhomogeneities within one spot caused by local variations in Pt-loading were visualised successfully.

Fast photo-induced color changes of Ag particles deposited on single-crystalline TiO2 surface

NASA Astrophysics Data System (ADS)

Bai, Y. J.; Liu, W. Z.; Chen, A.; Shi, L.; Liu, X. H.; Zi, J.

2018-05-01

It is well known that surface-plasmon enhanced photo-electrochemical effect or photo-thermal effect of metallic particles on a semiconductor substrate or in a suspension may result in color changes. Such character could be potentially applicable to colorimetric sensors, optical filters, and data storage devices. However, usually the response time for color changes is too long to be practically applied. In this letter, we found that the response rate of color changes could be controlled by the annealing condition of the semiconductor substrate, and changes larger than 10% in spectra were observed after only 1-min exposure to light. Furthermore, such fast response was applied to realize wavelength-dependent "write" and "read" applications with high spatial resolution.

Diamond surface functionalization with biomimicry - Amine surface tether and thiol moiety for electrochemical sensors

NASA Astrophysics Data System (ADS)

Sund, James B.; Causey, Corey P.; Wolter, Scott D.; Parker, Charles B.; Stoner, Brian R.; Toone, Eric J.; Glass, Jeffrey T.

2014-05-01

The surface of conducting diamond was functionalized with a terminal thiol group that is capable of binding and detecting nitrogen-oxygen species. The functionalization process employed multiple steps starting with doped diamond films grown by plasma enhanced chemical vapor deposition followed by hydrogen termination and photochemical attachment of a chemically protected amine alkene. The surface tether was deprotected to reveal the amine functionality, which enabled the tether to be extended with surface chemistry to add a terminal thiol moiety for electrochemical sensing applications. Each step of the process was validated using X-ray photoelectron spectroscopy analysis.

Carbon-Nanotube-Based Electrochemical Double-Layer Capacitor Technologies for Spaceflight Applications

NASA Technical Reports Server (NTRS)

Arepalli, S.; Fireman, H.; Huffman, C.; Maloney, P.; Nikolaev, P.; Yowell, L.; Kim, K.; Kohl, P. A.; Higgins, C. D.; Turano, S. P.

2005-01-01

Electrochemical double-layer capacitors, or supercapacitors, have tremendous potential as high-power energy sources for use in low-weight hybrid systems for space exploration. Electrodes based on single-wall carbon nanotubes (SWCNTs) offer exceptional power and energy performance due to the high surface area, high conductivity, and the ability to functionalize the SWCNTs to optimize capacitor properties. This paper will report on the preparation of electrochemical capacitors incorporating SWCNT electrodes and their performance compared with existing commercial technology. Preliminary results indicate that substantial increases in power and energy density are possible. The effects of nanotube growth and processing methods on electrochemical capacitor performance is also presented. The compatibility of different SWCNTs and electrolytes was studied by varying the type of electrolyte ions that accumulate on the high-surface-area electrodes.

Extrinsic pseudocapacitve Li-ion storage of SnS anode via lithiation-induced structural optimization on cycling

NASA Astrophysics Data System (ADS)

Lian, Qingwang; Zhou, Gang; Liu, Jiatu; Wu, Chen; Wei, Weifeng; Chen, Libao; Li, Chengchao

2017-10-01

Here, we report a new enhanced extrinsic pseudocapacitve Li-ion storage mechanism via lithiation-induced structural optimization strategy. The flower-like C@SnS and bulk SnS exhibit initial capacity decay and subsequent increase of capacity on cycling. After a long-term lithiation/delithiation process, flower-like C@SnS and bulk SnS exhibit improved rate performance and reversible capacity in comparison with those of initial state. Moreover, a high capacity of 530 mAh g-1 is still remained even after 1550 cycles at a high current density of 5.0 A g-1 for flower-like C@SnS after pre-lithiation of 350 cycles. According to the comprehensive analysis of structural evolution and electrochemical performance, it demonstrates that SnS electrodes experience crystal size reduction and further amorphization on cycling, which enhances the reversibility of conversion reaction for SnS, leading to increasing capacity. On the other hand, surface-dominated extrinsic pseudocapacitive contribution results in enhanced rate performance because electrodes expose a large fraction of Li+ sites on surface or near-surface region with structural optimization on cycling. This study reveals that extrinsic pseudocapacitance of SnS can be stimulated via lithiation-induced structural optimization, which gives rise to high-rate and long-lived performances.

DNA microdevice for electrochemical detection of Escherichia coli 0157:H7 molecular markers.

PubMed

Berganza, J; Olabarria, G; García, R; Verdoy, D; Rebollo, A; Arana, S

2007-04-15

An electrochemical DNA sensor based on the hybridization recognition of a single-stranded DNA (ssDNA) probe immobilized onto a gold electrode to its complementary ssDNA is presented. The DNA probe is bound on gold surface electrode by using self-assembled monolayer (SAM) technology. An optimized mixed SAM with a blocking molecule preventing the nonspecific adsorption on the electrode surface has been prepared. In this paper, a DNA biosensor is designed by means of the immobilization of a single stranded DNA probe on an electrochemical transducer surface to recognize specifically Escherichia coli (E. coli) 0157:H7 complementary target DNA sequence via cyclic voltammetry experiments. The 21 mer DNA probe including a C6 alkanethiol group at the 5' phosphate end has been synthesized to form the SAM onto the gold surface through the gold sulfur bond. The goal of this paper has been to design, characterise and optimise an electrochemical DNA sensor. In order to investigate the oligonucleotide probe immobilization and the hybridization detection, experiments with different concentration of DNA and mismatch sequences have been performed. This microdevice has demonstrated the suitability of oligonucleotide Self-assembled monolayers (SAMs) on gold as immobilization method. The DNA probes deposited on gold surface have been functional and able to detect changes in bases sequence in a 21-mer oligonucleotide.

Morphology in electrochemically grown conducting polymer films

DOEpatents

Rubinstein, Israel; Gottesfeld, Shimshon; Sabatani, Eyal

1992-01-01

A conducting polymer film with an improved space filling is formed on a metal electrode surface. A self-assembling monolayer is formed directly on the metal surface where the monolayer has a first functional group that binds to the metal surface and a second chemical group that forms a chemical bonding site for molecules forming the conducting polymer. The conducting polymer is then conventioonally deposited by electrochemical deposition. In one example, a conducting film of polyaniline is formed on a gold electrode surface with an intermediate monolayer of p-aminothiophenol.

Morphology in electrochemically grown conducting polymer films

DOEpatents

Rubinstein, I.; Gottesfeld, S.; Sabatani, E.

1992-04-28

A conducting polymer film with an improved space filling is formed on a metal electrode surface. A self-assembling monolayer is formed directly on the metal surface where the monolayer has a first functional group that binds to the metal surface and a second chemical group that forms a chemical bonding site for molecules forming the conducting polymer. The conducting polymer is then conventionally deposited by electrochemical deposition. In one example, a conducting film of polyaniline is formed on a gold electrode surface with an intermediate monolayer of p-aminothiophenol. 2 figs.

Passivation of Si(111) surfaces with electrochemically grafted thin organic films

NASA Astrophysics Data System (ADS)

Roodenko, K.; Yang, F.; Hunger, R.; Esser, N.; Hinrichs, K.; Rappich, J.

2010-09-01

Ultra thin organic films (about 5 nm thick) of nitrobenzene and 4-methoxydiphenylamine were deposited electrochemically on p-Si(111) surfaces from benzene diazonium compounds. Studies based on atomic force microscopy, infrared spectroscopic ellipsometry and x-ray photoelectron spectroscopy showed that upon exposure to atmospheric conditions the oxidation of the silicon interface proceed slower on organically modified surfaces than on unmodified hydrogen passivated p-Si(111) surfaces. Effects of HF treatment on the oxidized organic/Si interface and on the organic layer itself are discussed.

Development of a Sensitive Electrochemical Enzymatic Reaction-Based Cholesterol Biosensor Using Nano-Sized Carbon Interdigitated Electrodes Decorated with Gold Nanoparticles

PubMed Central

Sharma, Deepti; Lee, Jongmin; Seo, Junyoung; Shin, Heungjoo

2017-01-01

We developed a versatile and highly sensitive biosensor platform. The platform is based on electrochemical-enzymatic redox cycling induced by selective enzyme immobilization on nano-sized carbon interdigitated electrodes (IDEs) decorated with gold nanoparticles (AuNPs). Without resorting to sophisticated nanofabrication technologies, we used batch wafer-level carbon microelectromechanical systems (C-MEMS) processes to fabricate 3D carbon IDEs reproducibly, simply, and cost effectively. In addition, AuNPs were selectively electrodeposited on specific carbon nanoelectrodes; the high surface-to-volume ratio and fast electron transfer ability of AuNPs enhanced the electrochemical signal across these carbon IDEs. Gold nanoparticle characteristics such as size and morphology were reproducibly controlled by modulating the step-potential and time period in the electrodeposition processes. To detect cholesterol selectively using AuNP/carbon IDEs, cholesterol oxidase (ChOx) was selectively immobilized via the electrochemical reduction of the diazonium cation. The sensitivity of the AuNP/carbon IDE-based biosensor was ensured by efficient amplification of the redox mediators, ferricyanide and ferrocyanide, between selectively immobilized enzyme sites and both of the combs of AuNP/carbon IDEs. The presented AuNP/carbon IDE-based cholesterol biosensor exhibited a wide sensing range (0.005–10 mM) and high sensitivity (~993.91 µA mM−1 cm−2; limit of detection (LOD) ~1.28 µM). In addition, the proposed cholesterol biosensor was found to be highly selective for the cholesterol detection. PMID:28914766

The role of stress in self-ordered porous anodic oxide formation and corrosion of aluminum

NASA Astrophysics Data System (ADS)

Capraz, Omer Ozgur

The phenomenon of plastic flow induced by electrochemical reactions near room temperature is significant in porous anodic oxide (PAO) films, charging of lithium batteries and stress-corrosion cracking (SCC). As this phenomenon is poorly understood, fundamental insight into flow from our work may provide useful information for these problems. In-situ monitoring of the stress state allows direct correlation between stress and the current or potential, thus providing fundamental insight into technologically important deformation and failure mechanisms induced by electrochemical reactions. A phase-shifting curvature interferometry was designed to investigate the stress generation mechanisms on different systems. Resolution of our curvature interferometry was found to be ten times more powerful than that obtained by state-of-art multiple deflectometry technique and the curvature interferometry helps to resolve the conflicting reports in the literature. During this work, formation of surface patterns during both aqueous corrosion of aluminum and formation of PAO films were investigated. Interestingly, for both cases, stress induced plastic flow controls the formation of surface patterns. Pore formation mechanisms during anodizing of the porous aluminum oxide films was investigated . PAO films are formed by the electrochemical oxidation of metals such as aluminum and titanium in a solution where oxide is moderately soluble. They have been used extensively to design numerous devices for optical, catalytic, and biological and energy related applications, due to their vertically aligned-geometry, high-specific surface area and tunable geometry by adjusting process variables. These structures have developed empirically, in the absence of understanding the process mechanism. Previous experimental studies of anodizing-induced stress have extensively focused on the measurement of average stress, however the measurement of stress evolution during anodizing does not provide sufficient information to understand the potential stress mechanisms. We developed a new method, which enables us to discriminate the potential stress mechanisms during anodizing and characterize the evolution of the stress profile during film growth. Using stress measurement and characterization techniques, we demonstrated the evolution of the stress profile during the film formation and discussed the role of stress on the PAO film formation. Compressive stress builds up linearly during the anodizing, while barrier oxide film gets thicker until the onset of the pore initiation. Both barrier layer thickness and the integrated oxide stress decreased rapidly to the steady-state period when pore initiation began. The morphology change and stress transients points out the transition from elastic to plastic oxide behavior, similar to those observed in other situations such as lithium intercalation into silicon. The stress profile is consistent with the stress gradient needed to drive plastic flow observed experimentally. We also addressed the dependence of overall stress generation on applied current density. Apparently, stress caused by expansion or contraction of oxide and metal interface depends on the volume change due to overall reactions. In the last chapter, the stress generation during alkaline Al corrosion will be discussed. The enhancement of mechanical degradation by corrosion is the basis for the damage process such as stress-corrosion cracking. Understanding the synergistic effect of stress on stress-corrosion cracking mechanism is necessary to design new materials to improve the safety and viability of existing energy conversion systems. the high-resolution in-situ stress measurements during Al corrosion in alkaline solution was presented, supported by characterization techniques and Fast Fourier Transform analysis. Unprecedented curvature resolution of curvature interferometry permits the monitoring of stress during extended periods of corrosion of thick metal samples. Evolution of concaved-shaped surface patterns is in a great harmony with recorded tensile stress. Furthermore, absolute value of tensile stress onset of the plasticity depends on the dissolution rate of metal and yield stress of metal. The measurements reveal corrosion-induced tensile stress generation, leading to surface plasticity. This finding is evidence that corrosion can directly bring about plasticity, and may be relevant to mechanism of corrosion-induced degradation.

Neural Cell Chip Based Electrochemical Detection of Nanotoxicity

PubMed Central

Kafi, Md. Abdul; Cho, Hyeon-Yeol; Choi, Jeong Woo

2015-01-01

Development of a rapid, sensitive and cost-effective method for toxicity assessment of commonly used nanoparticles is urgently needed for the sustainable development of nanotechnology. A neural cell with high sensitivity and conductivity has become a potential candidate for a cell chip to investigate toxicity of environmental influences. A neural cell immobilized on a conductive surface has become a potential tool for the assessment of nanotoxicity based on electrochemical methods. The effective electrochemical monitoring largely depends on the adequate attachment of a neural cell on the chip surfaces. Recently, establishment of integrin receptor specific ligand molecules arginine-glycine-aspartic acid (RGD) or its several modifications RGD-Multi Armed Peptide terminated with cysteine (RGD-MAP-C), C(RGD)4 ensure farm attachment of neural cell on the electrode surfaces either in their two dimensional (dot) or three dimensional (rod or pillar) like nano-scale arrangement. A three dimensional RGD modified electrode surface has been proven to be more suitable for cell adhesion, proliferation, differentiation as well as electrochemical measurement. This review discusses fabrication as well as electrochemical measurements of neural cell chip with particular emphasis on their use for nanotoxicity assessments sequentially since inception to date. Successful monitoring of quantum dot (QD), graphene oxide (GO) and cosmetic compound toxicity using the newly developed neural cell chip were discussed here as a case study. This review recommended that a neural cell chip established on a nanostructured ligand modified conductive surface can be a potential tool for the toxicity assessments of newly developed nanomaterials prior to their use on biology or biomedical technologies. PMID:28347059

Adsorption of cadmium by activated carbon cloth: influence of surface oxidation and solution pH.

PubMed

Rangel-Mendez, J R; Streat, M

2002-03-01

The surface of activated carbon cloth (ACC), based on polyacrylonitrile fibre as a precursor, was oxidised using nitric acid, ozone and electrochemical oxidation to enhance cadmium ion exchange capacity. Modified adsorbents were physically and chemically characterised by pH titration, direct titration, X-ray photoelectron spectroscopy, elemental analysis, surface area and porosimetry, and scanning electron microscopy. BET surface area decreased after oxidation, however, the total ion exchange capacity increased by a factor of approximately 3.5 compared to the commercial as-received ACC. A very significant increase in cadmium uptake, by a factor of 13, was observed for the electrochemically oxidised ACC. Equilibrium sorption isotherms were determined at pH 4, 5 and 6 and these showed that cadmium uptake increased with increasing pH. There was clear evidence of physical damage to ozone-oxidised fibre, however, acid and electrochemically oxidised samples were completely stable.

A novel phenomenological multi-physics model of Li-ion battery cells

NASA Astrophysics Data System (ADS)

Oh, Ki-Yong; Samad, Nassim A.; Kim, Youngki; Siegel, Jason B.; Stefanopoulou, Anna G.; Epureanu, Bogdan I.

2016-09-01

A novel phenomenological multi-physics model of Lithium-ion battery cells is developed for control and state estimation purposes. The model can capture electrical, thermal, and mechanical behaviors of battery cells under constrained conditions, e.g., battery pack conditions. Specifically, the proposed model predicts the core and surface temperatures and reaction force induced from the volume change of battery cells because of electrochemically- and thermally-induced swelling. Moreover, the model incorporates the influences of changes in preload and ambient temperature on the force considering severe environmental conditions electrified vehicles face. Intensive experimental validation demonstrates that the proposed multi-physics model accurately predicts the surface temperature and reaction force for a wide operational range of preload and ambient temperature. This high fidelity model can be useful for more accurate and robust state of charge estimation considering the complex dynamic behaviors of the battery cell. Furthermore, the inherent simplicity of the mechanical measurements offers distinct advantages to improve the existing power and thermal management strategies for battery management.

Insights into the Surface Reactivity of Cermet and Perovskite Electrodes in Oxidizing, Reducing, and Humid Environments.

PubMed

Paloukis, Fotios; Papazisi, Kalliopi M; Dintzer, Thierry; Papaefthimiou, Vasiliki; Saveleva, Viktoriia A; Balomenou, Stella P; Tsiplakides, Dimitrios; Bournel, Fabrice; Gallet, Jean-Jacques; Zafeiratos, Spyridon

2017-08-02

Understanding the surface chemistry of electrode materials under gas environments is important in order to control their performance during electrochemical and catalytic applications. This work compares the surface reactivity of Ni/YSZ and La 0.75 Sr 0.25 Cr 0.9 Fe 0.1 O 3 , which are commonly used types of electrodes in solid oxide electrochemical devices. In situ synchrotron-based near-ambient pressure photoemission and absorption spectroscopy experiments, assisted by theoretical spectral simulations and combined with microscopy and electrochemical measurements, are used to monitor the effect of the gas atmosphere on the chemical state, the morphology, and the electrical conductivity of the electrodes. It is shown that the surface of both electrode types readjusts fast to the reactive gas atmosphere and their surface composition is notably modified. In the case of Ni/YSZ, this is followed by evident changes in the oxidation state of nickel, while for La 0.75 Sr 0.25 Cr 0.9 Fe 0.1 O 3 , a fine adjustment of the Cr valence and strong Sr segregation is observed. An important difference between the two electrodes is their capacity to maintain adsorbed hydroxyl groups on their surface, which is expected to be critical for the electrocatalytic properties of the materials. The insight gained from the surface analysis may serve as a paradigm for understanding the effect of the gas environment on the electrochemical performance and the electrical conductivity of the electrodes.

Electrochemical Approach for Effective Antifouling and Antimicrobial Surfaces.

PubMed

Gaw, Sheng Long; Sarkar, Sujoy; Nir, Sivan; Schnell, Yafit; Mandler, Daniel; Xu, Zhichuan J; Lee, Pooi See; Reches, Meital

2017-08-09

Biofouling, the adsorption of organisms to a surface, is a major problem today in many areas of our lives. This includes: (i) health, as biofouling on medical device leads to hospital-acquired infections, (ii) water, since the accumulation of organisms on membranes and pipes in desalination systems harms the function of the system, and (iii) energy, due to the heavy load of the organic layer that accumulates on marine vessels and causes a larger consumption of fuel. This paper presents an effective electrochemical approach for generating antifouling and antimicrobial surfaces. Distinct from previously reported antifouling or antimicrobial electrochemical studies, we demonstrate the formation of a hydrogen gas bubble layer through the application of a low-voltage square-waveform pulses to the conductive surface. This electrochemically generated gas bubble layer serves as a separation barrier between the surroundings and the target surface where the adhesion of bacteria can be deterred. Our results indicate that this barrier could effectively reduce the adsorption of bacteria to the surface by 99.5%. We propose that the antimicrobial mechanism correlates with the fundamental of hydrogen evolution reaction (HER). HER leads to an arid environment that does not allow the existence of live bacteria. In addition, we show that this drought condition kills the preadhered bacteria on the surface due to water stress. This work serves as the basis for the exploration of future self-sustainable antifouling techniques such as incorporating it with photocatalytic and photoelectrochemical reactions.

Renewable-reagent electrochemical sensor

DOEpatents

Wang, Joseph; Olsen, Khris B.

1999-01-01

A new electrochemical probe(s) design allowing for continuous (renewable) reagent delivery. The probe comprises an integrated membrane-sampling/electrochemical sensor that prevents interferences from surface-active materials and greatly extends the linear range. The probe(s) is useful for remote or laboratory-based monitoring in connection with microdialysis sampling and electrochemical measurements of metals and organic compounds that are not readily detected in the absence of reacting with the compound. Also disclosed is a method of using the probe(s).

Method of depositing epitaxial layers on a substrate

DOEpatents

Goyal, Amit

2003-12-30

An epitaxial article and method for forming the same includes a substrate having a textured surface, and an electrochemically deposited substantially single orientation epitaxial layer disposed on and in contact with the textured surface. The epitaxial article can include an electromagnetically active layer and an epitaxial buffer layer. The electromagnetically active layer and epitaxial buffer layer can also be deposited electrochemically.

Lithographically defined microporous carbon structures

DOEpatents

Burckel, David Bruce; Washburn, Cody M.; Polsky, Ronen; Brozik, Susan M.; Wheeler, David R.

2013-01-08

A lithographic method is used to fabricate porous carbon structures that can provide electrochemical electrodes having high surface area with uniform and controllable dimensions, providing enormous flexibility to tailor the electrodes toward specific applications. Metal nanoparticles deposited on the surface of the porous carbon electrodes exhibit ultra small dimensions with uniform size distribution. The resulting electrodes are rugged, electrically conductive and show excellent electrochemical behavior.

Electrochemical method for defect delineation in silicon-on-insulator wafers

DOEpatents

Guilinger, Terry R.; Jones, Howland D. T.; Kelly, Michael J.; Medernach, John W.; Stevenson, Joel O.; Tsao, Sylvia S.

1991-01-01

An electrochemical method for defect delineation in thin-film SOI or SOS wafers in which a surface of a silicon wafer is electrically connected so as to control the voltage of the surface within a specified range, the silicon wafer is then contacted with an electrolyte, and, after removing the electrolyte, defects and metal contamination in the silicon wafer are identified.

Improved electrochemical properties of amorphous Mg 65Ni 27La 8 electrodes: Surface modification using graphite

NASA Astrophysics Data System (ADS)

Wu, D. C.; Li, Lu; Liang, G. Y.; Guo, Y. L.; Wu, H. B.

Amorphous Mg 65Ni 27La 8 alloy is prepared by melt-spinning. The alloy surface is modified using different contents of graphite to improve the performances of the Mg 65Ni 27La 8 electrodes. In detail, the electrochemical properties of (Mg 65Ni 27La 8) + xC (x = 0-0.4) electrodes are studied systematically, where x is the mass ratio of graphite to alloy. Experimental results reveal that the discharge capacity, cycle life, discharge potential characteristics and electrochemical kinetics of the electrodes are all improved. The surface modification enhances the electrocatalytic activity of the alloy, reduces the contact resistance of the electrodes and obstructs the formation of Mg(OH) 2 on the alloy surface. An optimal content of graphite has been obtained. The (Mg 65Ni 27La 8) + 0.25 C electrode has the largest discharge capacity of 827 mA h g -1, which is 1.47 times as large as that of the electrode without graphite, and the best electrochemical kinetics. Further increasing of graphite content will lead to the increase of contact resistance and activation energy for charge-transfer reaction of the electrode, resulting in the degradation of electrode performance.

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.

Electrochemical behavior and biological response of Mesenchymal Stem Cells on cp-Ti after N-ions implantation

NASA Astrophysics Data System (ADS)

Rizwan, M.; Ahmad, A.; Deen, K. M.; Haider, W.

2014-11-01

Titanium and its alloys are most widely used as implant materials due to their excellent biocompatibility, mechanical properties and chemical stability. In this study Nitrogen ions of known dosage were implanted over cp-Ti by Pelletron accelerator with beam energy of 0.25 MeV.The atomic force microscopy of bare and nitrogen implanted specimens confirmed increase in surface roughness with increase in nitrogen ions concentration. X-ray diffraction patterns of ions implanted surfaces validated the formation of TiN0.3 and Ti3N2-xnitride phases. The tendency to form passive film and electrochemical behavior of these surfaces in ringer lactate (RL) solution was evaluated by Potentiodynamic polarization and electrochemical impedance spectroscopy respectively. It is proved that nitrogen ions implantation was beneficial to reduce corrosion rate and stabilizing passive film by increasing charge transfer resistance in RL. It was concluded that morphology and proliferation of Mesenchymal Stem Cells on nitrogen ions implanted surfaces strongly depends on surface roughness and nitride phases.

Surface structure and electrochemical characteristics of Ti-V-Cr bcc-type solid solution alloys sintered with Ni

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

Tsuji, Yoichiro; Yamamoto, Osamu; Matsuda, Hiromu

2000-07-01

Ti-V-Cr bcc-type solid solution alloys can absorb a large amount of hydrogen and be applied to active materials of the negative electrode in Ni-MH batteries. However, because of the insolubility of Ni into these alloys, the electrochemical characteristics like discharge capacity and cycle life were poor. In order to increase the discharge capacity of hydrogen absorbing alloy electrodes, Ti-V-Cr bcc-type alloy powders were sintered with Ni in order to form Ni contained surface layer on the alloy surface. As sintering temperature rose up, the surface composition changed from TiNi to Ti{sub 2}Ni. TiNi surface layer showed better electrochemical characteristics. Formore » the Ni adding method, Ni electroless plating was preferred because of good adhesion. As a result of optimized conditions, a discharge capacity of 570 mAh/g and an improvement of cycle life were achieved.« less

Electrochemical machining process for forming surface roughness elements on a gas turbine shroud

DOEpatents

Lee, Ching-Pang; Johnson, Robert Alan; Wei, Bin; Wang, Hsin-Pang

2002-01-01

The back side recessed cooling surface of a shroud defining in part the hot gas path of a turbine is electrochemically machined to provide surface roughness elements and spaces therebetween to increase the heat transfer coefficient. To accomplish this, an electrode with insulating dielectric portions and non-insulating portions is disposed in opposition to the cooling surface. By passing an electrolyte between the cooling surface and electrode and applying an electrical current between the electrode and a shroud, roughness elements and spaces therebetween are formed in the cooling surface in opposition to the insulating and non-insulating portions of the electrode, hence increasing the surface area and heat transfer coefficient of the shroud.

Synthesis of porous NiO/CeO2 hybrid nanoflake arrays as a platform for electrochemical biosensing

NASA Astrophysics Data System (ADS)

Cui, Jiewu; Luo, Jinbao; Peng, Bangguo; Zhang, Xinyi; Zhang, Yong; Wang, Yan; Qin, Yongqiang; Zheng, Hongmei; Shu, Xia; Wu, Yucheng

2015-12-01

Porous NiO/CeO2 hybrid nanoflake arrays fabricated by a facile hydrothermal method were employed as substrates for electrochemical biosensors. The resulting NiO/CeO2 hybrid nanoflake arrays with a large specific surface area and good biocompatibility presented an excellent platform for electrochemical biosensing.Porous NiO/CeO2 hybrid nanoflake arrays fabricated by a facile hydrothermal method were employed as substrates for electrochemical biosensors. The resulting NiO/CeO2 hybrid nanoflake arrays with a large specific surface area and good biocompatibility presented an excellent platform for electrochemical biosensing. Electronic supplementary information (ESI) available: Optical photographs of the as-prepared samples, SEM, TEM, EDS, XRD and BET data of the samples are presented, I-t curves of glucose biosensors based on NiO and NiO/CeO2 NFAs, EIS results of different electrodes. See DOI: 10.1039/c5nr05924k

Electrochemically Active Polyaniline (PANi) Coated Carbon Nanopipes and PANi Nanofibers Containing Composite.

PubMed

Ramana, G Venkata; Kumar, P Sampath; Srikanth, Vadali V S S; Padya, Balaji; Jain, P K

2015-02-01

A composite constituted by carbon nanopipes (CNPs) and polyaniline nanofibers (PANi NFs) is synthesized using in-situ chemical oxidative polymerization. Owing to its electrochemical activity the composite is found to be suitable as a working electrode material in hybrid type supercapacitors. Microstructural and phase analyses of the composite showed that (i) CNP surfaces are coated with PANi and (ii) PANi coated CNPs are distributed among PANi NFs. The composite shows an excellent electrochemical activity and a high specific capacitance of ~224.39 F/g. The electro-chemical activity of the composite is explicated in correlation with crystallinity, intrinsic oxidation state, and doping degree of PANi in the composite. The electro-chemical activity of the composite is also explicated in correlation with BET surface area and ordered meso-porosity pertaining to the composite. Charge/discharge curves indicate that the specific capacitance of the composite is a result of electric double-layer capacitance offered by CNPs and Faradaic pseudo capacitance offered by PANi NFs.

Study of oxide surfaces using time of flight positron annihilation induced Auger electron spectroscopy

NASA Astrophysics Data System (ADS)

Nadesalingam, Manori Prasadika

Transition metal oxides (TMOs) exhibit a rich collection of interesting and intriguing properties which can be used for wide variety of applications. In this dissertation, I will discuss the first PAES measurements on vacuum anneal induced changes in the surface layers of Cu2O/Ta, Cu 2O/TCO and oxidized Cu(100) prepared by spray coated, electrochemically deposition and thermal oxidation techniques respectively. PAES measurements on Cu2O/TCO shows that the a very large increase in the intensity of the Cu (M2,3 VV) Auger peak after annealing at 250°C. Similar but significantly smaller changes were observed in the EAES spectra consistent with the fact that PAES is primarily sensitive to the top-most atomic layer due to the fact that the positrons are trapped just outside the surface prior to annihilation while EAES samples several atomic layers. While PAES measurements on oxidized Cu(100) show a large monotonic increase in the intensity of the annihilation induced Cu (M2,3 VV) Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300°C. The intensity then decreases monotonically as the annealing temperature is increase to ˜500°C. These results provide a clear demonstration of the thermal reduction of the copper oxide surface after annealing at 300°C followed by re-oxidation of the copper surface at the higher annealing temperatures presumably due to the diffusion of subsurface oxygen to the surface.

Rotaxane and catenane host structures for sensing charged guest species.

PubMed

Langton, Matthew J; Beer, Paul D

2014-07-15

CONSPECTUS: The promise of mechanically interlocked architectures, such as rotaxanes and catenanes, as prototypical molecular switches and shuttles for nanotechnological applications, has stimulated an ever increasing interest in their synthesis and function. The elaborate host cavities of interlocked structures, however, can also offer a novel approach toward molecular recognition: this Account describes the use of rotaxane and catenane host systems for binding charged guest species, and for providing sensing capability through an integrated optical or electrochemical reporter group. Particular attention is drawn to the exploitation of the unusual dynamic properties of interlocked molecules, such as guest-induced shuttling or conformational switching, as a sophisticated means of achieving a selective and functional sensor response. We initially survey interlocked host systems capable of sensing cationic guests, before focusing on our accomplishments in synthesizing rotaxanes and catenanes designed for the more challenging task of selective anion sensing. In our group, we have developed the use of discrete anionic templation to prepare mechanically interlocked structures for anion recognition applications. Removal of the anion template reveals an interlocked host system, possessing a unique three-dimensional geometrically restrained binding cavity formed between the interlocked components, which exhibits impressive selectivity toward complementary anionic guest species. By incorporating reporter groups within such systems, we have developed both electrochemical and optical anion sensors which can achieve highly selective sensing of anionic guests. Transition metals, lanthanides, and organic fluorophores integrated within the mechanically bonded structural framework of the receptor are perturbed by the binding of the guest, with a concomitant change in the emission profile. We have also exploited the unique dynamics of interlocked hosts by demonstrating that an anion-induced conformational change can be used as a means of signal transduction. Electrochemical sensing has been realized by integration of the redox-active ferrocene functionality within a range of rotaxane and catenanes; binding of an anion perturbs the metallocene, leading to a cathodic shift in the ferrocene/ferrocenium redox couple. In order to obtain practical sensors for target charged guest species, confinement of receptors at a surface is necessary in order to develop robust, reuseable devices. Surface confinement also offers advantages over solution based receptors, including amplification of signal, enhanced guest binding thermodynamics and the negation of solubility problems. We have fabricated anion-templated rotaxanes and catenanes on gold electrode surfaces and demonstrated that the resulting mechanically bonded self-assembled monolayers are electrochemically responsive to the binding of anions, a crucial first step toward the advancement of sophisticated, highly selective, anion sensory devices. Rotaxane and catenane host molecules may be engineered to offer a superior level of molecular recognition, and the incorporation of optical or electrochemical reporter groups within these interlocked frameworks can allow for guest sensing. Advances in synthetic templation strategies has facilitated the synthesis of interlocked architectures and widened their interest as prototype molecular machines. However, their unique host-guest properties are only now beginning to be exploited as a sophisticated approach to chemical sensing. The development of functional host-guest sensory systems such as these is of great interest to the interdisciplinary field of supramolecular chemistry.

The Sulphur Poisoning Behaviour of Gadolinia Doped Ceria Model Systems in Reducing Atmospheres

PubMed Central

Gerstl, Matthias; Nenning, Andreas; Iskandar, Riza; Rojek-Wöckner, Veronika; Bram, Martin; Hutter, Herbert; Opitz, Alexander Karl

2016-01-01

An array of analytical methods including surface area determination by gas adsorption using the Brunauer, Emmett, Teller (BET) method, combustion analysis, XRD, ToF-SIMS, TEM and impedance spectroscopy has been used to investigate the interaction of gadolinia doped ceria (GDC) with hydrogen sulphide containing reducing atmospheres. It is shown that sulphur is incorporated into the GDC bulk and might lead to phase changes. Additionally, high concentrations of silicon are found on the surface of model composite microelectrodes. Based on these data, a model is proposed to explain the multi-facetted electrochemical degradation behaviour encountered during long term electrochemical measurements. While electrochemical bulk properties of GDC stay largely unaffected, the surface polarisation resistance is dramatically changed, due to silicon segregation and reaction with adsorbed sulphur. PMID:28773771

Static and Dynamic Measurement of Dopamine Adsorption in Carbon Fiber Microelectrodes Using Electrochemical Impedance Spectroscopy.

PubMed

Rivera-Serrano, Nilka; Pagan, Miraida; Colón-Rodríguez, Joanisse; Fuster, Christian; Vélez, Román; Almodovar-Faria, Jose; Jiménez-Rivera, Carlos; Cunci, Lisandro

2018-02-06

In this study, electrochemical impedance spectroscopy was used for the first time to study the adsorption of dopamine in carbon fiber microelectrodes. In order to show a proof-of-concept, static and dynamic measurements were taken at potentials ranging from -0.4 to 0.8 V versus Ag|AgCl to demonstrate the versatility of this technique to study dopamine without the need of its oxidation. We used electrochemical impedance spectroscopy and single frequency electrochemical impedance to measure different concentrations of dopamine as low as 1 nM. Moreover, the capacitance of the microelectrodes surface was found to decrease due to dopamine adsorption, which is dependent on its concentration. The effect of dissolved oxygen and electrochemical oxidation of the surface in the detection of dopamine was also studied. Nonoxidized and oxidized carbon fiber microelectrodes were prepared and characterized by optical microscopy, scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Optimum working parameters of the electrodes, such as frequency and voltage, were obtained for better measurement. Electrochemical impedance of dopamine was determined at different concentration, voltages, and frequencies. Finally, dynamic experiments were conducted using a flow cell and single frequency impedance in order to study continuous and real-time measurements of dopamine.

Electrochemical characterization of bulk and thin film copper in ammonia- and nitric acid-based slurries for chemical mechanical planarization of interconnects

NASA Astrophysics Data System (ADS)

Sainio, Carlyn Anne

Copper will be replacing aluminum as the interconnect material in silicon integrated circuits. Chemical mechanical planarization (CMP) in combination with an inlaid metal interconnection scheme has been utilized to pattern copper interconnects. The thesis describes an attempt to understand the electrochemistry of copper in slurries used for CMP. Steady-state electrochemical potential measurements, linear polarization resistance determinations, and potentiodynamic and potentiostatic polarization scans have been used in order to characterize the mechanism by which copper is removed during CMP. Electrochemical measurements were implemented on a rotating disk assembly to simulate conditions during CMP. Experiments were performed on both bulk copper samples and blanket copper thin films sputter deposited onto silicon wafers. Electrochemical potential measurements have been used in conjunction with potential-pH diagrams to determine the possible copper species which are stable during CMP. Electrochemical results were correlated to CMP experiments to determine slurry compositions with optimum potential-pH ranges for copper planarization. The results indicate that such studies present an opportunity to isolate the electrochemical and chemical effects from the mechanical effects in the CMP of metals and to determine the dependencies of each of these effects on the other. CMP of copper was controlled by the removal of native or non-native surface films. High CMP rates were achieved by matching the rates of film formation and copper and film dissolution. During CMP, surface films are abraded, allowing increased dissolution of copper until the surface film reforms. When the surface was indented by abrasive particles, the corrosion rate of the exposed copper increased by two orders of magnitude. Etchants (i.e. ammonia or nitric acid) were necessary for high CMP rates (120-240 nm/min) and to minimize scratching. CMP rates of copper in 1 volume percent NHsb4OH and 0.7 volume percent HNOsb3 with 0.0016 weight percent KMnOsb4 were comparable. Electrochemical characterization can narrow the possible slurry compositions that may be used for polishing. Also, the possibility of implementing electrochemical techniques to detect the endpoint of polishing was investigated. Although electrochemical measurements in ammonia-based slurries did not indicate when tantalum was exposed, similar measurements may be used to determine when polishing pads should be replaced.

Phase field kinetics of lithium electrodeposits

NASA Astrophysics Data System (ADS)

Ely, David R.; Jana, Aniruddha; García, R. Edwin

2014-12-01

A phase field description is formulated to describe the growth kinetics of an heterogeneously nucleated distribution of lithium electrodeposits. The underlying variational principle includes the bulk electrochemical contributions to the free energy of transformation of the system, the electrolyte-dendrite interfacial energy, and the substrate work of adhesion energetics. Results demonstrate that the rate of electrodeposition at the tip of an isolated dendrite is higher than the rate corresponding to the average overpotential, while the back contact is electrochemically shielded, thus favoring elongated, needle-like shapes. For large populations of electrochemically interacting deposits, two spatially distinct regions of behavior develop: one directly facing the counter-electrode where the local surficial electrodeposition dominates the local kinetics; and a second region, in the vicinity of the substrate-deposit interface, where the electrochemical shielding induced by the tip enables lateral electrochemical lithium exchange dendrite coalescence for small contact angle deposits, and dendrite dewetting and electrodissolution for large contact angle deposits. The underlying physical mechanisms through which some lithium nuclei detach from the depositing substrate, self-induce electrodissolution, while other continue to grow and coalesce are described for different contact angles.

Electrochemical Control of Peptide Self-Organization on Atomically Flat Solid Surfaces: A Case Study with Graphite.

PubMed

Seki, Takakazu; So, Christopher R; Page, Tamon R; Starkebaum, David; Hayamizu, Yuhei; Sarikaya, Mehmet

2018-02-06

The nanoscale self-organization of biomolecules, such as proteins and peptides, on solid surfaces under controlled conditions is an important issue in establishing functional bio/solid soft interfaces for bioassays, biosensors, and biofuel cells. Electrostatic interaction between proteins and surfaces is one of the most essential parameters in the adsorption and self-assembly of proteins on solid surfaces. Although the adsorption of proteins has been studied with respect to the electrochemical surface potential, the self-assembly of proteins or peptides forming well-organized nanostructures templated by lattice structure of the solid surfaces has not been studied in the relation to the surface potential. In this work, we utilize graphite-binding peptides (GrBPs) selected by the phage display method to investigate the relationship between the electrochemical potential of the highly ordered pyrolytic graphite (HOPG) and peptide self-organization forming long-range-ordered structures. Under modulated electrical bias, graphite-binding peptides form various ordered structures, such as well-ordered nanowires, dendritic structures, wavy wires, amorphous (disordered) structures, and islands. A systematic investigation of the correlation between peptide sequence and self-organizational characteristics reveals that the presence of the bias-sensitive amino acid modules in the peptide sequence has a significant effect on not only surface coverage but also on the morphological features of self-assembled structures. Our results show a new method to control peptide self-assembly by means of applied electrochemical bias as well as peptide design-rules for the construction of functional soft bio/solid interfaces that could be integrated in a wide range of practical implementations.

In vitro electrochemical corrosion and cell viability studies on nickel-free stainless steel orthopedic implants.

PubMed

Salahinejad, Erfan; Hadianfard, Mohammad Jafar; Macdonald, Digby Donald; Sharifi-Asl, Samin; Mozafari, Masoud; Walker, Kenneth J; Rad, Armin Tahmasbi; Madihally, Sundararajan V; Tayebi, Lobat

2013-01-01

The corrosion and cell viability behaviors of nanostructured, nickel-free stainless steel implants were studied and compared with AISI 316L. The electrochemical studies were conducted by potentiodynamic polarization and electrochemical impedance spectroscopic measurements in a simulated body fluid. Cytocompatibility was also evaluated by the adhesion behavior of adult human stem cells on the surface of the samples. According to the results, the electrochemical behavior is affected by a compromise among the specimen's structural characteristics, comprising composition, density, and grain size. The cell viability is interpreted by considering the results of the electrochemical impedance spectroscopic experiments.

CO oxidation on stepped-Pt(111) under electrochemical conditions: insights from theory and experiment.

PubMed

Busó-Rogero, C; Herrero, E; Bandlow, J; Comas-Vives, A; Jacob, Timo

2013-11-14

The co-adsorption of CO and OH on two Pt stepped surfaces vicinal to the (111) orientation has been evaluated by means of density functional theory (DFT) calculations. Focusing on Pt(533) and Pt(221), which contain (100) and (111)-steps, respectively, we find that (111)-steps should be more reactive towards CO oxidation than surfaces containing (100)-steps. The DFT results are compared with electrochemical experiments on the CO adsorption and oxidation on these vicinal surfaces.

Electrochemical control of a DNA Holliday Junction nanoswitch by Mg2+ ions.

PubMed

Ferapontova, E E; Mountford, C P; Crain, J; Buck, A H; Dickinson, P; Beattie, J S; Ghazal, P; Terry, J G; Walton, A J; Mount, A R

2008-11-15

The molecular conformation of a synthetic branched, 4-way DNA Holliday junction (HJ) was electrochemically switched between the open and closed (stacked) conformers. Switching was achieved by electrochemically induced quantitative release of Mg(2+) ions from the oxidised poly(N-methylpyrrole) film (PPy), which contained polyacrylate as an immobile counter anion and Mg(2+) ions as charge compensating mobile cations. This increase in the Mg(2+) concentration screened the electrostatic repulsion between the widely separated arms in the open HJ configuration, inducing switching to the closed conformation. Upon electrochemical reduction of PPy, entrapment of Mg(2+) ions back into the PPy film induced the reverse HJ switching from the closed to open state. The conformational transition was monitored using fluorescence resonance energy transfer (FRET) between donor and acceptor dyes each located at the terminus of one of the arms. The demonstrated electrochemical control of the conformation of the used probe-target HJ complex, previously reported as a highly sequence specific nanodevice for detecting of unlabelled target [Buck, A.H., Campbell, C.J., Dickinson, P., Mountford, C.P., Stoquert, H.C., Terry, J.G., Evans, S.A.G., Keane, L., Su, T.J., Mount, A.R., Walton, A.J., Beattie, J.S., Crain, J., Ghazal, P., 2007. Anal. Chem., 79, 4724-4728], allows the development of electronically addressable DNA nanodevices and label-free gene detection assays.

Determination of the Electrochemical Area of Screen-Printed Electrochemical Sensing Platforms.

PubMed

García-Miranda Ferrari, Alejandro; Foster, Christopher W; Kelly, Peter J; Brownson, Dale A C; Banks, Craig E

2018-06-08

Screen-printed electrochemical sensing platforms, due to their scales of economy and high reproducibility, can provide a useful approach to translate laboratory-based electrochemistry into the field. An important factor when utilising screen-printed electrodes (SPEs) is the determination of their real electrochemical surface area, which allows for the benchmarking of these SPEs and is an important parameter in quality control. In this paper, we consider the use of cyclic voltammetry and chronocoulometry to allow for the determination of the real electrochemical area of screen-printed electrochemical sensing platforms, highlighting to experimentalists the various parameters that need to be diligently considered and controlled in order to obtain useful measurements of the real electroactive area.

Detection of radiation-induced changes in electrochemical properties of austenitic stainless steels using miniaturized specimens and the single-loop electrochemical potentiokinetic reactivation method

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

Inazumi, T.; Bell, G.E.C.; Kenik, E.A.

1993-01-01

Single-loop electrochemical potentiokinetic reactivation testing of miniaturized (TEM) specimens can provide reliable data comparable to data obtained with larger specimens. Significant changes in electrochemical properties (increased reactivation current and Flade potential) were detected for PCA and type 316 stainless steels irradiated at 200--420[degrees]C up to 7--9 dpa. Irradiations in the FFTF Materials Open Test Assembly and in the Oak Ridge Research Reactor are reported on. 45 figs., 5 tabs., 52 refs.

Detection of radiation-induced changes in electrochemical properties of austenitic stainless steels using miniaturized specimens and the single-loop electrochemical potentiokinetic reactivation method

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

Inazumi, T.; Bell, G.E.C.; Kenik, E.A.

1993-01-01

Single-loop electrochemical potentiokinetic reactivation testing of miniaturized (TEM) specimens can provide reliable data comparable to data obtained with larger specimens. Significant changes in electrochemical properties (increased reactivation current and Flade potential) were detected for PCA and type 316 stainless steels irradiated at 200--420{degrees}C up to 7--9 dpa. Irradiations in the FFTF Materials Open Test Assembly and in the Oak Ridge Research Reactor are reported on. 45 figs., 5 tabs., 52 refs.

Controllable preparation of a nano-hydroxyapatite coating on carbon fibers by electrochemical deposition and chemical treatment.

PubMed

Wang, Xudong; Zhao, Xueni; Wang, Wanying; Zhang, Jing; Zhang, Li; He, Fuzhen; Yang, Jianjun

2016-06-01

A nano-hydroxyapatite (HA) coating with appropriate thickness and morphology similar to that of human bone tissue was directly prepared onto the surfaces of carbon fibers (CFs). A mixed solution of nitric acid, hydrochloric acid, sulfuric acid, and hydrogen peroxide (NHSH) was used in the preparation process. The coating was fabricated by combining NHSH treatment and electrochemical deposition (ECD). NHSH treatment is easy to operate, produces rapid reaction, and highly effective. This method was first used to induce the nucleation and growth of HA crystals on the CF surfaces. Numerous O-containing functional groups, such as hydroxyl (-OH) and carboxyl (-COOH) groups, were grafted onto the CF surfaces by NHSH treatment (NHSH-CFs); as such, the amounts of these groups on the functionalized CFs increased by nearly 8- and 12-fold, respectively, compared with those on untreated CFs. After treatment, the NHSH-CFs not only acquired larger specific surface areas but retained surfaces free from serious corrosion or breakage. Hence, NHSH-CFs are ideal depositional substrates of HA coating during ECD. ECD was successfully used to prepare a nano-rod-like HA coating on the NHSH-CF surfaces. The elemental composition, structure, and morphology of the HA coating were effectively controlled by adjusting various technological parameters, such as the current density, deposition time, and temperature. The average central diameter of HA crystals and the coating density increased with increasing deposition time. The average central diameter of most HA crystals on the NHSH-CFs varied from approximately 60 nm to 210 nm as the deposition time increased from 60 min to 180 min. Further studies on a possible deposition mechanism revealed that numerous O-containing functional groups on the NHSH-CF surfaces could associate with electrolyte ions (Ca(2+)) to form special chemical bonds. These bonds can induce HA coating deposition and improve the interfacial bonding strength between the HA coating and NHCH-CFs. The results of this study and the proposed preparation of uniform and dense nano-HA coating provide theoretical and practical guidance for future investigations of active HA coatings on fiber materials for medical products and implants. This work also lays the foundation for the wider use of HA-coated CFs/HA composite implants in clinical application. Copyright © 2016 Elsevier B.V. All rights reserved.

Electrochemically enhanced antibody immobilization on polydopamine thin film for sensitive surface plasmon resonance immunoassay.

PubMed

Chen, Daqun; Mei, Yihong; Hu, Weihua; Li, Chang Ming

2018-05-15

For sensitive immunoassay, it is essentially important to immobilize antibody on a surface with high density and full retention of their recognition activity. Bio-inspired polydopamine (PDA) thin film has been widely utilized as a reactive coating to immobilize antibody on various surfaces. We herein report that the antibody immobilization capacity of PDA thin film is electrochemically enhanced by applying an oxidative potential to convert the surface catechol group to reactive quinone group. Quantitative surface plasmon resonance (SPR) investigation unveils that upon proper electrochemical oxidization, the antibody loading capacity of PDA film is significantly improved (up to 27%) and is very close to the theoretically maximal capacity of a planar surface if concentrated antibody solution is used. Using prostate-specific antigen (PSA) as a model target, it is further demonstrated that the SPR immunoassay sensitivity is greatly enhanced due to the improved antibody immobilization. This work offers an efficient strategy to enhance the reactivity of PDA film towards nucleophiles, and may also facilitate its immunoassay application among others. Copyright © 2018 Elsevier B.V. All rights reserved.

Fabrication of solid oxide fuel cell by electrochemical vapor deposition

DOEpatents

Riley, B.; Szreders, B.E.

1988-04-26

In a high temperature solid oxide fuel cell (SOFC), the deposition of an impervious high density thin layer of electrically conductive interconnector material, such as magnesium doped lanthanum chromite, and of an electrolyte material, such as yttria stabilized zirconia, onto a porous support/air electrode substrate surface is carried out at high temperatures (/approximately/1100/degree/ /minus/ 1300/degree/C) by a process of electrochemical vapor deposition. In this process, the mixed chlorides of the specific metals involved react in the gaseous state with water vapor resulting in the deposit of an impervious thin oxide layer on the support tube/air electrode substrate of between 20--50 microns in thickness. An internal heater, such as a heat pipe, is placed within the support tube/air electrode substrate and induces a uniform temperature profile therein so as to afford precise and uniform oxide deposition kinetics in an arrangement which is particularly adapted for large scale, commercial fabrication of SOFCs.

From tunable core-shell nanoparticles to plasmonic drawbridges: Active control of nanoparticle optical properties

PubMed Central

Byers, Chad P.; Zhang, Hui; Swearer, Dayne F.; Yorulmaz, Mustafa; Hoener, Benjamin S.; Huang, Da; Hoggard, Anneli; Chang, Wei-Shun; Mulvaney, Paul; Ringe, Emilie; Halas, Naomi J.; Nordlander, Peter; Link, Stephan; Landes, Christy F.

2015-01-01

The optical properties of metallic nanoparticles are highly sensitive to interparticle distance, giving rise to dramatic but frequently irreversible color changes. By electrochemical modification of individual nanoparticles and nanoparticle pairs, we induced equally dramatic, yet reversible, changes in their optical properties. We achieved plasmon tuning by oxidation-reduction chemistry of Ag-AgCl shells on the surfaces of both individual and strongly coupled Au nanoparticle pairs, resulting in extreme but reversible changes in scattering line shape. We demonstrated reversible formation of the charge transfer plasmon mode by switching between capacitive and conductive electronic coupling mechanisms. Dynamic single-particle spectroelectrochemistry also gave an insight into the reaction kinetics and evolution of the charge transfer plasmon mode in an electrochemically tunable structure. Our study represents a highly useful approach to the precise tuning of the morphology of narrow interparticle gaps and will be of value for controlling and activating a range of properties such as extreme plasmon modulation, nanoscopic plasmon switching, and subnanometer tunable gap applications. PMID:26665175

Pomelo peels-derived porous activated carbon microsheets dual-doped with nitrogen and phosphorus for high performance electrochemical capacitors

NASA Astrophysics Data System (ADS)

Wang, Zhen; Tan, Yongtao; Yang, Yunlong; Zhao, Xiaoning; Liu, Ying; Niu, Lengyuan; Tichnell, Brandon; Kong, Lingbin; Kang, Long; Liu, Zhen; Ran, Fen

2018-02-01

In this work, biomass pomelo peel is used to fabricate the porous activated carbon microsheets, and diammonium hydrogen phosphate (DHP) is employed to dual-dope carbon with nitrogen and phosphorus elements. With the benefit of DHP inducement and dual-doping of nitrogen and phosphorus, the prepared carbon material has a higher carbon yield, and exhibits higher specific surface area (about 807.7 m2/g), and larger pore volume (about 0.4378 cm3/g) with hierarchically structure of interconnected thin microsheets compared to the pristine carbon. The material exhibits not only high specific capacitance (240 F/g at 0.5 A/g), but also superior cycling performance (approximately 100% of capacitance retention after 10,000 cycles at 2 A/g) in 2 M KOH aqueous electrolyte. Furthermore, the assembled symmetric electrochemical capacitor in 1 M Na2SO4 aqueous electrolyte exhibits a high energy density of 11.7 Wh/kg at a power density of 160 W/kg.

Lateral electrochemical etching of III-nitride materials for microfabrication

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

Han, Jung

Conductivity-selective lateral etching of III-nitride materials is described. Methods and structures for making vertical cavity surface emitting lasers with distributed Bragg reflectors via electrochemical etching are described. Layer-selective, lateral electrochemical etching of multi-layer stacks is employed to form semiconductor/air DBR structures adjacent active multiple quantum well regions of the lasers. The electrochemical etching techniques are suitable for high-volume production of lasers and other III-nitride devices, such as lasers, HEMT transistors, power transistors, MEMs structures, and LEDs.

Electrochemical Corrosion of Stainless Steel in Thiosulfate Solutions Relevant to Gold Leaching

NASA Astrophysics Data System (ADS)

Choudhary, Lokesh; Wang, Wei; Alfantazi, Akram

2016-01-01

This study aims to characterize the electrochemical corrosion behavior of stainless steel in the ammoniacal thiosulfate gold leaching solutions. Electrochemical corrosion response was investigated using potentiodynamic polarization and electrochemical impedance spectroscopy, while the semi-conductive properties and the chemical composition of the surface film were characterized using Mott-Schottky analysis and X-ray photoelectron spectroscopy, respectively. The morphology of the corroded specimens was analyzed using scanning electron microscopy. The stainless steel 316L showed no signs of pitting in the ammoniacal thiosulfate solutions.

Renewable-reagent electrochemical sensor

DOEpatents

Wang, J.; Olsen, K.B.

1999-08-24

A new electrochemical probe(s) design allowing for continuous (renewable) reagent delivery is described. The probe comprises an integrated membrane sampling/electrochemical sensor that prevents interferences from surface-active materials and greatly extends the linear range. The probe(s) is useful for remote or laboratory-based monitoring in connection with microdialysis sampling and electrochemical measurements of metals and organic compounds that are not readily detected in the absence of reacting with the compound. Also disclosed is a method of using the probe(s). 19 figs.

Nanoscale visualization of redox activity at lithium-ion battery cathodes.

PubMed

Takahashi, Yasufumi; Kumatani, Akichika; Munakata, Hirokazu; Inomata, Hirotaka; Ito, Komachi; Ino, Kosuke; Shiku, Hitoshi; Unwin, Patrick R; Korchev, Yuri E; Kanamura, Kiyoshi; Matsue, Tomokazu

2014-11-17

Intercalation and deintercalation of lithium ions at electrode surfaces are central to the operation of lithium-ion batteries. Yet, on the most important composite cathode surfaces, this is a rather complex process involving spatially heterogeneous reactions that have proved difficult to resolve with existing techniques. Here we report a scanning electrochemical cell microscope based approach to define a mobile electrochemical cell that is used to quantitatively visualize electrochemical phenomena at the battery cathode material LiFePO4, with resolution of ~100 nm. The technique measures electrode topography and different electrochemical properties simultaneously, and the information can be combined with complementary microscopic techniques to reveal new perspectives on structure and activity. These electrodes exhibit highly spatially heterogeneous electrochemistry at the nanoscale, both within secondary particles and at individual primary nanoparticles, which is highly dependent on the local structure and composition.

Fabrication and characterization of PbO2 electrode modified with [Fe(CN)6](3-) and its application on electrochemical degradation of alkali lignin.

PubMed

Hao, Xu; Quansheng, Yuan; Dan, Shao; Honghui, Yang; Jidong, Liang; Jiangtao, Feng; Wei, Yan

2015-04-09

PbO2 electrode modified by [Fe(CN)6](3-) (marked as FeCN-PbO2) was prepared by electro-deposition method and used for the electrochemical degradation of alkali lignin (AL). The surface morphology and the structure of the electrodes were characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD), respectively. The stability and electrochemical activity of FeCN-PbO2 electrode were characterized by accelerated life test, linear sweep voltammetry, electrochemical impedance spectrum (EIS) and AL degradation. The results showed that [Fe(CN)6](3-) increased the average grain size of PbO2 and formed a compact surface coating. The service lifetime of FeCN-PbO2 electrode was 287.25 h, which was longer than that of the unmodified PbO2 electrode (100.5h). The FeCN-PbO2 electrode showed higher active surface area and higher oxygen evolution potential than that of the unmodified PbO2 electrode. In electrochemical degradation tests, the apparent kinetics coefficient of FeCN-PbO2 electrode was 0.00609 min(-1), which was higher than that of unmodified PbO2 electrode (0.00419 min(-1)). The effects of experimental parameters, such as applied current density, initial AL concentration, initial pH value and solution temperature, on electrochemical degradation of AL by FeCN-PbO2 electrode were evaluated. Copyright © 2015 Elsevier B.V. All rights reserved.

Surface design and engineering of hierarchical hybrid nanostructures for asymmetric supercapacitors with improved electrochemical performance.

PubMed

Achilleos, Demetra S; Hatton, T Alan

2015-06-01

With the current rising world demand for energy sufficiency, there is an increased necessity for the development of efficient energy storage devices. To address these needs, the scientific community has focused on the improvement of the electrochemical properties of the most well known energy storage devices; the Li-ion batteries and electrochemical capacitors, also called supercapacitors. Despite the fact that supercapacitors exhibit high power densities, good reversibility and long cycle life, they still exhibit lower energy densities than batteries, which limit their practical application. Various strategies have been employed to circumvent this problem, specifically targetting an increase in the specific capacitance and the broadening of the potential window of operation of these systems. In recent years, sophisticated surface design and engineering of hierarchical hybrid nanostructures has facilitated significant improvements in the specific and volumetric storage capabilities of supercapacitors. These nanostructured electrodes exhibit higher surface areas for ion adsorption and reduced ion diffusion lengths for the electrolyte ions. Significant advances have also been achieved in broadening the electrochemical window of operation of these systems, as realized via the development of asymmetric two-electrode cells consisting of nanocomposite positive and negative electrodes with complementary electrochemical windows, which operate in environmentally benign aqueous media. We provide an overview of the diverse approaches, in terms of chemistry and nanoscale architecture, employed recently for the development of asymmetric supercapacitors of improved electrochemical performance. Copyright © 2014 Elsevier Inc. All rights reserved.

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

PubMed

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

2015-07-28

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

Enhanced Cyclability of Lithium-Oxygen Batteries with Electrodes Protected by Surface Films Induced via In Situ Electrochemical Process

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

Liu, Bin; Xu, Wu; Tao, Jinhui

Although the rechargeable lithium-oxygen (Li-O2) batteries have extremely high theoretical specific energy, the practical application of these batteries is still limited by the instability of their carbon-based air-electrode, Li metal anode, and electrolytes towards reduced oxygen species. Here we demonstrate a simple one-step in-situ electrochemical pre-charging strategy to generate thin protective films on both carbon nanotubes (CNTs) air-electrode and Li metal anode simultaneously under an inert atmosphere. Li-O2 cells after such pre-treatment demonstrate significantly extended cycle life of 110 and 180 cycles under the capacity-limited protocol of 1000 mAh g-1 and 500 mAh g-1, respectively, which is far more thanmore » those without pre-treatment. The thin-films formed from decomposition of electrolyte during in-situ electrochemical pre-charging process in an inert environment can protect both CNTs air-electrode and Li metal anode prior to conventional Li-O2 discharge/charge cycling where reactive reduced oxygen species are formed. This work provides a new approach for protections of carbon-based air-electrode and Li metal anode in practical Li-O2 batteries, and may also be applied to other battery systems.« less

Phase transition of a cobalt-free perovskite as a high-performance cathode for intermediate-temperature solid oxide fuel cells.

PubMed

Jiang, Shanshan; Zhou, Wei; Niu, Yingjie; Zhu, Zhonghua; Shao, Zongping

2012-10-01

It is generally recognized that the phase transition of a perovskite may be detrimental to the connection between cathode and electrolyte. Moreover, certain phase transitions may induce the formation of poor electronic and ionic conducting phase(s), thereby lowering the electrochemical performance of the cathode. Here, we present a study on the phase transition of a cobalt-free perovskite (SrNb(0.1)Fe(0.9)O(3-δ), SNF) and evaluate its effect on the electrochemical performance of the fuel cell. SNF exists as a primitive perovskite structure with space group P4mm (99) at room temperature. As evidenced by in situ high-temperature X-ray diffraction measurements over the temperature range of 600 to 1000 °C, SNF undergoes a transformation to a tetragonal structure with a space group I4/m (87). This phase transition is accompanied by a moderate change in the volume, allowing a good cathode/electrolyte interface on thermal cycling. According to the electrochemical impedance spectroscopy evaluation, the I4/m phase exhibits positive effects on the cathode's performance, showing the highest oxygen reduction reaction activity of cobalt-free cathodes reported so far. This activity improvement is attributed to enhanced oxygen surface processes. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical studies on nanometal oxide-activated carbon composite electrodes for aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Ho, Mui Yen; Khiew, Poi Sim; Isa, Dino; Chiu, Wee Siong

2014-11-01

In present study, the electrochemical performance of eco-friendly and cost-effective titanium oxide (TiO2)-based and zinc oxide-based nanocomposite electrodes were studied in neutral aqueous Na2SO3 electrolyte, respectively. The electrochemical properties of these composite electrodes were studied using cyclic voltammetry (CV), galvanostatic charge-discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that these two nanocomposite electrodes achieve the highest specific capacitance at fairly low oxide loading onto activated carbon (AC) electrodes, respectively. Considerable enhancement of the electrochemical properties of TiO2/AC and ZnO/AC nanocomposite electrodes is achieved via synergistic effects contributed from the nanostructured metal oxides and the high surface area mesoporous AC. Cations and anions from metal oxides and aqueous electrolyte such as Ti4+, Zn2+, Na+ and SO32- can occupy some pores within the high-surface-area AC electrodes, forming the electric double layer at the electrode-electrolyte interface. Additionally, both TiO2 and ZnO nanoparticles can provide favourable surface adsorption sites for SO32- anions which subsequently facilitate the faradaic processes for pseudocapacitive effect. These two systems provide the low cost material electrodes and the low environmental impact electrolyte which offer the increased charge storage without compromising charge storage kinetics.

Effect of protein adsorption on the corrosion behavior of 70Cu-30Ni alloy in artificial seawater.

PubMed

Torres Bautista, Blanca E; Carvalho, Maria L; Seyeux, Antoine; Zanna, Sandrine; Cristiani, Pierangela; Tribollet, Bernard; Marcus, Philippe; Frateur, Isabelle

2014-06-01

Copper alloys often used in cooling circuits of industrial plants can be affected by biocorrosion induced by biofilm formation. The objective of this work was to study the influence of protein adsorption, which is the first step in biofilm formation, on the electrochemical behavior of 70Cu-30Ni (wt.%) alloy in static artificial seawater and on the chemical composition of oxide layers. For that purpose, electrochemical measurements performed after 1h of immersion were combined to surface analyses. A model is proposed to analyze impedance data. In the presence of bovine serum albumin (BSA, model protein), the anodic charge transfer resistance deduced from EIS data at Ecorr is slightly higher, corresponding to lower corrosion current. Without BSA, two oxidized layers are shown by XPS and ToF-SIMS: an outer layer mainly composed of copper oxide (Cu2O redeposited layer) and an inner layer mainly composed of oxidized nickel, with a global thickness of ~30nm. The presence of BSA leads to a mixed oxide layer (CuO, Cu2O, Ni(OH)2) with a lower thickness (~10nm). Thus, the protein induces a decrease of the dissolution rate at Ecorr and hence a decrease of the amount of redeposited Cu2O and of the oxide layer thickness. © 2013.

Light-Induced Conversion of Chemical Permeability to Enhance Electron and Molecular Transfer in Nanoscale Assemblies

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

Balgley, Renata; de Ruiter, Graham; Evmenenko, Guennadi

In this paper, we demonstrate how photochemically enhancing the permeability of metal–organic assemblies results in a significant enhancement of the electrochemical activity of metal complexes located within the assembly. The molecular assemblies consist of different layers of redox-active metal complexes ([M(mbpy-py)3][PF6]2; M = Ru or Os) that are separated by redox-inactive spacers consisting of 1,4-bis[2-(4-pyridyl)ethenyl]benzene (BPEB) and PdCl2 of variable thicknesses (0–13.4 nm). UV-irradiation (λ = 254 nm) of our assemblies induces a photochemical reaction in the redox-inactive spacer increasing the permeability of the assembly. The observed increase was evident by trapping organic (nBu4NBF4) and inorganic (NiCl2) salts inside themore » assemblies, and by evaluating the electrochemical response of quinones absorbed inside the molecular assemblies before and after UV irradiation. The increase in permeability is reflected by higher currents and a change in the directionality of electron transfer, i.e., from mono- to bidirectional, between the redox-active metal complexes and the electrode surface. The supramolecular structure of the assemblies dominates the overall electron transfer properties and overrules possible electron transfer mediated by the extensive π-conjugation of its individual organic components.« less

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

Stephen W. Feldberg; Lewis, Ernie R.

In this study, the principle of unchanging total concentration as described by Oldham and Feldberg [J. Phys. Chem. B, 103, 1699 (1999)] is invoked to analyze systems comprising a redox pair (X z1 1 and X z2 2) plus one or more non-electroactive species (X z3 3,X z4 4...X zjmax jmax) where X zj j is the j th species with charge z j and concentration; c j. The principle states that if the diffusion coefficients for all species are identical and mass transport is governed by the Nernst-Planck expression, the total concentration does not change during any electrochemical perturbation,more » i.e.: Σ jmax j=1[X zj j]=Σ jmax j=1 c j = S P With this principle we deduce the electrochemically induced difference between the surface and bulk concentrations for each species. Those concentration differences are translated into density differences which are a function of the density of the solvent and of the concentration differences, molecular masses and the standard partial molar volumes of all species. Those density differences in turn can induce convection that will ultimately modify the observed current. However, we did not attempt to quantify details of the natural convection and current modification produced by those density differences.« less

Sulfur redox reactions on nanostructured highly oriented pyrolytic graphite (HOPG) electrodes: Direct evidence for superior electrocatalytic performance on defect sites

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

Wang, Gongwei; Zheng, Dong; Liu, Dan

Fundamental research of sulfur redox reactions on well-defined controlled model electrode surfaces can provide new information to design high-performance lithium-sulfur batteries. In this paper, we study the electrochemical reduction and oxidation of sulfur on the nanostructured HOPG electrodes with pure basal planes, step plans, and pure edge planes. Finally, our results directly indicate that electrochemical reduction and oxidation of sulfur is significantly affected by the carbon surface structure, namely, the electrochemical reversibility of sulfur redox reaction is much better on edge plane, compared with basal plane and step plane.

Sulfur redox reactions on nanostructured highly oriented pyrolytic graphite (HOPG) electrodes: Direct evidence for superior electrocatalytic performance on defect sites

DOE PAGES

Wang, Gongwei; Zheng, Dong; Liu, Dan; ...

2017-04-28

Fundamental research of sulfur redox reactions on well-defined controlled model electrode surfaces can provide new information to design high-performance lithium-sulfur batteries. In this paper, we study the electrochemical reduction and oxidation of sulfur on the nanostructured HOPG electrodes with pure basal planes, step plans, and pure edge planes. Finally, our results directly indicate that electrochemical reduction and oxidation of sulfur is significantly affected by the carbon surface structure, namely, the electrochemical reversibility of sulfur redox reaction is much better on edge plane, compared with basal plane and step plane.

Selective high-resolution electrodeposition on semiconductor defect patterns.

PubMed

Schmuki, P; Erickson, L E

2000-10-02

We report a new principle and technique that allows one to electrodeposit material patterns of arbitrary shape down to the submicrometer scale. We demonstrate that an electrochemical metal deposition reaction can be initiated selectively at surface defects created in a p-type Si(100) substrate by Si (++) focused ion beam bombardment. The key principle is that, for cathodic electrochemical polarization of p-type material in the dark, breakdown of the blocking Schottky barrier at the semiconductor/electrolyte interface occurs at significantly lower voltages at implanted locations than for an unimplanted surface. This difference in the threshold voltages is exploited to achieve selective electrochemical deposition.

Planar fuel cell utilizing nail current collectors for increased active surface area

DOEpatents

George, Thomas J.; Meacham, G. B. Kirby

2002-03-26

A plurality of nail current collector members are useful in the gas flow passages of an electrochemical device to optimize the active surfaces of the device and to provide structural support. In addition, the thicknesses of cathode and anode layers within the electrochemical device are varied according to current flow through the device to reduce resistance and increase operating efficiency.

Electrochemical polishing of thread fastener test specimens of nickel-chromium iron alloys

DOEpatents

Kephart, Alan R.

1991-01-01

An electrochemical polishing device and method for selective anodic dissolution of the surface of test specimens comprised, for example, of nickel-chromium-iron alloys, which provides for uniform dissolution at the localized sites to remove metal through the use of a coiled wire electrode (cathode) placed in the immediate proximity of the working, surface resulting in a polished and uniform grain boundary.

Planar fuel cell utilizing nail current collectors for increased active surface area

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

George, Thomas J.; Meacham, G.B. Kirby

1999-11-26

A plurality of nail current collector members are useful in the gas flow passages of an electrochemical device to optimize the active surfaces of the device and to provide structural support. In addition, the thicknesses of cathode and anode layers within the electrochemical device are varied according to current flow through the device to reduce resistance and increase operating efficiency.

Synthesis of gold nanoparticles on the surface of pyrolytic graphite using penicillin as a stabilizing reagent and the catalytic oxidation of α-naphthylamine

NASA Astrophysics Data System (ADS)

Song, Y. Z.; Song, Y.; Cheng, Z. P.; Zhou, J. F.; Wei, C.

2013-01-01

Electrochemical synthesis of gold nanoparticles on the surface of pyrolytic graphite using penicillin as a stabilizing reagent was proposed. The gold nanoparticles were characterized by scanning electron microscopy, cyclic voltammetry, IR spectra, UV spectra, and powder X-ray diffraction spectra. The electro-chemical catalysis of penicillin for α-naphthylamine was demonstrated.

SPE (tm) regenerative hydrogen/oxygen fuel cells for extraterrestrial surface and microgravity applications

NASA Technical Reports Server (NTRS)

Mcelroy, J. F.

1990-01-01

Viewgraphs on SPE regenerative hydrogen/oxygen fuel cells for extraterrestrial surface and microgravity applications are presented. Topics covered include: hydrogen-oxygen regenerative fuel cell energy storage system; electrochemical cell reactions; SPE cell voltage stability; passive water removal SPE fuel cell; fuel cell performance; SPE water electrolyzers; hydrophobic oxygen phase separator; hydrophilic/electrochemical hydrogen phase separator; and unitized regenerative fuel cell.

Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

NASA Astrophysics Data System (ADS)

Gupta, Sanju; Price, Carson

2015-10-01

Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO)1, (PPy/ErGO)1, (PAni/GO)1 and (PPy/GO)1. The rationale design is to create thin films that possess interconnected graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, Cs, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent Cs of ≥350 F g-1 as compared with constituents (˜70 F g-1) at discharge current density of 0.3 A g-1 that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine electrochemical (re)activity of surface ion adsorption sites density at solid/liquid interface.

Simultaneous noncontact topography and electrochemical imaging by SECM/SICM featuring ion current feedback regulation.

PubMed

Takahashi, Yasufumi; Shevchuk, Andrew I; Novak, Pavel; Murakami, Yumi; Shiku, Hitoshi; Korchev, Yuri E; Matsue, Tomokazu

2010-07-28

We described a hybrid system of scanning electrochemical microscopy (SECM) and scanning ion conductance microscopy (SICM) with ion current feedback nanopositioning control for simultaneous imaging of noncontact topography and spatial distribution of electrochemical species. A nanopipette/nanoring electrode probe provided submicrometer resolution of the electrochemical measurement on surfaces with complex topology. The SECM/SICM probe had an aperture radius of 220 nm. The inner and outer radii of the SECM Au nanoring electrode were 330 and 550 nm, respectively. Characterization of the probe was performed with scanning electron microscopy (SEM), cyclic voltammetry (CV), and approach curve measurements. SECM/SICM was applied to simultaneous imaging of topography and electrochemical responses of enzymes (horse radish peroxidase (HRP) and glucose oxidase (GOD)) and single live cells (A6 cells, superior cervical ganglion (SCG) cells, and cardiac myocytes). The measurements revealed the distribution of activity of the enzyme spots on uneven surfaces with submicrometer resolution. SECM/SICM acquired high resolution topographic images of cells together with the map of electrochemical signals. This combined technique was also applied to the evaluation of the permeation property of electroactive species through cellular membranes.

Highly cytocompatible and flexible three-dimensional graphene/polydimethylsiloxane composite for culture and electrochemical detection of L929 fibroblast cells.

PubMed

Waiwijit, Uraiwan; Maturos, Thitima; Pakapongpan, Saithip; Phokharatkul, Ditsayut; Wisitsoraat, Anurat; Tuantranont, Adisorn

2016-08-01

Recently, three-dimensional graphene interconnected network has attracted great interest as a scaffold structure for tissue engineering due to its high biocompatibility, high electrical conductivity, high specific surface area and high porosity. However, free-standing three-dimensional graphene exhibits poor flexibility and stability due to ease of disintegration during processing. In this work, three-dimensional graphene is composited with polydimethylsiloxane to improve the structural flexibility and stability by a new simple two-step process comprising dip coating of polydimethylsiloxane on chemical vapor deposited graphene/Ni foam and wet etching of nickel foam. Structural characterizations confirmed an interconnected three-dimensional multi-layer graphene structure with thin polydimethylsiloxane scaffold. The composite was employed as a substrate for culture of L929 fibroblast cells and its cytocompatibility was evaluated by cell viability (Alamar blue assay), reactive oxygen species production and vinculin immunofluorescence imaging. The result revealed that cell viability on three-dimensional graphene/polydimethylsiloxane composite increased with increasing culture time and was slightly different from a polystyrene substrate (control). Moreover, cells cultured on three-dimensional graphene/polydimethylsiloxane composite generated less ROS than the control at culture times of 3-6 h. The results of immunofluorescence staining demonstrated that fibroblast cells expressed adhesion protein (vinculin) and adhered well on three-dimensional graphene/polydimethylsiloxane surface. Good cell adhesion could be attributed to suitable surface properties of three-dimensional graphene/polydimethylsiloxane with moderate contact angle and small negative zeta potential in culture solution. The results of electrochemical study by cyclic voltammetry showed that an oxidation current signal with no apparent peak was induced by fibroblast cells and the oxidation current at an oxidation potential of +0.9 V increased linearly with increasing cell number. Therefore, the three-dimensional graphene/polydimethylsiloxane composite exhibits high cytocompatibility and can potentially be used as a conductive substrate for cell-based electrochemical sensing. © The Author(s) 2016.

Trial application of electrochemical chloride extraction on concrete bridge components in Virginia.

DOT National Transportation Integrated Search

2000-01-01

Electrochemical chloride extraction is a new technique for mitigating chloride-induced corrosion of the reinforcing bars in concrete bridges. To demonstrate the feasibility of applying this technique on full-sized concrete bridge members and to ident...

Combinatorial localized dissolution analysis: Application to acid-induced dissolution of dental enamel and the effect of surface treatments.

PubMed

Parker, Alexander S; Al Botros, Rehab; Kinnear, Sophie L; Snowden, Michael E; McKelvey, Kim; Ashcroft, Alexander T; Carvell, Mel; Joiner, Andrew; Peruffo, Massimo; Philpotts, Carol; Unwin, Patrick R

2016-08-15

A combination of scanning electrochemical cell microscopy (SECCM) and atomic force microscopy (AFM) is used to quantitatively study the acid-induced dissolution of dental enamel. A micron-scale liquid meniscus formed at the end of a dual barrelled pipette, which constitutes the SECCM probe, is brought into contact with the enamel surface for a defined period. Dissolution occurs at the interface of the meniscus and the enamel surface, under conditions of well-defined mass transport, creating etch pits that are then analysed via AFM. This technique is applied to bovine dental enamel, and the effect of various treatments of the enamel surface on acid dissolution (1mM HNO3) is studied. The treatments investigated are zinc ions, fluoride ions and the two combined. A finite element method (FEM) simulation of SECCM mass transport and interfacial reactivity, allows the intrinsic rate constant for acid-induced dissolution to be quantitatively determined. The dissolution of enamel, in terms of Ca(2+) flux ( [Formula: see text] ), is first order with respect to the interfacial proton concentration and given by the following rate law: [Formula: see text] , with k0=0.099±0.008cms(-1). Treating the enamel with either fluoride or zinc ions slows the dissolution rate, although in this model system the partly protective barrier only extends around 10-20nm into the enamel surface, so that after a period of a few seconds dissolution of modified surfaces tends towards that of native enamel. A combination of both treatments exhibits the greatest protection to the enamel surface, but the effect is again transient. Copyright © 2016 Elsevier Inc. All rights reserved.

Kinetically Controlled Synthesis of Pt-Based One-Dimensional Hierarchically Porous Nanostructures with Large Mesopores as Highly Efficient ORR Catalysts

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

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

2016-12-28

Rational design and construction of Pt-based porous nanostructures with large mesopores have triggered significant considerations because of their high surface area and more efficient mass transport. Hydrochloric acid-induced kinetic reduction of metal precursors in the presence of soft template F-127 and hard template tellurium nanowires has been successfully demonstrated to construct one-dimensional hierarchical porous PtCu alloy nanostructures with large mesopores. Moreover, the electrochemical experiments demonstrated that the resultant PtCu hierarchically porous nanostructures with optimized composition exhibit enhanced electrocatalytic performance for oxygen reduction reaction.

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

Masuda, Takuya; PRESTO, Japan Science and Technology Agency; Yoshikawa, Hideki

In situ electrochemical X-ray photoelectron spectroscopy (XPS) apparatus, which allows XPS at solid/liquid interfaces under potential control, was constructed utilizing a microcell with an ultra-thin Si membrane, which separates vacuum and a solution. Hard X-rays from a synchrotron source penetrate into the Si membrane surface exposed to the solution. Electrons emitted at the Si/solution interface can pass through the membrane and be analyzed by an analyzer placed in vacuum. Its operation was demonstrated for potential-induced Si oxide growth in water. Effect of potential and time on the thickness of Si and Si oxide layers was quantitatively determined at sub-nanometer resolution.

Development of an optimized electrochemical process for subsequent coating of 316 stainless steel for stent applications.

PubMed

Haïdopoulos, M; Turgeon, S; Sarra-Bournet, C; Laroche, G; Mantovani, D

2006-07-01

Metallic endovascular stents are used as medical devices to scaffold biological lumen, most often diseased arteries, after balloon angioplasty. They are commonly made of 316L stainless steel or Nitinol, two alloys containing nickel, an element classified as potentially toxic and carcinogenic by the International Agency for Research on Cancer. Although they are largely implanted, the long-term safety of such metallic elements is still controversial, since the corrosion processes may lead to the release of several metallic ions, including nickel ions in diverse oxidation states. To avoid metallic ion release in the body, the strategy behind this work was to develop a process aiming the complete isolation of the stainless steel device from the body fluids by a thin, cohesive and strongly adherent coating of RF-plasma-polymerized fluoropolymer. Nevertheless, prior to the polymer film deposition, an essential aspect was the development of a pre-treatment for the metallic substrate, based on the electrochemical polishing process, aiming the removal of any fragile interlayer, including the native oxide layer and the carbon contaminated layer, in order to obtain a smooth, defect-free surface to optimize the adhesion of the plasma-deposited thin film. In this work, the optimized parameters for electropolishing, such as the duration and the temperature of the electrolysis, and the complementary acid dipping were presented and accurately discussed. Their effects on roughness as well as on the evolution of surface topography were investigated by Atomic Force Microscopy, stylus profilometry and Scanning Electron Microscopy. The modifications induced on the surface atomic concentrations were studied by X-ray Photoelectron Spectroscopy. The improvements in terms of the surface morphology after the pre-treatment were also emphasized, as well as the influence of the original stainless steel surface finish.

AFM, CLSM and EIS characterization of the immobilization of antibodies on indium-tin oxide electrode and their capture of Legionella pneumophila.

PubMed

Souiri, Mina; Blel, Nesrine; Sboui, Dejla; Mhamdi, Lotfi; Epalle, Thibaut; Mzoughi, Ridha; Riffard, Serge; Othmane, Ali

2014-01-01

The microscopic surface molecular structures and properties of monoclonal anti-Legionella pneumophila antibodies on an indium-tin oxide (ITO) electrode surface were studied to elaborate an electrochemical immunosensor for Legionella pneumophila detection. A monoclonal anti-Legionella pneumophila antibody (MAb) has been immobilized onto an ITO electrode via covalent chemical bonds between antibodies amino-group and the ring of (3-Glycidoxypropyl) trimethoxysilane (GPTMS). The functionalization of the immunosensor was characterized by atomic force microscopy (AFM), water contact angle measurement, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in the presence of [Fe(CN)₆](3-/4-) as a redox probe. Specific binding of Legionella pneumophila sgp 1 cells onto the antibody-modified ITO electrode was shown by confocal laser scanning microscopy (CLSM) imaging and EIS. AFM images evidenced the dense and relatively homogeneous morphology on the ITO surface. The formation of the complex epoxysilane-antibodies acting as barriers for the electron transfer between the electrode surface and the redox species in the solution induced a significant increase in the charge transfer resistance (Rct) compared to all the electric elements. A linear relationship between the change in charge transfer resistance (ΔRct=Rct after immunoreactions - Rct control) and the logarithmic concentration value of L. pneumophila was observed in the range of 5 × 10(1)-5 × 10(4) CFU mL(-1) with a limit of detection 5 × 10(1)CFU mL(-1). The present study has demonstrated the successful deposition of an anti-L. pneumophila antibodies on an indium-tin oxide surface, opening its subsequent use as immuno-captor for the specific detection of L. pneumophila in environmental samples. © 2013 Elsevier B.V. All rights reserved.

Investigation of passive films on nickel Alloy 690 in lead-containing environments

NASA Astrophysics Data System (ADS)

Peng, B.; Lu, B. T.; Luo, J. L.; Lu, Y. C.; Ma, H. Y.

2008-09-01

Passive films formed on Alloy UNS N06690 were investigated in simulated crevice chemistries. It was found the role of lead in corrosion processes is strongly dependent on the pH value of the testing solutions. At pH 1.5 the effect of lead is narrowly noticeable; while at pH 12.7, lead has a significant influence on the electrochemical performance of alloy UNS N06690. The lead alters the surface morphologies at both pH and account for higher hydroxide content in the surface film at pH 12.7. The lead incorporation hinders the formation of spinel oxides during the passivation in alkaline solution. Nanoindentation tests indicate a significant lead-induced degradation in the mechanical properties of passive films. The passivation degradation is attributed to detrimental effects of lead via interrupting the dehydration process and hindering the formation of protective layers on the alloy surface.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Recent Development of Advanced Electrode Materials by Atomic Layer Deposition for Electrochemical Energy Storage.

PubMed

Guan, Cao; Wang, John

2016-10-01

Electrode materials play a decisive role in almost all electrochemical energy storage devices, determining their overall performance. Proper selection, design and fabrication of electrode materials have thus been regarded as one of the most critical steps in achieving high electrochemical energy storage performance. As an advanced nanotechnology for thin films and surfaces with conformal interfacial features and well controllable deposition thickness, atomic layer deposition (ALD) has been successfully developed for deposition and surface modification of electrode materials, where there are considerable issues of interfacial and surface chemistry at atomic and nanometer scale. In addition, ALD has shown great potential in construction of novel nanostructured active materials that otherwise can be hardly obtained by other processing techniques, such as those solution-based processing and chemical vapor deposition (CVD) techniques. This review focuses on the recent development of ALD for the design and delivery of advanced electrode materials in electrochemical energy storage devices, where typical examples will be highlighted and analyzed, and the merits and challenges of ALD for applications in energy storage will also be discussed.

Electrochemical Polishing Applications and EIS of a Vitamin B{sub 4}-Based Ionic Liquid

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

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-01-01

Modern particle accelerators require minimal interior surface roughness for Niobium superconducting radio frequency (SRF) cavities. Polishing of the Nb is currently achieved via electrochemical polishing with concentrated mixtures of sulfuric and hydrofluoric acids. This acid-based approach is effective at reducing the surface roughness to acceptable levels for SRF use, but due to acid-related hazards and extra costs (including safe disposal of used polishing solutions), an acid-free method would be preferable. This study focuses on an alternative electrochemical polishing method for Nb, using a novel ionic liquid solution containing choline chloride, also known as Vitamin B{sub 4} (VB{sub 4}). Potentiostatic electrochemicalmore » impedance spectroscopy (EIS) was also performed on the VB4-based system. Nb polished using the VB4-based method was found to have a final surface roughness comparable to that achieved via the acid-based method, as assessed by atomic force microscopy (AFM). These findings indicate that acid-free VB{sub 4}-based electrochemical polishing of Nb represents a promising replacement for acid-based methods of SRF cavity preparation.« less

Recent Development of Advanced Electrode Materials by Atomic Layer Deposition for Electrochemical Energy Storage

PubMed Central

2016-01-01

Electrode materials play a decisive role in almost all electrochemical energy storage devices, determining their overall performance. Proper selection, design and fabrication of electrode materials have thus been regarded as one of the most critical steps in achieving high electrochemical energy storage performance. As an advanced nanotechnology for thin films and surfaces with conformal interfacial features and well controllable deposition thickness, atomic layer deposition (ALD) has been successfully developed for deposition and surface modification of electrode materials, where there are considerable issues of interfacial and surface chemistry at atomic and nanometer scale. In addition, ALD has shown great potential in construction of novel nanostructured active materials that otherwise can be hardly obtained by other processing techniques, such as those solution‐based processing and chemical vapor deposition (CVD) techniques. This review focuses on the recent development of ALD for the design and delivery of advanced electrode materials in electrochemical energy storage devices, where typical examples will be highlighted and analyzed, and the merits and challenges of ALD for applications in energy storage will also be discussed. PMID:27840793

Quantification of microscopic surface features of single point diamond turned optics with subsequent chemical polishing

NASA Astrophysics Data System (ADS)

Cardenas, Nelson; Kyrish, Matthew; Taylor, Daniel; Fraelich, Margaret; Lechuga, Oscar; Claytor, Richard; Claytor, Nelson

2015-03-01

Electro-Chemical Polishing is routinely used in the anodizing industry to achieve specular surface finishes of various metals products prior to anodizing. Electro-Chemical polishing functions by leveling the microscopic peaks and valleys of the substrate, thereby increasing specularity and reducing light scattering. The rate of attack is dependent of the physical characteristics (height, depth, and width) of the microscopic structures that constitute the surface finish. To prepare the sample, mechanical polishing such as buffing or grinding is typically required before etching. This type of mechanical polishing produces random microscopic structures at varying depths and widths, thus the electropolishing parameters are determined in an ad hoc basis. Alternatively, single point diamond turning offers excellent repeatability and highly specific control of substrate polishing parameters. While polishing, the diamond tool leaves behind an associated tool mark, which is related to the diamond tool geometry and machining parameters. Machine parameters such as tool cutting depth, speed and step over can be changed in situ, thus providing control of the spatial frequency of the microscopic structures characteristic of the surface topography of the substrate. By combining single point diamond turning with subsequent electro-chemical etching, ultra smooth polishing of both rotationally symmetric and free form mirrors and molds is possible. Additionally, machining parameters can be set to optimize post polishing for increased surface quality and reduced processing times. In this work, we present a study of substrate surface finish based on diamond turning tool mark spatial frequency with subsequent electro-chemical polishing.

Active corrosion protection performance of an epoxy coating applied on the mild steel modified with an eco-friendly sol-gel film impregnated with green corrosion inhibitor loaded nanocontainers

NASA Astrophysics Data System (ADS)

Izadi, M.; Shahrabi, T.; Ramezanzadeh, B.

2018-05-01

In this study the corrosion resistance, active protection, and cathodic disbonding performance of an epoxy coating were improved through surface modification of steel by a hybrid sol-gel system filled with green corrosion inhibitors loaded nanocontainer as intermediate layer on mild steel substrate. The green inhibitor loaded nanocontainers (GIN) were used to induce active inhibition performance in the protective coating system. The corrosion protection performance of the coated panels was investigated by electrochemical impedance spectroscopy (EIS), salt spray, and cathodic disbonding tests. It was observed that the corrosion inhibition performance of the coated mild steel panels was significantly improved by utilization of active multilayer coating system. The inhibitor release from nanocontainers at the epoxy-silane film/steel interface resulted in the anodic and cathodic reactions restriction, leading to the lower coating delamination from the substrate and corrosion products progress. Also, the active inhibition performance of the coating system was approved by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and energy dispersive X-ray (EDS) analysis on the panels with artificial defects. The inhibitive agents were released to the scratch region and blocked the active sites on the metal surface.

In-situ electrochemical study of interaction of tribology and corrosion in artificial hip prosthesis simulators.

PubMed

Yan, Yu; Dowson, Duncan; Neville, Anne

2013-02-01

The second generation Metal-on-Metal (MoM) hip replacements have been considered as an alternative to commonly used Polyethylene-on-Metal (PoM) joint prostheses due to polyethylene wear debris induced osteolysis. However, the role of corrosion and the biofilm formed under tribological contact are still not fully understood. Enhanced metal ion concentrations have been reported widely from hair, blood and urine samples of patients who received metal hip replacements and in isolated cases when abnormally high levels have caused adverse local tissue reactions. An understanding of the origin of metal ions is really important in order to design alloys for reduced ion release. Reciprocating pin-on-plate wear tester is a standard instrument to assess the interaction of corrosion and wear. However, more realistic hip simulator can provide a better understanding of tribocorrosion process for hip implants. It is very important to instrument the conventional hip simulator to enable electrochemical measurements. In this study, simple reciprocating pin-on-plate wear tests and hip simulator tests were compared. It was found that metal ions originated from two sources: (a) a depassivation of the contacting surfaces due to tribology (rubbing) and (b) corrosion of nano-sized wear particles generated from the contacting surfaces. Copyright © 2012 Elsevier Ltd. All rights reserved.

Synthesis and Electrochemical Analyses of Manganese Oxides for Super-Capacitors.

PubMed

Kim, Taewoo; Hwang, Hyein; Jang, Jaeyong; Park, Inyeong; Shim, Sang Eun; Baeck, Sung-Hyeon

2015-11-01

δ-Phase and α-phase manganese oxides were prepared using a hydrothermal method and their electrochemical properties were characterized. The influence of calcination temperature on the properties of manganese oxides was studied. Crystallinities were studied by X-ray diffraction, and scanning and transmission electron microscopy were utilized to examine morphologies. Average pore sizes and specific surface areas of samples were analyzed using the Barret-Joyner-Halenda and Brunauer-Emmett-Teller methods, respectively. After calcination in the range 300 degrees C to 600 degrees C, changes in morphology and crystallinity were observed. The flower-like shape of as synthesized samples became nanorod-like and the δ-phase changed to the α-phase. These changes may have been due to the removal of water during calcination. Furthermore, a transition stage in which the two phases coexisted was observed. Synthesized manganese oxides were mixed with carbon by sonification, to increase electric conductivity and to induce a synergistic effect between pseudo-capacitor and electric double layer capacitor (EDLC). Specific capacitances and rate durability of each composite were investigated by cyclic voltammetry in 1 M Na2SO4 electrolyte at different scan rates. MnO2 calcined at 400 degrees C exhibited the highest capacitance, probably due to its high surface area and more porous structure.

Enhancing the sensitivity of needle-implantable electrochemical glucose sensors via surface rebuilding.

PubMed

Vaddiraju, Santhisagar; Legassey, Allen; Qiang, Liangliang; Wang, Yan; Burgess, Diane J; Papadimitrakopoulos, Fotios

2013-03-01

Needle-implantable sensors have shown to provide reliable continuous glucose monitoring for diabetes management. In order to reduce tissue injury during sensor implantation, there is a constant need for device size reduction, which imposes challenges in terms of sensitivity and reliability, as part of decreasing signal-to-noise and increasing layer complexity. Herein, we report sensitivity enhancement via electrochemical surface rebuilding of the working electrode (WE), which creates a three-dimensional nanoporous configuration with increased surface area. The gold WE was electrochemically rebuilt to render its surface nanoporous followed by decoration with platinum nanoparticles. The efficacy of such process was studied using sensor sensitivity against hydrogen peroxide (H2O2). For glucose detection, the WE was further coated with five layers, namely, (1) polyphenol, (2) glucose oxidase, (3) polyurethane, (4) catalase, and (5) dexamethasone-releasing poly(vinyl alcohol)/poly(lactic-co-glycolic acid) composite. The amperometric response of the glucose sensor was noted in vitro and in vivo. Scanning electron microscopy revealed that electrochemical rebuilding of the WE produced a nanoporous morphology that resulted in a 20-fold enhancement in H2O2 sensitivity, while retaining >98% selectivity. This afforded a 4-5-fold increase in overall glucose response of the glucose sensor when compared with a control sensor with no surface rebuilding and fittable only within an 18 G needle. The sensor was able to reproducibly track in vivo glycemic events, despite the large background currents typically encountered during animal testing. Enhanced sensor performance in terms of sensitivity and large signal-to-noise ratio has been attained via electrochemical rebuilding of the WE. This approach also bypasses the need for conventional and nanostructured mediators currently employed to enhance sensor performance. © 2013 Diabetes Technology Society.

ac electroosmotic pumping induced by noncontact external electrodes.

PubMed

Wang, Shau-Chun; Chen, Hsiao-Ping; Chang, Hsueh-Chia

2007-09-21

Electroosmotic (EO) pumps based on dc electroosmosis is plagued by bubble generation and other electrochemical reactions at the electrodes at voltages beyond 1 V for electrolytes. These disadvantages limit their throughput and offset their portability advantage over mechanical syringe or pneumatic pumps. ac electroosmotic pumps at high frequency (>100 kHz) circumvent the bubble problem by inducing polarization and slip velocity on embedded electrodes,1 but they require complex electrode designs to produce a net flow. We report a new high-throughput ac EO pump design based on induced-polarization on the entire channel surface instead of just on the electrodes. Like dc EO pumps, our pump electrodes are outside of the load section and form a cm-long pump unit consisting of three circular reservoirs (3 mm in diameter) connected by a 1x1 mm channel. The field-induced polarization can produce an effective Zeta potential exceeding 1 V and an ac slip velocity estimated as 1 mmsec or higher, both one order of magnitude higher than earlier dc and ac pumps, giving rise to a maximum throughput of 1 mulsec. Polarization over the entire channel surface, quadratic scaling with respect to the field and high voltage at high frequency without electrode bubble generation are the reasons why the current pump is superior to earlier dc and ac EO pumps.

The impact of surface composition on Tafel kinetics leading to enhanced electrochemical insertion of hydrogen in palladium

NASA Astrophysics Data System (ADS)

Dmitriyeva, Olga; Hamm, Steven C.; Knies, David L.; Cantwell, Richard; McConnell, Matt

2018-05-01

Our previous work experimentally demonstrated the enhancement of electrochemical hydrogen insertion into palladium by modifying the chemical composition of the cathode surface with Pb, Pt and Bi, referred to as surface promoters. The experiment demonstrated that an optimal combination of the surface promoters led to an increase in hydrogen fugacity of more than three orders of magnitude, while maintaining the same current density. This manuscript discusses the application of Density Functional Theory (DFT) to elucidate the thermodynamics and kinetics of observed enhancement of electrochemical hydrogen insertion into palladium. We present theoretical simulations that: (1) establish the elevation of hydrogen's chemical potential on Pb and Bi surfaces to enhance hydrogen insertion, (2) confirm the increase of a Tafel activation barrier that results in a decrease of the reaction rate at the given hydrogen overpotential, and (3) explain why the surface promoter's coverage needs to be non-uniform, namely to allow hydrogen insertion into palladium bulk while simultaneously locking hydrogen below the surface (the corking effect). The discussed DFT-based method can be used for efficient scanning of different material configurations to design a highly effective hydrogen storage system.

High Surface Area Dendrite Nanoelectrodes for Electrochemistry

NASA Astrophysics Data System (ADS)

Nesbitt, Nathan; Glover, Jennifer; Goyal, Saurabh; Simidjiysky, Svetoslav; Naughton, Michael

2014-03-01

Solution-based electrodeposition of metal using a low ion concentration, surface passivation agents, and/or electrochemical crystal conditioning has allowed for the formation of high surface area metal electrodes, useful for Raman spectroscopy and electrochemical sensors. Additionally, high frequency electrical oscillations have been used to electrically connect co-planar electrodes, a process called directed electrochemical nanowire assembly (DENA). These approaches aim to control the crystal face that metal atoms in solution will nucleate onto, thus causing anisotropic growth of metal crystals. However, DENA has not been used to create high surface area electrodes, and no study has been conducted on the effect of micron-scale surface topography on the initial nucleation of metal crystals on the electrode surface. When DENA is used to create a high surface area electrode, such a texture has a strong impact on the subsequent topography of the three dimensional dendritic structures by limiting the areal density of crystals on the electrode surface. Such structures both demonstrate unique physics concerning the nucleation of metal dendrites, and offer a unique and highly facile fabrication method of high surface area electrodes, useful for chemical and biological sensing. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1258923).

Effect of tungsten on the corrosion behavior of sulfuric acid-resistant steels for flue gas desulfurization system

NASA Astrophysics Data System (ADS)

Ji, Woo-Soo; Jang, Young-Wook; Kim, Jung-Gu

2011-06-01

Flue gas desulfurization systems (FGDs) are operated in severely corrosive environments that cause sulfuric acid dew-point corrosion. The corrosion behavior of low-alloy steels was tested using electrochemical techniques (electrochemical impedance spectroscopy, potentiodynamic tests, potentiostatic tests), and the corrosion products were analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy. The electrochemical results showed that alloying W with small amounts of Sb, Cu, and Co improves the corrosion resistance of steels. The results of surface analyses showed that the surface of the steels alloyed with W consisted of W oxides and higher amounts of Sb and Cu oxides. This suggests that the addition of W promotes the formation of a protective WO3 film, in addition to Sb2O5 and CuO films on the surface.

Electrochemical characterization of p(+)n and n(+)p diffused InP structures

NASA Technical Reports Server (NTRS)

Wilt, David M.; Faur, Maria; Faur, Mircea; Goradia, M.; Vargas-Aburto, Carlos

1993-01-01

The relatively well documented and widely used electrolytes for characterization and processing of Si and GaAs-related materials and structures by electrochemical methods are of little or no use with InP because the electrolytes presently used either dissolve the surface preferentially at the defect areas or form residual oxides and introduce a large density of surface states. Using an electrolyte which was newly developed for anodic dissolution of InP, and was named the 'FAP' electrolyte, accurate characterization of InP related structures including nature and density of surface states, defect density, and net majority carrier concentration, all as functions of depth was performed. A step-by-step optimization of n(+)p and p(+)n InP structures made by thermal diffusion was done using the electrochemical techniques, and resulted in high performance homojunction InP structures.

Probing local bias-induced transitions using photothermal excitation contact resonance atomic force microscopy and voltage spectroscopy

DOE PAGES

Li, Qian; Jesse, Stephen; Tselev, Alexander; ...

2015-01-05

In this paper, nanomechanical properties are closely related to the states of matter, including chemical composition, crystal structure, mesoscopic domain configuration, etc. Investigation of these properties at the nanoscale requires not only static imaging methods, e.g., contact resonance atomic force microscopy (CR-AFM), but also spectroscopic methods capable of revealing their dependence on various external stimuli. Here we demonstrate the voltage spectroscopy of CR-AFM, which was realized by combining photothermal excitation (as opposed to the conventional piezoacoustic excitation method) with the band excitation technique. We applied this spectroscopy to explore local bias-induced phenomena ranging from purely physical to surface electromechanical andmore » electrochemical processes. Our measurements show that the changes in the surface properties associated with these bias-induced transitions can be accurately assessed in a fast and dynamic manner, using resonance frequency as a signature. Finally, with many of the advantages offered by photothermal excitation, contact resonance voltage spectroscopy not only is expected to find applications in a broader field of nanoscience but also will provide a basis for future development of other nanoscale elastic spectroscopies.« less

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

Chen, Zonghai; Amine, Khalil; Belharouak, Ilias

An active material for an electrochemical device wherein a surface of the active material is modified by a surface modification agent, wherein the surface modification agent is an organometallic compound.

Electrochemical immunoassay for tumor markers based on hydrogels.

PubMed

Yin, Shuang; Ma, Zhanfang

2018-05-08

Hydrogel-based electrochemical immunoassays exhibit a large surface-to-volume ratio, excellent biocompatibility, unique stimuli-responsive behavior, high permeability and hydrophilicity and, thus, have shown great potential in the sensitive and accurate detection of tumor markers. Electrochemical immunosensing techniques for tumor markers based on hydrogels have greatly progressed in recent years. Areas covered: In this review, the authors describe the recent advances of hydrogel-based electrochemical immunosensing interface of tumor markers based on the different functions of hydrogels including conductive, catalytic, redox, stimuli-responsive and antifouling hydrogels. Expert commentary: Hydrogels have been successfully employed in electrochemical immunoassay of tumor markers, which is accountable to their unique properties. For further exploitation of hydrogel-based electrochemical biosensors, more variety of hydrogels need be fabricated with improved functionality.

Electrochemical sensor for monitoring electrochemical potentials of fuel cell components

DOEpatents

Kunz, Harold R.; Breault, Richard D.

1993-01-01

An electrochemical sensor comprised of wires, a sheath, and a conduit can be utilized to monitor fuel cell component electric potentials during fuel cell shut down or steady state. The electrochemical sensor contacts an electrolyte reservoir plate such that the conduit wicks electrolyte through capillary action to the wires to provide water necessary for the electrolysis reaction which occurs thereon. A voltage is applied across the wires of the electrochemical sensor until hydrogen evolution occurs at the surface of one of the wires, thereby forming a hydrogen reference electrode. The voltage of the fuel cell component is then determined with relation to the hydrogen reference electrode.

In Vitro Electrochemical Corrosion and Cell Viability Studies on Nickel-Free Stainless Steel Orthopedic Implants

PubMed Central

Salahinejad, Erfan; Hadianfard, Mohammad Jafar; Macdonald, Digby Donald; Sharifi-Asl, Samin; Mozafari, Masoud; Walker, Kenneth J.; Rad, Armin Tahmasbi; Madihally, Sundararajan V.; Tayebi, Lobat

2013-01-01

The corrosion and cell viability behaviors of nanostructured, nickel-free stainless steel implants were studied and compared with AISI 316L. The electrochemical studies were conducted by potentiodynamic polarization and electrochemical impedance spectroscopic measurements in a simulated body fluid. Cytocompatibility was also evaluated by the adhesion behavior of adult human stem cells on the surface of the samples. According to the results, the electrochemical behavior is affected by a compromise among the specimen's structural characteristics, comprising composition, density, and grain size. The cell viability is interpreted by considering the results of the electrochemical impedance spectroscopic experiments. PMID:23630603

IN VIVO SEVERE CORROSION AND HYDROGEN EMBRITTLEMENT OF RETRIEVED MODULAR BODY TITANIUM ALLOY HIP-IMPLANTS

PubMed Central

Rodrigues, Danieli C.; Urban, Robert M.; Jacobs, Joshua J.; Gilbert, Jeremy L.

2009-01-01

Titanium alloys are widely used in total-joint replacements due to a combination of outstanding mechanical properties, biocompatibility, passivity and corrosion resistance. Nevertheless, retrieval studies have pointed out that these materials can be subjected to localized or general corrosion in modular interfaces when mechanical abrasion of the oxide film (fretting) occurs. Modularity adds large crevice environments, which are subject to micromotion between contacting interfaces and differential aeration of the surface. Titanium alloys are also known to be susceptible to hydrogen absorption, which can induce precipitation of hydrides and subsequent brittle failure. In this work, the surface of three designs of retrieved hip-implants with Ti-6Al-4V/Ti-6Al-4V modular taper interfaces in the stem were investigated for evidence of severe corrosion and precipitation of brittle hydrides during fretting-crevice corrosion in the modular connections. The devices were retrieved from patients and studied by means of scanning electron microscopy (SEM), x-ray diffraction (XRD) and chemical analysis. The surface qualitative investigation revealed severe corrosion attack in the mating interfaces with evidence of etching, pitting, delamination and surface cracking. In vivo hydrogen embrittlement was shown to be a mechanism of degradation in modular connections resulting from electrochemical reactions induced in the crevice environment of the tapers during fretting-crevice corrosion. PMID:18683224

Simultaneously Coupled Mechanical-Electrochemical-Thermal Simulation of Lithium-Ion Cells

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

Zhang, C.; Santhanagopalan, S.; Sprague, M. A.

2016-07-28

Understanding the combined electrochemical-thermal and mechanical response of a system has a variety of applications, for example, structural failure from electrochemical fatigue and the potential induced changes of material properties. For lithium-ion batteries, there is an added concern over the safety of the system in the event of mechanical failure of the cell components. In this work, we present a generic multi-scale simultaneously coupled mechanical-electrochemical-thermal model to examine the interaction between mechanical failure and electrochemical-thermal responses. We treat the battery cell as a homogeneous material while locally we explicitly solve for the mechanical response of individual components using a homogenizationmore » model and the electrochemical-thermal responses using an electrochemical model for the battery. A benchmark problem is established to demonstrate the proposed modeling framework. The model shows the capability to capture the gradual evolution of cell electrochemical-thermal responses, and predicts the variation of those responses under different short-circuit conditions.« less

Simultaneously Coupled Mechanical-Electrochemical-Thermal Simulation of Lithium-Ion Cells: Preprint

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

Zhang, Chao; Santhanagopalan, Shriram; Sprague, Michael A.

2016-08-01

Understanding the combined electrochemical-thermal and mechanical response of a system has a variety of applications, for example, structural failure from electrochemical fatigue and the potential induced changes of material properties. For lithium-ion batteries, there is an added concern over the safety of the system in the event of mechanical failure of the cell components. In this work, we present a generic multi-scale simultaneously coupled mechanical-electrochemical-thermal model to examine the interaction between mechanical failure and electrochemical-thermal responses. We treat the battery cell as a homogeneous material while locally we explicitly solve for the mechanical response of individual components using a homogenizationmore » model and the electrochemical-thermal responses using an electrochemical model for the battery. A benchmark problem is established to demonstrate the proposed modeling framework. The model shows the capability to capture the gradual evolution of cell electrochemical-thermal responses, and predicts the variation of those responses under different short-circuit conditions.« less

Electrochemical hydrogenation of a homogeneous nickel complex to form a surface adsorbed hydrogen-evolving species

DOE PAGES

Martin, Daniel J.; McCarthy, Brian D.; Donley, Carrie L.; ...

2014-12-04

Here, a Ni(ii) complex with nitrogen and sulfur donor ligands degrades electrochemically in the presence of acid in acetonitrile to form an electrode adsorbed film that catalytically evolves hydrogen.

Using sewage sludge pyrolytic gas to modify titanium alloy to obtain high-performance anodes in bio-electrochemical systems

NASA Astrophysics Data System (ADS)

Gu, Yuan; Ying, Kang; Shen, Dongsheng; Huang, Lijie; Ying, Xianbin; Huang, Haoqian; Cheng, Kun; Chen, Jiazheng; Zhou, Yuyang; Chen, Ting; Feng, Huajun

2017-12-01

Titanium is under consideration as a potential stable bio-anode because of its high conductivity, suitable mechanical properties, and electrochemical inertness in the operating potential window of bio-electrochemical systems; however, its application is limited by its poor electron-transfer capacity with electroactive bacteria and weak ability to form biofilms on its hydrophobic surface. This study reports an effective and low-cost way to convert a hydrophobic titanium alloy surface into a hydrophilic surface that can be used as a bio-electrode with higher electron-transfer rates. Pyrolytic gas of sewage sludge is used to modify the titanium alloy. The current generation, anodic biofilm formation surface, and hydrophobicity are systematically investigated by comparing bare electrodes with three modified electrodes. Maximum current density (15.80 A/m2), achieved using a modified electrode, is 316-fold higher than that of the bare titanium alloy electrode (0.05 A/m2) and that achieved by titanium alloy electrodes modified by other methods (12.70 A/m2). The pyrolytic gas-modified titanium alloy electrode can be used as a high-performance and scalable bio-anode for bio-electrochemical systems because of its high electron-transfer rates, hydrophilic nature, and ability to achieve high current density.

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

Method for vacuum pressing electrochemical cell components

NASA Technical Reports Server (NTRS)

Andrews, Craig C. (Inventor); Murphy, Oliver J. (Inventor)

2004-01-01

Assembling electrochemical cell components using a bonding agent comprising aligning components of the electrochemical cell, applying a bonding agent between the components to bond the components together, placing the components within a container that is essentially a pliable bag, and drawing a vacuum within the bag, wherein the bag conforms to the shape of the components from the pressure outside the bag, thereby holding the components securely in place. The vacuum is passively maintained until the adhesive has cured and the components are securely bonded. The bonding agent used to bond the components of the electrochemical cell may be distributed to the bonding surface from distribution channels in the components. To prevent contamination with bonding agent, some areas may be treated to produce regions of preferred adhesive distribution and protected regions. Treatments may include polishing, etching, coating and providing protective grooves between the bonding surfaces and the protected regions.

Electrochemical Polishing Applications and EIS of a Novel Choline Chloride-Based Ionic Liquid

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

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-06-01

Minimal surface roughness is a critical feature for high-field superconducting radio frequency (SRF) cavities used to engineer particle accelerators. Current methods for polishing Niobium cavities typically utilize solutions containing a mixture of concentrated sulfuric and hydrofluoric acid. Polishing processes such as these are effective, yet there are many hazards and costs associated with the use (and safe disposal) of the concentrated acid solutions. An alternative method for electrochemical polishing of the cavities was explored using a novel ionic liquid solution containing choline chloride. Potentiostatic electrochemical impedance spectroscopy (EIS) was used to analyze the ionic polishing solution. Final surface roughness ofmore » the Nb was found to be comparable to that of the acid-polishing method, as assessed by atomic force microscopy (AFM). This indicates that ionic liquid-based electrochemical polishing of Nb is a viable replacement for acid-based methods for preparation of SRF cavities.« less

Fabrication and Performance Study on Individual Zno Nanowires Based Bioelectrode

NASA Astrophysics Data System (ADS)

Zhao, Yanguang; Yan, Xiaoqin; Kang, Zhuo; Lin, Pei

2012-08-01

One-dimensional zinc oxide nanowires (ZnO NWs) have unique advantages for use in biosensors as follows: oxide stable surface, excellent biosafety, high specific surface area, high isoelectric point (IEP = 9.5). In this work, we have prepared a kind of electrochemical bioelectrode based on individual ZnO NWs. Here, ZnO NWs with high quality were successfully synthesized by CVD method, which were characterized by scanning electron microscopy, X-ray diffraction and photoluminescence. Then the Raman spectra and electrical characterization demonstrated the adsorption of uricase on ZnO wires. At last, a series of electrochemical measurements were carried out by using an electrochemical workstation with a conventional three-electrode system to obtain the cyclic voltammetry characteristics of the bioelectrodes. The excellent performance of the fabricated bioelectrode implies the potential application for single ZnO nanowire to construct electrochemical biosensor for the detection of uric acid.

An Electrochemical Impedimetric Aptasensing Platform for Sensitive and Selective Detection of Small Molecules Such as Chloramphenicol

PubMed Central

Pilehvar, Sanaz; Dierckx, Tarryn; Blust, Ronny; Breugelmans, Tom; De Wael, Karolien

2014-01-01

We report on the aptadetection of chloramphenicol (CAP) using electrochemical impedance spectroscopy. The detection principle is based on the changes of the interfacial properties of the electrode after the interaction of the ssDNA aptamers with the target molecules. The electrode surface is partially blocked due to the formation of the aptamer-CAP complex, resulting in an increase of the interfacial electron-transfer resistance of the redox probe detected by electrochemical impedance spectroscopy or cyclic voltammetry. We observed that the ratio of polarization resistance had a linear relationship with the concentrations of CAP in the range of 1.76–127 nM, and a detection limit of 1.76 nM was obtained. The covalent binding of CAP-aptamer on the electrode surface combined with the unique properties of aptamers and impedimetric transduction leads to the development of a stable and sensitive electrochemical aptasensor for CAP. PMID:25004156

Electrochemical Reconstitution of Biomolecules for Applications as Electrocatalysts for the Bionanofuel Cell

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; King, Glen C.; Watt, Gerald D.; Chu, Sang-Hyon; Park, Yeonjoon; Thibeault, Sheila

2004-01-01

Platinum-cored ferritins were synthesized as electrocatalysts by electrochemical biomineralization of immobilized apoferritin with platinum. The platinum cored ferritin was fabricated by exposing the immobilized apoferritin to platinum ions at a reduction potential. On the platinum-cored ferritin, oxygen is reduced to water with four protons and four electrons generated from the anode. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This results in a smaller catalyst loading of the electrodes for fuel cells or other electrochemical devices. In addition, the catalytic activity of the ferritin-stabilized platinum nanoparticles is enhanced by the large surface area and particle size phenomena. The work presented herein details the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritin with different inorganic cores, and the fabrication of self-assembled 2-D arrays with thiolated ferritin.

Current Progress of Nanomaterials in Molecularly Imprinted Electrochemical Sensing.

PubMed

Zhong, Chunju; Yang, Bin; Jiang, Xinxin; Li, Jianping

2018-01-02

Nanomaterials have received much attention during the past decade because of their excellent optical, electronic, and catalytic properties. Nanomaterials possess high chemical reactivity, also high surface energy. Thus, provide a stable immobilization platform for biomolecules, while preserving their reactivity. Due to the conductive and catalytic properties, nanomaterials can also enhance the sensitivity of molecularly imprinted electrochemical sensors by amplifying the electrode surface, increasing the electron transfer, and catalyzing the electrochemical reactions. Molecularly imprinted polymers that contain specific molecular recognition sites can be designed for a particular target analyte. Incorporating nanomaterials into molecularly imprinted polymers is important because nanomaterials can improve the response signal, increase the sensitivity, and decrease the detection limit of the sensors. This study describes the classification of nanomaterials in molecularly imprinted polymers, their analytical properties, and their applications in the electrochemical sensors. The progress of the research on nanomaterials in molecularly imprinted polymers and the application of nanomaterials in molecularly imprinted polymers is also reviewed.

Superior supercapacitors based on nitrogen and sulfur co-doped hierarchical porous carbon: Excellent rate capability and cycle stability

NASA Astrophysics Data System (ADS)

Zhang, Deyi; Han, Mei; Wang, Bing; Li, Yubing; Lei, Longyan; Wang, Kunjie; Wang, Yi; Zhang, Liang; Feng, Huixia

2017-08-01

Vastly improving the charge storage capability of supercapacitors without sacrificing their high power density and cycle performance would bring bright application prospect. Herein, we report a nitrogen and sulfur co-doped hierarchical porous carbon (NSHPC) with very superior capacitance performance fabricated by KOH activation of nitrogen and sulfur co-doped ordered mesoporous carbon (NSOMC). A high electrochemical double-layer (EDL) capacitance of 351 F g-1 was observed for the reported NSHPC electrodes, and the capacitance remains at 288 F g-1 even under a large current density of 20 A g-1. Besides the high specific capacitance and outstanding rate capability, symmetrical supercapacitor cell based on the NSHPC electrodes also exhibits an excellent cycling performance with 95.61% capacitance retention after 5000 times charge/discharge cycles. The large surface area caused by KOH activation (2056 m2 g-1) and high utilized surface area owing to the ideal micro/mesopores ratio (2.88), large micropores diameter (1.38 nm) and short opened micropores structure as well as the enhanced surface wettability induced by N and S heteroatoms doping and improved conductivity induced by KOH activation was found to be responsible for the very superior capacitance performance.

Attomolar electrochemical detection of the BCR/ABL fusion gene based on an amplifying self-signal metal nanoparticle-conducting polymer hybrid composite.

PubMed

Avelino, Karen Y P S; Frias, Isaac A M; Lucena-Silva, Norma; Gomes, Renan G; de Melo, Celso P; Oliveira, Maria D L; Andrade, César A S

2016-12-01

In the last ten years, conjugated polymers started to be used in the immobilization of nucleic acids via non-covalent interactions. In the present study, we describe the construction and use of an electrochemical DNA biosensor based on a nanostructured polyaniline-gold composite, specifically developed for the detection of the BCR/ABL chimeric oncogene. This chromosome translocation is used as a biomarker to confirm the clinical diagnosis of both chronic myelogenous leukemia (CML) and acute lymphocytic leukemia (ALL). The working principle of the biosensor rests on measuring the conductivity resulting from the non-covalent interactions between the hybrid nanocomposite and the DNA probe. The nanostructured platform exhibits a large surface area that enhances the conductivity. Positive cases, which result from the hybridization between DNA probe and targeted gene, induce changes in the amperometric current and in the charge transfer resistance (R CT ) responses. Atomic force microscopy (AFM) images showed changes in the genosensor surface after exposure to cDNA sample of patient with leukemia, evidencing the hybridization process. This new hybrid sensing-platform displayed high specificity and selectivity, and its detection limit is estimated to be as low as 69.4 aM. The biosensor showed excellent analytical performance for the detection of the BCR/ABL oncogene in clinical samples of patients with leukemia. Hence, this electrochemical sensor appears as a simple and attractive tool for the molecular diagnosis of the BCR/ABL oncogene even in early-stage cases of leukemia and for the monitoring of minimum levels of residual disease. Copyright © 2016 Elsevier B.V. All rights reserved.

High-sensitive electrochemical detection of point mutation based on polymerization-induced enzymatic amplification.

PubMed

Feng, Kejun; Zhao, Jingjin; Wu, Zai-Sheng; Jiang, Jianhui; Shen, Guoli; Yu, Ruqin

2011-03-15

Here a highly sensitive electrochemical method is described for the detection of point mutation in DNA. Polymerization extension reaction is applied to specifically initiate enzymatic electrochemical amplification to improve the sensitivity and enhance the performance of point mutation detection. In this work, 5'-thiolated DNA probe sequences complementary to the wild target DNA are assembled on the gold electrode. In the presence of wild target DNA, the probe is extended by DNA polymerase over the free segment of target as the template. After washing with NaOH solution, the target DNA is removed while the elongated probe sequence remains on the sensing surface. Via hybridizing to the designed biotin-labeled detection probe, the extended sequence is capable of capturing detection probe. After introducing streptavidin-conjugated alkaline phosphatase (SA-ALP), the specific binding between streptavidin and biotin mediates a catalytic reaction of ascorbic acid 2-phosphate (AA-P) substrate to produce a reducing agent ascorbic acid (AA). Then the silver ions in solution are reduced by AA, leading to the deposition of silver metal onto the electrode surface. The amount of deposited silver which is determined by the amount of wild target can be quantified by the linear sweep voltammetry (LSV). The present approach proved to be capable of detecting the wild target DNA down to a detection limit of 1.0×10(-14) M in a wide target concentration range and identifying -28 site (A to G) of the β-thalassemia gene, demonstrating that this scheme offers a highly sensitive and specific approach for point mutation detection. Copyright © 2010 Elsevier B.V. All rights reserved.

Ferroionic states: coupling between surface electrochemical and bulk ferroelectric functionalities on the nanoscale.

NASA Astrophysics Data System (ADS)

Kalinin, Sergei

Ferroelectricity on the nanoscale has remained a subject of much fascination in condensed matter physics for the last several decades. It is well-recognized that stability of the ferroelectric state necessitates effective polarization screening, and hence screening mechanism and screening charge dynamics become strongly coupled to ferroelectric phase stability and domain behavior. Previously, the role of the screening charge in macroscopic ferroelectrics was observed in phenomena such as potential retention above Curie temperature, back switching of ferroelectric domains, and chaos and intermittency during domain switching. In the last several years, multiple reports claiming ferroelectricity in ultrathin ferroelectrics based on formation of remanent polarization states, local hysteresis loops, and pressure induced switching were made. However, similar phenomena were reported for traditionally non-ferroelectric materials, creating significant level of uncertainty in the field. We pose that in the nanoscale systems, the ferroelectric state is fundamentally inseparable from electrochemical state of the surface, leading to emergence of coupled electrochemical-ferroelectric states. I will present the results of experimental and theoretical work exploring the basic mechanisms of emergence of these coupled states including the basic theory and phase-field formulation for domain evolution. I further discuss the thermodynamics and thickness evolution of this state, and demonstrate the experimental pathway to establish its presence based on spectroscopic version of piezoresponse force microscopy. Finally, the role of chemical screening on domain dynamics is explored using phase-field modelling. This analysis reconciles multiple prior studies, and set forward the predictive pathways for new generations of ferroelectric devices and applications. This research was sponsored by the Division of Materials Sciences and Engineering, BES, DOE, and was conducted at the Center for Nanophase Materials Sciences, sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division.

Deterministic analysis of processes at corroding metal surfaces and the study of electrochemical noise in these systems

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

Latanision, R.M.

1990-12-01

Electrochemical corrosion is pervasive in virtually all engineering systems and in virtually all industrial circumstances. Although engineers now understand how to design systems to minimize corrosion in many instances, many fundamental questions remain poorly understood and, therefore, the development of corrosion control strategies is based more on empiricism than on a deep understanding of the processes by which metals corrode in electrolytes. Fluctuations in potential, or current, in electrochemical systems have been observed for many years. To date, all investigations of this phenomenon have utilized non-deterministic analyses. In this work it is proposed to study electrochemical noise from a deterministicmore » viewpoint by comparison of experimental parameters, such as first and second order moments (non-deterministic), with computer simulation of corrosion at metal surfaces. In this way it is proposed to analyze the origins of these fluctuations and to elucidate the relationship between these fluctuations and kinetic parameters associated with metal dissolution and cathodic reduction reactions. This research program addresses in essence two areas of interest: (a) computer modeling of corrosion processes in order to study the electrochemical processes on an atomistic scale, and (b) experimental investigations of fluctuations in electrochemical systems and correlation of experimental results with computer modeling. In effect, the noise generated by mathematical modeling will be analyzed and compared to experimental noise in electrochemical systems. 1 fig.« less

Electrochemical characterization of pulsed layer deposited hydroxyapatite-zirconia layers on Ti-21Nb-15Ta-6Zr alloy for biomedical application

NASA Astrophysics Data System (ADS)

Izquierdo, Javier; Bolat, Georgiana; Cimpoesu, Nicanor; Trinca, Lucia Carmen; Mareci, Daniel; Souto, Ricardo Manuel

2016-11-01

A new titanium base Ti-21Nb-15Ta-6Zr alloy covered with hydroxyapatite-zirconia (HA-ZrO2) by pulsed laser deposition (PLD) technique was characterized regarding its corrosion resistance in simulated physiological Ringer's solution at 37 °C. For the sake of comparison, Ti-6Al-4V standard implant alloy, with and without hydroxyapatite-zirconia coating, was also characterized. Multiscale electrochemical analysis using both conventional averaging electrochemical techniques, namely electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization, and spatially-resolved microelectrochemical techniques (scanning electrochemical microscopy, SECM) were used to investigate the electrochemical behaviour of the materials. In addition, scanning electron microscopy evidenced that no relevant surface morphology changes occurred on the materials upon immersion in the simulated physiological solution, despite variations in their electrochemical behaviour. Although uncoated metals appear to show better performances during conventional corrosion tests, the response is still quite similar for the HA-ZrO2 coated materials while providing superior resistance towards electron transfer due to the formation of a more dense film on the surface, thus effectively behaving as a passive material. It is believed corrosion of the HA-ZrO2 coated Ti-21Nb-15Ta-6Zr alloy will have negligible effect upon biochemical and cellular events at the bone-implant interface and could facilitate osseointegration.

Impedance spectroscopy study of a catechol-modified activated carbon electrode as active material in electrochemical capacitor

NASA Astrophysics Data System (ADS)

Cougnon, C.; Lebègue, E.; Pognon, G.

2015-01-01

Modified activated carbon (Norit S-50) electrodes with electrochemical double layer (EDL) capacitance and redox capacitance contributions to the electric charge storage were tested in 1 M H2SO4 to quantify the benefit and the limitation of the surface redox reactions on the electrochemical performances of the resulting pseudo-capacitive materials. The electrochemical performances of an electrochemically anodized carbon electrode and a catechol-modified carbon electrode, which make use both EDL capacitance of the porous structure of the carbon and redox capacitance, were compared to the performances obtained for the pristine carbon. Nitrogen gas adsorption measurements have been used for studying the impact of the grafting on the BET surface area, pore size distribution, pore volume and average pore diameter. The electrochemical behavior of carbon materials was studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The EIS data were discussed by using a complex capacitance model that allows defining the characteristic time constant, the global capacitance and the frequency at which the maximum charge stored is reached. The EIS measurements were achieved at different dc potential values where a redox activity occurs and the evolution of the capacitance and the capacitive relaxation time with the electrode potential are presented. Realistic galvanostatic charge/discharge measurements performed at different current rates corroborate the results obtained by impedance.

Laser shock peening without coating induced residual stress distribution, wettability characteristics and enhanced pitting corrosion resistance of austenitic stainless steel

NASA Astrophysics Data System (ADS)

Prabhakaran, S.; Kulkarni, Aniket; Vasanth, G.; Kalainathan, S.; Shukla, Pratik; Vasudevan, Vijay K.

2018-01-01

Low energy laser shock peening without coating (LSPwC) was conducted on AISI 304 austenitic stainless steel specimens with varying pulse densities or overlapping. Highest magnitude of compressive residual stress (CRS) was achieved for an optimized pulse density of 2500 pulses/cm2 (75% overlapping). The 2-D and 3-D topographical analysis were indicative of the fact that controlled roughening of the surface was achieved after the LSPwC process. After the LSPwC process, the hydrophilic unpeened surface was converted into the hydrophobic surface, thus decreasing the wettability characteristics of the surface. The X-ray diffraction (XRD) results reveal that there is a beginning of the martensite transformation and the rise in the intensity value of the peaks after LSPwC indicates the presence of compressive residual stresses induced in the specimen. The optical microscope and high-resolution transmission electron microscope results provided evidence of grain refinement and deformation induced refinement features such as multidirectional mechanical twinning, dislocations lines, micro shear cells and stacking faults in the near and sub-surface areas. The average hardness value of the LSPwC specimens was found to be increased by 28% more than the untreated specimen. The potentiodynamic polarization revealed that there was a considerable amount of increase in the pitting corrosion resistance after the LSPwC process, thus, supporting to extend the fatigue life of the specimen. The electrochemical impedance spectroscopic (EIS) analysis depicts that the LSPwC process supports the formation of the strong passivation layer in 3.5% NaCl solution.

Electrocatalytic oxidation of cellulose at a gold electrode.

PubMed

Sugano, Yasuhito; Latonen, Rose-Marie; Akieh-Pirkanniemi, Marceline; Bobacka, Johan; Ivaska, Ari

2014-08-01

The electrochemical properties of cellulose dissolved in NaOH solution at a Au surface were investigated by cyclic voltammetry, FTIR spectroscopy, the electrochemical quartz crystal microbalance technique, and electrochemical impedance spectroscopy. The reaction products were characterized by SEM, TEM, and FTIR and NMR spectroscopy. The results imply that cellulose is irreversibly oxidized. Adsorption and desorption of hydroxide ions at the Au surface during potential cycling have an important catalytic role in the reaction (e.g., approach of cellulose to the electrode surface, electron transfer, adsorption/desorption of the reaction species at the electrode surface). Moreover, two types of cellulose derivatives were obtained as products. One is a water-soluble cellulose derivative in which some hydroxyl groups are oxidized to carboxylic groups. The other derivative is a water-insoluble hybrid material composed of cellulose and Au nanoparticles (≈4 nm). Furthermore, a reaction scheme of the electrocatalytic oxidation of cellulose at a gold electrode in a basic medium is proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploring Local Electrostatic Effects with Scanning Probe Microscopy: Implications for Piezoresponse Force Microscopy and Triboelectricity

DOE PAGES

Balke, Nina; Maksymovych, Petro; Jesse, Stephen; ...

2014-09-25

The implementation of contact mode Kelvin probe force microscopy (KPFM) utilizes the electrostatic interactions between tip and sample when the tip and sample are in contact with each other. Surprisingly, the electrostatic forces in contact are large enough to be measured even with tips as stiff as 4.5 N/m. As for traditional non-contact KPFM, the signal depends strongly on electrical properties of the sample, such as the dielectric constant, and the tip-properties, such as the stiffness. Since the tip is in contact with the sample, bias-induced changes in the junction potential between tip and sample can be measured with highermore » lateral and temporal resolution compared to traditional non-contact KPFM. Significant and reproducible variations of tip-surface capacitance are observed and attributed to surface electrochemical phenomena. Lastly, observations of significant surface charge states at zero bias and strong hysteretic electromechanical responses at non-ferroelectric surface have significant implications for fields such as triboelectricity and piezoresponse force microscopy.« less

First-Principles Modeling of Mn(II) Migration above and Dissolution from Li x Mn 2 O 4 (001) Surfaces

DOE PAGES

Leung, Kevin

2016-12-10

The density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (001) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on graphite anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is far from sufficient. Key steps that facilitate Mn(II) loss include concerted liquid/solid-state motions; proton-induced weakening of Mn–O bonds forming mobile OH – surface groups; and chemicalmore » reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI components facilitate electrochemical reduction and decomposition of LEDC. Our findings help inform future design of protective coatings, electrolytes, additives, and interfaces.« less

Block Copolymer Patterns as Templates for the Electrocatalyzed Deposition of Nanostructures on Electrodes and for the Generation of Surfaces of Controlled Wettability.

PubMed

Chandaluri, Chanchayya Gupta; Pelossof, Gilad; Tel-Vered, Ran; Shenhar, Roy; Willner, Itamar

2016-01-20

ITO electrodes modified with a nanopatterned film of polystyrene-block-poly(2-vinylpyridine), PS-b-P2VP, where the P2VP domains are quaternized with iodomethane, are used for selective deposition of redox-active materials. Electrochemical studies (cyclic voltammetry, Faradaic impedance measurements) indicate that the PS domains insulate the conductive surface toward redox labels in solution. In turn, the quaternized P2VP domains electrostatically attract negatively charged redox labels solubilized in the electrolyte solution, resulting in an effective electron transfer between the electrode and the redox label. This phenomenon is implemented for the selective deposition of the electroactive Prussian blue on the nanopatterned surface and for the electrochemical deposition of Au nanoparticles, modified with a monolayer of p-aminothiophenol/2-mercaptoethanesulfonic acid, on the quaternized P2VP domains. The patterned Prussian blue-modified surface enables controlling the wettability properties by the content of the electrochemically deposited Prussian blue. Controlled wettability is unattainable with the homopolymer-modified surface, attesting to the role of the nanopattern.

Pullulan as a potent green inhibitor for corrosion mitigation of aluminum composite: Electrochemical and surface studies.

PubMed

B P, Charitha; Rao, Padmalatha

2018-06-01

This work emphasizes the corrosion inhibition ability of pullulan, an environmentally benign fungal polysaccharide on acid corrosion of 6061Aluminum-15% (v) SiC (P) composite material (Al-CM). The electrochemical measurements such as potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) studies were carried out for the corrosion inhibition studies. Conditions were optimized to obtain maximum inhibition efficiency, by performing the experiment at varying concentrations of inhibitor, in the temperature range of 308K- 323K. Surface morphology studies were done to reaffirm the adsorption of inhibitor on the surface of composite material. Pullulan acted as mixed type of inhibitor with a maximum efficiency of 89% at 303K for the addition of 1.0 gL -1 of inhibitor. Evaluation of kinetic and thermodynamic parameters revealed that inhibitor underwent physical adsorption onto the surface of Al-CM and obeyed Freundlich adsorption isotherm. The surface characterization like SEM-EDX, AFM confirmed the adsorption of pullulan molecule. Pullulan can be considered as effective, eco friendly green inhibitor for the corrosion control of Al-CM. Copyright © 2018 Elsevier B.V. All rights reserved.

Formation of mixed organic layers by stepwise electrochemical reduction of diazonium compounds.

PubMed

Santos, Luis; Ghilane, Jalal; Lacroix, Jean Christophe

2012-03-28

This work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (β-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by β-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

Electrochemical cell structure including an ionomeric barrier

DOEpatents

Lambert, Timothy N.; Hibbs, Michael

2017-06-20

An apparatus includes an electrochemical half-cell comprising: an electrolyte, an anode; and an ionomeric barrier positioned between the electrolyte and the anode. The anode may comprise a multi-electron vanadium phosphorous alloy, such as VP.sub.x, wherein x is 1-5. The electrochemical half-cell is configured to oxidize the vanadium and phosphorous alloy to release electrons. A method of mitigating corrosion in an electrochemical cell includes disposing an ionomeric barrier in a path of electrolyte or ion flow to an anode and mitigating anion accumulation on the surface of the anode.

Macroporous mesh of nanoporous gold in electrochemical monitoring of superoxide release from skeletal muscle cells.

PubMed

Banan Sadeghian, Ramin; Han, Jiuhui; Ostrovidov, Serge; Salehi, Sahar; Bahraminejad, Behzad; Ahadian, Samad; Chen, Mingwei; Khademhosseini, Ali

2017-02-15

Real-time monitoring of metabolically relevant biochemicals released in minuscule amounts is of utmost diagnostic importance. Superoxide anion as a primary member of reactive oxygen species, has physiological and pathological effects that depend on its concentration and release rate. Here we present fabrication and successfully testing of a highly sensitive electrochemical biosensor featuring a three-dimensional macroporous mesh of nanoporous gold tailored to measure the dynamics of extracellular superoxide concentration. Wide and accessible surface of the mesh combined with high porosity of the thin nanoporous gold coating enables capturing the analyte in pico- to nano-molar ranges. The mesh is functionalized with cytochrome-c (cyt-c) and incorporated as a working electrode to measure the release rate of drug-induced superoxides from C2C12 cells through a porous membrane. The device displays a considerably improved superoxide sensitivity of 7.29nAnM - 1 cm - 2 and a low level of detection of 70pM. Such sensitivity is orders of magnitude higher than any similar enzyme-based electrochemical superoxide sensor and is attributed to the facile diffusion of the analyte through the well-spread nanofeatured gold skin. Superoxide generation rates captured from monolayer myoblast cultures containing about 4×10 4 cells, varied from 1.0 to 9.0nMmin - 1 in a quasi-linear fashion as a function of drug concentration. This work provides a platform for the development of highly sensitive molecular electrochemical biosensors. Copyright © 2016 Elsevier B.V. All rights reserved.

Electrochemically induced dual reactive barriers for transformation of TCE and mixture of contaminants in groundwater.

PubMed

Mao, Xuhui; Yuan, Songhu; Fallahpour, Noushin; Ciblak, Ali; Howard, Joniqua; Padilla, Ingrid; Loch-Caruso, Rita; Alshawabkeh, Akram N

2012-11-06

A novel reactive electrochemical flow system consisting of an iron anode and a porous cathode is proposed for the remediation of mixture of contaminants in groundwater. The system consists of a series of sequentially arranged electrodes, a perforated iron anode, a porous copper cathode followed by a mesh-type mixed metal oxide anode. The iron anode generates ferrous species and a chemically reducing environment, the porous cathode provides a reactive electrochemically reducing barrier, and the inert anode provides protons and oxygen to neutralize the system. The redox conditions of the electrolyte flowing through this system can be regulated by controlling the distribution of the electric current. Column experiments are conducted to evaluate the process and study the variables. The electrochemical reduction on a copper foam cathode produced an electrode-based reductive potential capable of reducing TCE and nitrate. Rational electrodes arrangement, longer residence time of electrolytes and higher surface area of the foam electrode improve the reductive transformation of TCE. More than 82.2% TCE removal efficiency is achieved for the case of low influent concentration (<7.5 mg/L) and high current (>45 mA). The ferrous species produced from the iron anode not only enhance the transformation of TCE on the cathode, but also facilitates transformation of other contaminants including dichromate, selenate and arsenite. Removal efficiencies greater than 80% are achieved for these contaminants in flowing contaminated water. The overall system, comprising the electrode-based and electrolyte-based barriers, can be engineered as a versatile and integrated remedial method for a relatively wide spectrum of contaminants and their mixtures.

Effects of surface coating of Y(OH) 3 on the electrochemical performance of spherical Ni(OH) 2

NASA Astrophysics Data System (ADS)

Fan, Jing; Yang, Yifu; Yu, Peng; Chen, Weihua; Shao, Huixia

The effects of surface coating of Y(OH) 3 on the electrochemical performance of spherical Ni(OH) 2 were studied by cyclic voltammetry (CV) with soft-embedded electrode (SE-E). The coating was performed by chemical surface precipitation under different conditions. The structure, morphology, chemical composition and electrochemical properties of two different samples with surface coating of Y(OH) 3 were characterized and compared. The results show that a two-step oxidation process exists in the oxidation procedure of spherical Ni(OH) 2 corresponding to the formation of Ni(III) and Ni(IV), respectively. The conversion of Ni(III) to Ni(IV) is regarded as a side reaction in which Ni(IV) species is not stable. The presence of Y(OH) 3 on the particle surface can restrain the side reactions, especially the formation of Ni(IV). The application of coated Ni(OH) 2 to sealed Ni-MH batteries yielded a charge acceptance of about 88% at 60 °C. The results manifest that the high-temperature performance of Ni(OH) 2 electrode is related to the distribution of the adding elements in surface oxide layer of Ni(OH) 2, the sample with dense and porous coating surface, larger relative surface content and higher utilization ratio of yttrium is more effective.

Titanium is not "the most biocompatible metal" under cathodic potential: The relationship between voltage and MC3T3 preosteoblast behavior on electrically polarized cpTi surfaces.

PubMed

Ehrensberger, Mark T; Sivan, Shiril; Gilbert, Jeremy L

2010-06-15

An electrochemically controlled system has been developed which allows for cell culture directly on electrically polarized metal surfaces with simultaneous control and assessment of the electrochemical current, potential, and impedance of the interface. This system was utilized in this study to assess the interactions between electrochemically polarized commercially pure titanium (cpTi) and MC3T3 preosteoblast cells. Cells were cultured on CpTi for 24 h at static potentials between -1000 mV and +1000 mV vs. Ag/AgCl and cell morphology (SEM and cell area) and viability (MTT and Live-Dead assay) were assessed along with the electrochemical current densities and surface oxide impedance properties. The results indicate that cathodic polarization in the range of -600 mV to -1000 mV markedly reduces the spreading and viability of cells cultured directly on cpTi within 24 h, while anodic polarization (-300 mV to +1000 mV) out to 72 h shows no difference in cell behavior as compared to the OCP condition. Analysis of the relationship between the cell outcomes and the electrochemical current densities and impedance indicated the presence of voltage-dependent electrochemical thresholds (cathodic current density, i(c) > 1.0 microA/cm(2), R(p) < 10(5) Omega cm(2)) which may control the biocompatibility of cpTi. In addition, these outcomes have direct clinical significance for modular orthopedic implants whose potential can shift, via fretting corrosion, down into the range of potentials exhibiting poor cell behavior. (c) 2009 Wiley Periodicals, Inc.

Quantum-Dot-Based Electrochemical Immunoassay for High-Throughput Screening of the Prostate-Specific Antigen

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

Wang, Jun; Liu, Guodong; Wu, Hong

2008-01-01

In this paper, we demonstrate an electrochemical high-throughput sensing platform for simple, sensitive detection of PSA based on QD labels. This sensing platform uses a microplate for immunoreactions and disposable screen-printed electrodes (SPE) for electrochemical stripping analysis of metal ions released from QD labels. With the 96-well microplate, capturing antibodies are conveniently immobilized to the well surface, and the process of immunoreaction is easily controlled. The formed sandwich complexes on the well surface are also easily isolated from reaction solutions. In particular, a microplate-based electrochemical assay can make it feasible to conduct a parallel analysis of several samples or multiplemore » protein markers. This assay offers a number of advantages including (1) simplicity, cost-effectiveness, (2) high sensitivity, (3) capability to sense multiple samples or targets in parallel, and (4) a potentially portable device with an SPE array implanted in the microplate. This PSA assay is sensitive because it uses two amplification processes: (1) QDs as a label for enhancing electrical signal since secondary antibodies are linked to QDs that contain a large number of metal atoms and (2) there is inherent signal amplification for electrochemical stripping analysis—preconcentration of metal ion onto the electrode surface for amplifying electrical signals. Therefore, the high sensitivity of this method, stemming from dual signal amplification via QD labels and pre-concentration, allows low concentration levels to be detected while using small sample volumes. Thus, this QD-based electrochemical detection approach offers a simple, rapid, cost-effective, and high throughput assay of PSA.« less

Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy

DOE PAGES

Lee, Sang Chul; Benck, Jesse D.; Tsai, Charlie; ...

2015-12-01

Amorphous MoS x is a highly active, earth-abundant catalyst for the electrochemical hydrogen evolution reaction. Previous studies have revealed that this material initially has a composition of MoS 3, but after electrochemical activation, the surface is reduced to form an active phase resembling MoS 2 in composition and chemical state. However, structural changes in the Mo Sx catalyst and the mechanism of the activation process remain poorly understood. In this study, we employ transmission electron microscopy (TEM) to image amorphous MoS x catalysts activated under two hydrogen-rich conditions: ex situ in an electrochemical cell and in situ in an environmentalmore » TEM. For the first time, we directly observe the formation of crystalline domains in the MoS x catalyst after both activation procedures as well as spatially localized changes in the chemical state detected via electron energy loss spectroscopy. Using density functional theory calculations, we investigate the mechanisms for this phase transformation and find that the presence of hydrogen is critical for enabling the restructuring process. Our results suggest that the surface of the amorphous MoS x catalyst is dynamic: while the initial catalyst activation forms the primary active surface of amorphous MoS 2, continued transformation to the crystalline phase during electrochemical operation could contribute to catalyst deactivation. Finally, these results have important implications for the application of this highly active electrocatalyst for sustainable H 2 generation.« less

An electrochemical sensing approach for scouting microbial chemolithotrophic metabolisms.

PubMed

Saavedra, Albert; Figueredo, Federico; Cortón, Eduardo; Abrevaya, Ximena C

2018-05-01

The present study was aimed to test an electrochemical sensing approach for the detection of an active chemolithotrophic metabolism (and therefore the presence of chemolithotrophic microorganisms) by using the corrosion of pyrite by Acidithiobacillus ferrooxidans as a model. Different electrochemical techniques were combined with adhesion studies and scanning electron microscopy (SEM). The experiments were performed in presence or absence of A. ferrooxidans and without or with ferrous iron in the culture medium (0 and 0.5 g L -1 , respectively). Electrochemical parameters were in agreement with voltammetric studies and SEM showing that it is possible to distinguish between an abiotically-induced corrosion process (AIC) and a microbiologically-induced corrosion process (MIC). The results show that our approach not only allows the detection of chemolithotrophic activity of A. ferrooxidans but also can characterize the corrosion process. This may have different kind of applications, from those related to biomining to life searching missions in other planetary bodies. Copyright © 2018 Elsevier B.V. All rights reserved.

Ultrasensitive electrochemical biosensor for detection of DNA from Bacillus subtilis by coupling target-induced strand displacement and nicking endonuclease signal amplification.

PubMed

Hu, Yuhua; Xu, Xueqin; Liu, Qionghua; Wang, Ling; Lin, Zhenyu; Chen, Guonan

2014-09-02

A simple, ultrasensitive, and specific electrochemical biosensor was designed to determine the given DNA sequence of Bacillus subtilis by coupling target-induced strand displacement and nicking endonuclease signal amplification. The target DNA (TD, the DNA sequence from the hypervarient region of 16S rDNA of Bacillus subtilis) could be detected by the differential pulse voltammetry (DPV) in a range from 0.1 fM to 20 fM with the detection limit down to 0.08 fM at the 3s(blank) level. This electrochemical biosensor exhibits high distinction ability to single-base mismatch, double-bases mismatch, and noncomplementary DNA sequence, which may be expected to detect single-base mismatch and single nucleotide polymorphisms (SNPs). Moreover, the applicability of the designed biosensor for detecting the given DNA sequence from Bacillus subtilis was investigated. The result obtained by electrochemical method is approximately consistent with that by a real-time quantitative polymerase chain reaction detecting system (QPCR) with SYBR Green.

Interface design for CMOS-integrated Electrochemical Impedance Spectroscopy (EIS) biosensors.

PubMed

Manickam, Arun; Johnson, Christopher Andrew; Kavusi, Sam; Hassibi, Arjang

2012-10-29

Electrochemical Impedance Spectroscopy (EIS) is a powerful electrochemical technique to detect biomolecules. EIS has the potential of carrying out label-free and real-time detection, and in addition, can be easily implemented using electronic integrated circuits (ICs) that are built through standard semiconductor fabrication processes. This paper focuses on the various design and optimization aspects of EIS ICs, particularly the bio-to-semiconductor interface design. We discuss, in detail, considerations such as the choice of the electrode surface in view of IC manufacturing, surface linkers, and development of optimal bio-molecular detection protocols. We also report experimental results, using both macro- and micro-electrodes to demonstrate the design trade-offs and ultimately validate our optimization procedures.

The Mathematical Modeling and Computer Simulation of Electrochemical Micromachining Using Ultrashort Pulses

NASA Astrophysics Data System (ADS)

Kozak, J.; Gulbinowicz, D.; Gulbinowicz, Z.

2009-05-01

The need for complex and accurate three dimensional (3-D) microcomponents is increasing rapidly for many industrial and consumer products. Electrochemical machining process (ECM) has the potential of generating desired crack-free and stress-free surfaces of microcomponents. This paper reports a study of pulse electrochemical micromachining (PECMM) using ultrashort (nanoseconds) pulses for generating complex 3-D microstructures of high accuracy. A mathematical model of the microshaping process with taking into consideration unsteady phenomena in electrical double layer has been developed. The software for computer simulation of PECM has been developed and the effects of machining parameters on anodic localization and final shape of machined surface are presented.

Chemically modified electrodes by nucleophilic substitution of chlorosilylated platinum oxide surfaces

NASA Astrophysics Data System (ADS)

Chen, Chun-Hsien; Hutchison, James H.; Postlethwaite, Timothy A.; Richardson, John N.; Murray, R. W.

1994-07-01

Chlorosilylated platinum oxide electrode surfaces can be generated by reaction of SiCl4 vapor with an electrochemically prepared monolayer of platinum oxide. A variety of nucleophilic agents (such as alcohols, amines, thiols, and Grignard reagents) can be used to displace chloride and thereby functionalize the metal surface. Electroactive surfaces prepared with ferrocene methanol as the nucleophile show that derivatization by small molecules can achieve coverages on the order of a full monolayer. Surfaces modified with long-chain alkyl groups efficiently block electrode reactions of redox probes dissolved in the contacting solution, but other electrochemical (double layer capacitance and surface coverage) and contact angle measurements suggest that these molecule films are not highly ordered, self-assembled monolayers.

Superconductivity in FeTe0.8S0.2 induced by battery-like reaction

NASA Astrophysics Data System (ADS)

Yamashita, Aichi; Demura, Satoshi; Tanaka, Masashi; Deguchi, Keita; Yamaki, Takuma; Hara, Hiroshi; Suzuki, Kouji; Zhang, Yunchao; Denholme, Saleem James; Okazaki, Hiroyuki; Fujioka, Masaya; Yamaguchi, Takahide; Takeya, Hiroyuki; Takano, Yoshihiko

2014-12-01

Superconductivity is successfully induced by utilizing a battery-like reaction found in a typical Li-ion battery. Excess Fe in FeTe0.8S0.2 is electrochemically de-intercalated by applying a voltage in a citric acid solution. The superconducting properties improve with an increase in the applied voltage up to 1.5 V. This result suggests that an electrochemical reaction can be used as a novel method to develop new superconducting materials.

Electro-chemical grinding

NASA Technical Reports Server (NTRS)

Feagans, P. L.

1972-01-01

Electro-chemical grinding technique has rotation speed control, constant feed rates, and contour control. Hypersonic engine parts of nickel alloys can be almost 100% machined, keeping tool pressure at virtual zero. Technique eliminates galling and permits constant surface finish and burr-free interrupted cutting.

Electrochemical capacitor

DOEpatents

Anderson, Marc A.; Liu, Kuo -Chuan; Mohr, Charles M.

1999-10-05

An inexpensive porous metal oxide material having high surface area, good conductivity and high specific capacitance is advantageously used in an electrochemical capacitor. The materials are formed in a sol-gel process which affords control over the properties of the resultant metal oxide materials.

Impact of electrolyte composition on the reactivity of a redox active polymer studied through surface interrogation and ion-sensitive scanning electrochemical microscopy.

PubMed

Burgess, Mark; Hernández-Burgos, Kenneth; Cheng, Kevin J; Moore, Jeffrey S; Rodríguez-López, Joaquín

2016-06-21

Elucidating the impact of interactions between the electrolyte and electroactive species in redox active polymers is key to designing better-performing electrodes for electrochemical energy storage and conversion. Here, we present on the improvement of the electrochemical activity of poly(para-nitrostyrene) (PNS) in solution and as a film by exploiting the ionic interactions between reduced PNS and K(+), which showed increased reactivity when compared to tetrabutylammonium (TBA(+))- and Li(+)-containing electrolytes. While cyclic voltammetry enabled the study of the effects of cations on the electrochemical reversibility and the reduction potential of PNS, scanning electrochemical microscopy (SECM) provided new tools to probe the ionic and redox reactivity of this system. Using an ion-sensitive Hg SECM tip allowed to probe the ingress of ions into PNS redox active films, while surface interrogation SECM (SI-SECM) measured the specific kinetics of PNS and a solution phase mediator in the presence of the tested electrolytes. SI-SECM measurements illustrated that the interrogation kinetics of PNS in the presence of K(+) compared to TBA(+) and Li(+) are greatly enhanced under the same surface concentration of adsorbed radical anion, exhibiting up to a 40-fold change in redox kinetics. We foresee using this new application of SECM methods for elucidating optimal interactions that enhance polymer reactivity for applications in redox flow batteries.

Synergetic enhancement of gold nanoparticles and 2-mercaptobenzothiazole as highly-sensitive sensing strategy for tetrabromobisphenol A

NASA Astrophysics Data System (ADS)

Chen, Xuerong; Ji, Liudi; Zhou, Yikai; Wu, Kangbing

2016-05-01

Various gold nanoparticles (AuNPs) were in-situ prepared on the electrode surface through electrochemical reduction under different potentials such as -0.60, -0.50, -0.40, -0.30 and -0.20 V. The reduction potentials heavily affect the surface morphology and electrochemical activity of AuNPs such as effective area and catalytic ability, as confirmed using atomic force microscopy and electrochemical impedance spectroscopy. The electrochemical behaviors of tetrabromobisphenol A (TBBPA), a widely-existed pollutant with severe adverse health effects, were studied. The oxidation activity of TBBPA enhances obviously on the surface of AuNPs, and the signal improvements of TBBPA show difference on the prepared AuNPs. Interestingly, the existence of 2-mercaptobenzothiazole (MBT) further improves the oxidation signals of TBBPA on AuNPs. The synergetic enhancement effects of AuNPs and MBT were studied using cyclic voltammetry and chronocoulometry. The numerous nano-scaled gold particles together with the strong hydrophobic interaction between TBBPA and the assembled MBT on AuNPs jointly provide highly-effective accumulation for TBBPA. As a result, a sensitive and simple electrochemical method was developed for the direct determination of TBBPA, with detection limit of 0.12 μg L-1 (0.22 nM). The practical applications in water samples manifest that this new sensing system is accurate and feasible.

Quadrilateral Micro-Hole Array Machining on Invar Thin Film: Wet Etching and Electrochemical Fusion Machining

PubMed Central

Choi, Woong-Kirl; Kim, Seong-Hyun; Choi, Seung-Geon; Lee, Eun-Sang

2018-01-01

Ultra-precision products which contain a micro-hole array have recently shown remarkable demand growth in many fields, especially in the semiconductor and display industries. Photoresist etching and electrochemical machining are widely known as precision methods for machining micro-holes with no residual stress and lower surface roughness on the fabricated products. The Invar shadow masks used for organic light-emitting diodes (OLEDs) contain numerous micro-holes and are currently machined by a photoresist etching method. However, this method has several problems, such as uncontrollable hole machining accuracy, non-etched areas, and overcutting. To solve these problems, a machining method that combines photoresist etching and electrochemical machining can be applied. In this study, negative photoresist with a quadrilateral hole array pattern was dry coated onto 30-µm-thick Invar thin film, and then exposure and development were carried out. After that, photoresist single-side wet etching and a fusion method of wet etching-electrochemical machining were used to machine micro-holes on the Invar. The hole machining geometry, surface quality, and overcutting characteristics of the methods were studied. Wet etching and electrochemical fusion machining can improve the accuracy and surface quality. The overcutting phenomenon can also be controlled by the fusion machining. Experimental results show that the proposed method is promising for the fabrication of Invar film shadow masks. PMID:29351235

In situ cell culture monitoring on a Ti-6Al-4V surface by electrochemical techniques.

PubMed

García-Alonso, M C; Saldaña, L; Alonso, C; Barranco, V; Muñoz-Morris, M A; Escudero, M L

2009-05-01

In this work, the in situ interaction between Ti-6Al-4V alloy and osteoblastic cells has been studied by electrochemical techniques as a function of time. The interaction has been monitored for cell adhesion and growth of human osteoblastic Saos-2 cells on Ti-6Al-4V samples. The study has been carried out by electrochemical techniques, e.g., studying the evolution of corrosion potential with exposure time and by electrochemical impedance spectroscopy. The impedance results have been analyzed by using different equivalent circuit models that simulate the interface state at each testing time. The adhesion of the osteoblastic cells on the Ti-6Al-4V alloy leads to surface areas with different cell coverage rates, thus showing the different responses in the impedance diagrams with time. The effect of the cells on the electrochemical response of Ti-6Al-4V alloy is clearly seen after 4 days of testing, in which two isolated and well-differentiated time constants are clearly observed. One of these is associated with the presence of the cells and the other with a passive film on the Ti-6Al-4V alloy. After 7 days of culture, the system is governed by a resistive component over a wide frequency range which is associated with an increase in the cell coverage rate on the surface due to the extracellular matrix.

Platinum nanoparticles functionalized nitrogen doped graphene platform for sensitive electrochemical glucose biosensing.

PubMed

Yang, Zhanjun; Cao, Yue; Li, Juan; Jian, Zhiqin; Zhang, Yongcai; Hu, Xiaoya

2015-04-29

In this work, we reported an efficient platinum nanoparticles functionalized nitrogen doped graphene (PtNPs@NG) nanocomposite for devising novel electrochemical glucose biosensor for the first time. The fabricated PtNPs@NG and biosensor were characterized using transmission electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, static water contact angle, UV-vis spectroscopy, electrochemical impedance spectra and cyclic voltammetry, respectively. PtNPs@NG showed large surface area and excellent biocompatibility, and enhanced the direct electron transfer between enzyme molecules and electrode surface. The glucose oxidase (GOx) immobilized on PtNPs@NG nanocomposite retained its bioactivity, and exhibited a surface controlled, quasi-reversible and fast electron transfer process. The constructed glucose biosensor showed wide linear range from 0.005 to 1.1mM with high sensitivity of 20.31 mA M(-1) cm(-2). The detection limit was calculated to be 0.002 mM at signal-to-noise of 3, which showed 20-fold decrease in comparison with single NG-based electrochemical biosensor for glucose. The proposed glucose biosensor also demonstrated excellent selectivity, good reproducibility, acceptable stability, and could be successfully applied in the detection of glucose in serum samples at the applied potential of -0.33 V. This research provided a promising biosensing platform for the development of excellent electrochemical biosensors. Copyright © 2015 Elsevier B.V. All rights reserved.

Fabrication and surface-modification of implantable microprobes for neuroscience studies

NASA Astrophysics Data System (ADS)

Cao, H.; Nguyen, C. M.; Chiao, J. C.

2012-06-01

In this work implantable micro-probes for central nervous system (CNS) studies were developed on silicon and polyimide substrates. The probes which contained micro-electrode arrays with different surface modifications were designed for implantation in the CNS. The electrode surfaces were modified with nano-scale structures that could greatly increase the active surface area in order to enhance the electrochemical current outputs while maintaining micro-scale dimensions of the electrodes and probes. The electrodes were made of gold or platinum, and designed with different sizes. The silicon probes were modified by silicon nanowires fabricated with the vapor-liquid-solid mechanism at high temperatures. With polyimide substrates, the nanostructure modification was carried out by applying concentrated gold or silver colloid solutions onto the micro-electrodes at room temperature. The surfaces of electrodes before and after modification were observed by scanning electron microscopy. The silicon nanowire-modified surface was characterized by cyclic voltammetry. Experiments were carried out to investigate the improvement in sensing performance. The modified electrodes were tested with H2O2, electrochemical L-glutamate and dopamine. Comparisons between electrodes with and without nanostructure modification were conducted showing that the modifications have enhanced the signal outputs of the electrochemical neurotransmitter sensors.

Electrochemical surface modification of carbon mesh anode to improve the performance of air-cathode microbial fuel cells.

PubMed

Luo, Jianmei; Chi, Meiling; Wang, Hongyu; He, Huanhuan; Zhou, Minghua

2013-12-01

A convenient and promising alternative to surface modification of carbon mesh anode was fulfilled by electrochemical oxidation in the electrolyte of nitric acid or ammonium nitrate at ambient temperature. It was confirmed that such an anode modification method was low cost and effective not only in improving the efficiency of power generation in microbial fuel cells (MFCs) for synthetic wastewater treatment, but also helping to reduce the period for MFCs start-up. The MFCs with anode modification in electrolyte of nitric acid performed the best, achieving a Coulombic efficiency enhancement of 71 %. As characterized, the electrochemical modification resulted in the decrease of the anode potential and internal resistance but the increase of current response and nitrogen-containing and oxygen-containing functional groups on the carbon surface, which might contribute to the enhancement on the performances of MFCs.

Theoretical, thermodynamic and electrochemical analysis of biotin drug as an impending corrosion inhibitor for mild steel in 15% hydrochloric acid

PubMed Central

Xu, Xihua; Sun, Zhipeng; Ansari, K. R.; Lin, Yuanhua

2017-01-01

The corrosion mitigation efficiency of biotin drug for mild steel in 15% hydrochloric acid was thoroughly investigated by weight loss and electrochemical methods. The surface morphology was studied by the contact angle, scanning electrochemical microscopy, atomic force microscopy and scanning electron microscopy methods. Quantum chemical calculation and Fukui analysis were done to correlate the experimental and theoretical data. The influence of the concentration of inhibitor, immersion time, temperature, activation energy, enthalpy and entropy has been reported. The mitigation efficiency of biotin obtained by all methods was in good correlation with each other. Polarization studies revealed that biotin acted as a mixed inhibitor. The adsorption of biotin was found to obey the Langmuir adsorption isotherm. Surface studies showed the hydrophobic nature of the steel with inhibitor and vindicated the formation of a film on the metal surface that reduced the corrosion rate. PMID:29308235

Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes**

PubMed Central

Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

2015-01-01

In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6Sr0.4FeO3−δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe0 on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity. PMID:25557533

A study of the effects of phosphates on copper corrosion in drinking water: Copper release, electrochemical, and surface analysis approach

NASA Astrophysics Data System (ADS)

Kang, Young C.

The following work is the study to evaluate the impact of corrosion inhibitors on the copper metal in drinking water and to investigate the corrosion mechanism in the presence and absence of inhibitors. Electrochemical experiments were conducted to understand the effect of specific corrosion inhibitors in synthetic drinking water which was prepared with controlled specific water quality parameters. Water chemistry was studied by Inductively Coupled Plasma--Atomic Emission Spectroscopy (ICP--AES) to investigate the copper leaching rate with time. Surface morphology, crystallinity of corrosion products, copper oxidation status, and surface composition were characterized by various solid surface analysis methods, such as Scanning Electron Microscopy/Energy--Dispersive Spectrometry (SEM/EDS), Grazing-Incidence-angle X-ray Diffraction (GIXRD), X-ray Photoelectron Spectroscopy (XPS), and Time-of-Flight Secondary Ions Mass Spectrometry (ToF-SIMS). The purpose of the first set of experiments was to test various electrochemical techniques for copper corrosion for short term before studying a long term loop system. Surface analysis techniques were carried out to identify and study the corrosion products that form on the fresh copper metal surface when copper coupons were exposed to test solutions for 2 days of experiments time. The second phase of experiments was conducted with a copper pipe loop system in a synthetic tap water over an extended period of time, i.e., 4 months. Copper release and electrochemically measured corrosion activity profiles were monitored carefully with and without corrosion inhibitor, polyphosphate. A correlation between the copper released into the solution and the electrochemically measured corrosion activities was also attempted. To investigate corrosion products on the copper pipe samples, various surface analysis techniques were applied in this study. Especially, static mass spectra acquisition and element distribution mapping were carried out by ToF-SIMS. Dynamic SIMS provided shallow depth profile of corroded copper sample. The third set of the experiments was related to electrochemical noise (EN) measurement through copper coupons to pipes. Calculating corrosion rate of a metal and predicting exactly how long it lasts are problematic since the metal corrosion may be caused by combined corrosion types. Many other metals undergo not only uniform corrosion, but localized corrosion. Uniform corrosion may be conducive for copper pipe to prevent it from further severe corrosion and form passivated film, but localized corrosion causes pinhole leaks and limits the copper pipe applications. The objective of this set of experiment is to discuss the application of electrochemical noise approaches to drinking water copper corrosion problems. Specially, a fundamental description of EN is presented including a discussion of how to interpret the results and technique limitations. Although it was indicated with electrochemical analysis that the corrosion activity was affected by orthophosphate addition in the short-term test, no copper-phosphate complex or compound was found by copper surface characterization. Apparently, orthophosphate can inhibit corrosion by adsorption on the copper surface, but cannot form solid complexes with copper in such a short time, 2 days. When polyphosphate was added into recirculating copper pipe system, copper level increased and polarization resistance decreased. Greenish blue residue on the copper pipe was suspected as copper phosphate complex and corrosion inhibition mechanism was proposed.

Electrochemical and passive behaviour of tin alloyed ferritic stainless steel in concrete environment

NASA Astrophysics Data System (ADS)

Luo, Hong; Su, Huaizhi; Li, Baosong; Ying, Guobing

2018-05-01

In the present work, the electrochemical behavior and semiconducting properties of a tin alloyed ferritic stainless steel in simulated concrete solution in presence of NaCl were estimated by conventional electrochemical methods such as potentiodynamic polarization, electrochemical impedance spectroscopy, and capacitance measurement (Mott-Schottky approach). The surface passive film was analyzed by X-ray photoelectron spectroscopy. The results revealed a good agreement between pitting corrosion, electrochemical behaviour, and electronic properties. The p and n-type bilayer structure passive film were observed. The increase of Sn4+ oxide species in the passive film shows no beneficial effects on the pitting corrosion. In addition, the dehydration of the passive film was further discussed.

Silver nanostructures synthesis via optically induced electrochemical deposition

NASA Astrophysics Data System (ADS)

Li, Pan; Liu, Na; Yu, Haibo; Wang, Feifei; Liu, Lianqing; Lee, Gwo-Bin; Wang, Yuechao; Li, Wen Jung

2016-06-01

We present a new digitally controlled, optically induced electrochemical deposition (OED) method for fabricating silver nanostructures. Projected light patterns were used to induce an electrochemical reaction in a specialized sandwich-like microfluidic device composed of one indium tin oxide (ITO) glass electrode and an optically sensitive-layer-covered ITO electrode. Silver polyhedral nanoparticles, triangular and hexagonal nanoplates, and nanobelts were controllably synthesized in specific positions at which projected light was illuminated. The silver nanobelts had rectangular cross-sections with an average width of 300 nm and an average thickness of 100 nm. By controlling the applied voltage, frequency, and time, different silver nanostructure morphologies were obtained. Based on the classic electric double-layer theory, a dynamic process of reduction and crystallization can be described in terms of three phases. Because it is template- and surfactant-free, the digitally controlled OED method facilitates the easy, low cost, efficient, and flexible synthesis of functional silver nanostructures, especially quasi-one-dimensional nanobelts.

Interphase evolution at two promising electrode materials for Li-ion batteries: LiFePO4 and LiNi1/2 Mn1/2O2.

PubMed

Dupré, Nicolas; Cuisinier, Marine; Martin, Jean-Frederic; Guyomard, Dominique

2014-07-21

The present review reports the characterization and control of interfacial processes occurring on olivine LiFePO(4) and layered LiNi(1/2) Mn(1/2)O(2), standing here as model compounds, during storage and electrochemical cycling. The formation and evolution of the interphase created by decomposition of the electrolyte is investigated by using spectroscopic tools such as magic-angle-spinning nuclear magnetic resonance ((7)Li,(19)F and (31)P) and electron energy loss spectroscopy, in parallel to X-ray photoelectron spectroscopy, to quantitatively describe the interphase and unravel its architecture. The influence of the pristine surface chemistry of the active material is carefully examined. The importance of the chemical history of the surface of the electrode material before any electrochemical cycling and the strong correlation between interface phenomena, the formation/evolution of an interphase, and the electrochemical behavior appear clearly from the use of these combined characterization probes. This approach allows identifying interface aging and failure mechanisms. Different types of surface modifications are then investigated, such as intrinsic modifications upon aging in air or methods based on the use of additives in the electrolyte or carbon coatings on the surface of the active materials. In each case, the species detected on the surface of the materials during storage and cycling are correlated with the electrochemical performance of the modified positive electrodes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Real-time electrochemical detection of extracellular nitric oxide in tobacco cells exposed to cryptogein, an elicitor of defence responses

PubMed Central

Besson-Bard, Angélique; Griveau, Sophie; Bedioui, Fethi; Wendehenne, David

2008-01-01

It was previously reported that cryptogein, an elicitor of defence responses, induces an intracellular production of nitric oxide (NO) in tobacco. Here, the possibility was explored that cryptogein might also trigger an increase of NO extracellular content through two distinct approaches, an indirect method using the NO probe 4,5-diaminofluorescein (DAF-2) and an electrochemical method involving a chemically modified microelectrode probing free NO in biological media. While the chemical nature of DAF-2-reactive compound(s) is still uncertain, the electrochemical modified microelectrodes provide real-time evidence that cryptogein induces an increase of extracellular NO. Direct measurement of free extracellular NO might offer important new insights into its role in plants challenged by biotic stresses. PMID:18653691

Highly sensitive electrochemical detection of cocaine on graphene/AuNP modified electrode via catalytic redox-recycling amplification.

PubMed

Jiang, Bingying; Wang, Min; Chen, Ying; Xie, Jiaqing; Xiang, Yun

2012-02-15

We demonstrated a new strategy for highly sensitive electrochemical detection of cocaine by using two engineered aptamers in connection to redox-recycling signal amplification. The graphene/AuNP nanocomposites were electrochemically deposited on a screen printed carbon electrode to enhance the electron transfers. The cocaine primary binding aptamers were self-assembled on the electrode surface through sulfur-Au interactions. The presence of the target cocaine and the biotin-modified secondary binding aptamers leads to the formation of sandwich complexes on the electrode surface. The streptavidin-conjugated alkaline phosphatases (ALPs) were used as labels to generate quantitative signals. The addition of the ALP substrate and the co-reactant NADH results in the formation of a redox cycle between the enzymatic product and the electrochemically oxidized species and the signal is thus significantly amplified. Because of the effective modification of the sensing surface and signal amplification, low nanomolar (1 nM) detection limit for cocaine is achieved. The proposed aptamer-based sandwich sensing approach for amplified detection of cocaine thus opens new opportunities for highly sensitive determination of other small molecules. Copyright © 2011 Elsevier B.V. All rights reserved.

Self-Organization of Ions at the Interface between Graphene and Ionic Liquid DEME-TFSI.

PubMed

Hu, Guangliang; Pandey, Gaind P; Liu, Qingfeng; Anaredy, Radhika S; Ma, Chunrui; Liu, Ming; Li, Jun; Shaw, Scott K; Wu, Judy

2017-10-11

Electrochemical effects manifest as nonlinear responses to an applied electric field in electrochemical devices, and are linked intimately to the molecular orientation of ions in the electric double layer (EDL). Herein, we probe the origin of the electrochemical effect using a double-gate graphene field effect transistor (GFET) of ionic liquid N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEME-TFSI) top-gate, paired with a ferroelectric Pb 0.92 La 0.08 Zr 0.52 Ti 0.48 O 3 (PLZT) back-gate of compatible gating efficiency. The orientation of the interfacial molecular ions can be extracted by measuring the GFET Dirac point shift, and their dynamic response to ultraviolet-visible light and a gate electric field was quantified. We have observed that the strong electrochemical effect is due to the TFSI anions self-organizing on a treated GFET surface. Moreover, a reversible order-disorder transition of TFSI anions self-organized on the GFET surface can be triggered by illuminating the interface with ultraviolet-visible light, revealing that it is a useful method to control the surface ion configuration and the overall performance of the device.

Electrochemical aptamer-based nanosensor fabricated on single Au nanowire electrodes for adenosine triphosphate assay.

PubMed

Wang, Dongmei; Xiao, Xiaoqing; Xu, Shen; Liu, Yong; Li, Yongxin

2018-01-15

In this work, single Au nanowire electrodes (AuNWEs) were fabricated by laser-assisted pulling/hydrofluoric acid (HF) etching process, which then were characterized by transmission electron microscopy (TEM), electrochemical method and finite-element simulation. The as-prepared single AuNWEs were used to construct electrochemical aptamer-based nanosensors (E-AB nanosensors) based on the formation of Au-S bond that duplex DNA tagged with methylene blue (MB) was modified on the surface of electrode. In the presence of adenosine triphosphate (ATP), the MB-labeled aptamer dissociated from the duplex DNA due to the strong specific affinity between aptamer and target, which lead to the reduction of MB electrochemical signals. Moreover, BSA was employed to further passivate electrode surface bonding sites for the stable of the sensor. The as-prepared E-AB nanosensor has been used for ATP assay with excellent sensitivity and selectivity, even in a complex system like cerebrospinal fluid of rat brain. Considering the unique properties of good stability, larger surface area and smaller overall dimensions, this E-AB nanosensor should be an ideal platform for widely sensing applications in living bio-system. Copyright © 2017 Elsevier B.V. All rights reserved.

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface

PubMed Central

Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.; Yano, Junko; Hussain, Zahid; Liu, Zhi; Crumlin, Ethan J.

2016-01-01

The electrochemical double layer plays a critical role in electrochemical processes. Whilst there have been many theoretical models predicting structural and electrical organization of the electrochemical double layer, the experimental verification of these models has been challenging due to the limitations of available experimental techniques. The induced potential drop in the electrolyte has never been directly observed and verified experimentally, to the best of our knowledge. In this study, we report the direct probing of the potential drop as well as the potential of zero charge by means of ambient pressure X-ray photoelectron spectroscopy performed under polarization conditions. By analyzing the spectra of the solvent (water) and a spectator neutral molecule with numerical simulations of the electric field, we discern the shape of the electrochemical double layer profile. In addition, we determine how the electrochemical double layer changes as a function of both the electrolyte concentration and applied potential. PMID:27576762

A Corona Discharge Initiated Electrochemical Electrospray Ionization Technique

PubMed Central

Lloyd, John R.; Hess, Sonja

2009-01-01

We report here the development of a corona discharge (CD) initiated electrochemical (EC) electrospray ionization (ESI) technique using a standard electrospray ion source. This is a new ionization technique distinct from ESI, electrochemistry inherent to ESI, APCI, and techniques using hydroxyl radicals produced under atmospheric pressure conditions. By maximizing the observable CD at the tip of a stainless steel ESI capillary, efficient electrochemical oxidation of electrochemically active compounds is observed. For electrochemical oxidation to be observed, the ionization potential of the analyte must be lower than Fe. Ferrocene labeled compounds were chosen as the electrochemically active moiety. The electrochemical cell in the ESI source was robust and generated ions with selectivity according to the ionization potential of the analytes and up to zeptomolar sensitivity. Our results indicate that CD initiated electrochemical ionization has the potential to become a powerful technique to increase the dynamic range, sensitivity and selectivity of ESI experiments. Synopsis Using a standard ESI source a corona discharge initiated electrochemical ionization technique was established resulting from the electrochemistry occurring at the CD electrode surface. PMID:19747843

Direct comparison of current-induced spin polarization in topological insulator Bi2Se3 and InAs Rashba states

DOE PAGES

Li, C. H.; van ‘t Erve, O. M. J.; Rajput, S.; ...

2016-11-17

Three-dimensional topological insulators (TIs) exhibit time-reversal symmetry protected, linearly dispersing Dirac surface states with spin–momentum locking. Band bending at the TI surface may also lead to coexisting trivial two-dimensional electron gas (2DEG) states with parabolic energy dispersion. A bias current is expected to generate spin polarization in both systems, although with different magnitude and sign. Here we compare spin potentiometric measurements of bias current-generated spin polarization in Bi2Se3(111) where Dirac surface states coexist with trivial 2DEG states, and in InAs(001) where only trivial 2DEG states are present. We observe spin polarization arising from spin–momentum locking in both cases, with oppositemore » signs of the measured spin voltage. We present a model based on spin dependent electrochemical potentials to directly derive the sign expected for the Dirac surface states, and show that the dominant contribution to the current-generated spin polarization in the TI is from the Dirac surface states.« less

Plasma surface modification of polypropylene track-etched membrane to improve its performance properties

NASA Astrophysics Data System (ADS)

Kravets, L. I.; Elinson, V. M.; Ibragimov, R. G.; Mitu, B.; Dinescu, G.

2018-02-01

The surface and electrochemical properties of polypropylene track-etched membrane treated by plasma of nitrogen, air and oxygen are studied. The effect of the plasma-forming gas composition on the surface morphology is considered. It has been found that the micro-relief of the membrane surface formed under the gas-discharge etching, changes. Moreover, the effect of the non-polymerizing gas plasma leads to formation of oxygen-containing functional groups, mostly carbonyl and carboxyl. It is shown that due to the formation of polar groups on the surface and its higher roughness, the wettability of the plasma-modified membranes improves. In addition, the presence of polar groups on the membrane surface layer modifies its electrochemical properties so that conductivity of plasma-treated membranes increase.

Applications of KPFM-Based Approaches for Surface Potential and Electrochemical Measurements in Liquid

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

Collins, Liam F.; Weber, Stefan A. L.; Rodriguez, Brian

Kelvin probe force microscopy (KPFM) has been widely used to map nanoscale surface potentials of materials in ambient and ultra-high vacuum environments. However, to study and ultimately understand charge-related processes, e.g., in biological systems or to further improve energy storage devices such as electrochemical batteries, nanoscale surface potential measurements in liquid environments are required. Here, we describe the various implementations of KPFM-based approaches for measuring surface potentials in liquid environments. We provide practical guidelines for surface potential measurements and describe what other information can be obtained. Finally, we discuss potential applications and limitations of existing approaches and present possible solutionsmore » for the successful implementation of liquid KPFM.« less

Spatially-resolved mapping of history-dependent coupled electrochemical and electronical behaviors of electroresistive NiO

DOE PAGES

Sugiyama, Issei; Kim, Yunseok; Jesse, Stephen; ...

2014-10-22

Bias-induced oxygen ion dynamics underpins a broad spectrum of electroresistive and memristive phenomena in oxide materials. Although widely studied by device-level and local voltage-current spectroscopies, the relationship between electroresistive phenomena, local electrochemical behaviors, and microstructures remains elusive. Here, the interplay between history-dependent electronic transport and electrochemical phenomena in a NiO single crystalline thin film with a number of well-defined defect types is explored on the nanometer scale using an atomic force microscopy-based technique. A variety of electrochemically-active regions were observed and spatially resolved relationship between the electronic and electrochemical phenomena was revealed. The regions with pronounced electroresistive activity were furthermore » correlated with defects identified by scanning transmission electron microscopy. Using fully coupled mechanical-electrochemical modeling, we illustrate that the spatial distribution of strain plays an important role in electrochemical and electroresistive phenomena. In conclusion, these studies illustrate an approach for simultaneous mapping of the electronic and ionic transport on a single defective structure level such as dislocations or interfaces, and pave the way for creating libraries of defect-specific electrochemical responses.« less

Surface-Charge-Mediated Formation of H-TiO2 @Ni(OH)2 Heterostructures for High-Performance Supercapacitors.

PubMed

Ke, Qingqing; Guan, Cao; Zhang, Xiao; Zheng, Minrui; Zhang, Yong-Wei; Cai, Yongqing; Zhang, Hua; Wang, John

2017-02-01

An electrochemically favorable Ni(OH) 2 with porously hierarchical structure and ultrathin nanosheets in a core-shell structure H-TiO 2 @Ni(OH) 2 is achieved through modulating the surface chemical activity of TiO 2 by hydrogenation, which creates a defect-rich surface of TiO 2 , thereby facilitating the subsequent nucleation and growth of Ni(OH) 2 . These configuration-tailored H-TiO 2 @Ni(OH) 2 core-shell nanowires exhibit a superior electrochemical performance and good flexibility. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlling the Electrochemically Active Area of Carbon Fiber Microelectrodes by the Electrodeposition and Selective Removal of an Insulating Photoresist

PubMed Central

Lambie, Bradley A.; Orwar, Owe; Weber, Stephen G.

2008-01-01

A new and simple method permits control of the electrochemically active area of a carbon fiber microelectrode. An electrophoretic photoresist insulates the 10 μm diameter carbon fiber microelectrodes. Photolysis of the photoresist followed by immersion of the exposed area into a developing solution reveals electroactive carbon fiber surface. The electroactive surface area exposed can be controlled with a good degree of reproducibility. PMID:16841943

Advances toward industrialization of novel molten salt electrochemical processes.

PubMed

Ito, Yasuhiko; Nishikiori, Tokujiro; Tsujimura, Hiroyuki

2016-08-15

We have invented various novel molten salt electrochemical processes, that can be put to practical use in the fields of energy and materials. These processes are promising from both technological and commercial viewpoints, and they are currently under development for industrial application. To showcase current developments in work toward industrialization, we focus here on three of these processes: (1) electrolytic synthesis of ammonia from water and nitrogen under atmospheric pressure, (2) electrochemical formation of carbon film, and (3) plasma-induced discharge electrolysis to produce nanoparticles.

Integration of graphene onto silicon through electrochemical reduction of graphene oxide layers in non-aqueous medium

NASA Astrophysics Data System (ADS)

Marrani, Andrea Giacomo; Coico, Anna Chiara; Giacco, Daniela; Zanoni, Robertino; Scaramuzzo, Francesca Anna; Schrebler, Ricardo; Dini, Danilo; Bonomo, Matteo; Dalchiele, Enrique A.

2018-07-01

Wafer-scale integration of reduced graphene oxide with H-terminated Si(1 1 1) surfaces has been accomplished by electrochemical reduction of a thin film of graphene oxide deposited onto Si by drop casting. Two reduction methods have been assayed and carried out in an acetonitrile solution. The initial deposit was subjected either to potential cycling in a 0.1 M TBAPF6/CH3CN solution at scan rates values of 20 mV s-1 and 50 mV s-1, or to a potentiostatic polarization at Eλ,c = -3 V for 450 s. The resulting interface has been characterized in its surface composition, morphology and electrochemical behavior by X-ray photoelectron spectroscopy, Raman spectroscopy, atomic force microscopy and electrochemical measurements. The results evidence that few-layer graphene deposits on H-Si(1 1 1) were obtained after reduction, and use of organic instead of aqueous medium led to a very limited surface oxidation of the Si substrate and a very low oxygen-to-carbon ratio. The described approach is fast, simple, economic, scalable and straightforward, as one reduction cycle is already effective in promoting the establishment of a graphene-Si interface. It avoids thermal treatments at high temperatures, use of aggressive chemicals and the presence of metal contaminants, and enables preservation of Si(1 1 1) surface from oxidation.

Ultrasensitive electrochemical detection of DNA based on Zn²⁺ assistant DNA recycling followed with hybridization chain reaction dual amplification.

PubMed

Qian, Yong; Wang, Chunyan; Gao, Fenglei

2015-01-15

A new strategy to combine Zn(2+) assistant DNA recycling followed with hybridization chain reaction dual amplification was designed for highly sensitive electrochemical detection of target DNA. A gold electrode was used to immobilize molecular beacon (MB) as the recognition probe and perform the amplification procedure. In the presence of the target DNA, the hairpin probe 1 was opened, and the DNAzyme was liberated from the caged structure. The activated DNAzyme hybridized with the MB and catalyzed its cleavage in the presence of Zn(2+) cofactor and resulting in a free DNAzyme strand. Finally, each target-induced activated DNAzyme underwent many cycles triggering the cleavage of MB, thus forming numerous MB fragments. The MB fragments triggered the HCR and formed a long double-helix DNA structure. Because both H1 and H2 were labeled by biotin, a lot of SA-ALP was captured on the electrode surface, thus catalyzing a silver deposition process for electrochemical stripping analysis. This novel cascade signal amplification strategy can detect target DNA down to the attomolar level with a dynamic range spanning 6 orders of magnitude. This highly sensitive and specific assay has a great potential to become a promising DNA quantification method in biomedical research and clinical diagnosis. Copyright © 2014 Elsevier B.V. All rights reserved.

Fabrication of graphene/polyaniline composite multilayer films by electrostatic layer-by-layer assembly

NASA Astrophysics Data System (ADS)

Cong, Jiaojiao; Chen, Yuze; Luo, Jing; Liu, Xiaoya

2014-10-01

A novel graphene/polyaniline composite multilayer film was fabricated by electrostatic interactions induced layer-by-layer self-assembly technique, using water dispersible and negatively charged chemically converted graphene (CCG) and positively charged polyaniline (PANI) as building blocks. CCG was achieved through partly reduced graphene oxide, which remained carboxyl group on its surface. The remaining carboxyl groups not only retain the dispersibility of CCG, but also allow the growth of the multilayer films via electrostatic interactions between graphene and PANI. The structure and morphology of the obtained CCG/PANI multilayer film are characterized by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, Ultraviolet-visible absorption spectrum (UV-vis), scanning electron microscopy (SEM), Raman spectroscopy and X-Ray Diffraction (XRD). The electrochemical properties of the resulting film are studied using cyclic voltammetry (CV), which showed that the resulting CCG/PANI multilayer film kept electroactivity in neutral solution and showed outstanding cyclic stability up to 100 cycles. Furthermore, the composite film exhibited good electrocatalytic ability toward ascorbic acid (AA) with a linear response from 1×10-4 to 1.2×10-3 M with the detect limit of 5×10-6 M. This study provides a facile and effective strategy to fabricate graphene/PANI nanocomposite film with good electrochemical property, which may find potential applications in electronic devices such as electrochemical sensor.

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.

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.

Sensitive electrochemical aptamer cytosensor for highly specific detection of cancer cells based on the hybrid nanoelectrocatalysts and enzyme for signal amplification.

PubMed

Sun, Duanping; Lu, Jing; Zhong, Yuwen; Yu, Yanyan; Wang, Yu; Zhang, Beibei; Chen, Zuanguang

2016-01-15

Human cancer is becoming a leading cause of death in the world and the development of a straightforward strategy for early detection of cancer is urgently required. Herein, a sandwich-type electrochemical aptamer cytosensor was developed for detection of human liver hepatocellular carcinoma cells (HepG2) based on the hybrid nanoelectrocatalysts and enzyme for signal amplification. The thiolated TLS11a aptamers were used as a selective bio-recognition element, attached to the gold nanoparticles (AuNPs) modified the glassy carbon electrode (GCE) surface. Meanwhile, the electrochemical nanoprobes were fabricated through the G-quadruplex/hemin/aptamer complexes and horseradish peroxidase (HRP) immobilized on the surfaces of Au@Pd core-shell nanoparticle-modified magnetic Fe3O4/MnO2 beads (Fe3O4/MnO2/Au@Pd). After the target cells were captured, the hybrid nanoprobes were further assembled to form an aptamer-cell-nanoprobes sandwich-like system on the electrode surface. Then, hybrid Fe3O4/MnO2/Au@Pd nanoelectrocatalysts, G-quadruplex/hemin HRP-mimicking DNAzymes and the natural HRP enzyme efficiently catalyzed the oxidation of hydroquinone (HQ) with H2O2, amplifying the electrochemical signals and improving the detection sensitivity. This electrochemical cytosensor delivered a wide detection range of 1×10(2)-1×10(7)cellsmL(-1), high sensitivity with a low detection limit of 15cellsmL(-1), good selectivity and repeatability. Finally, an electrochemical reductive desorption method was performed to break gold-thiol bond and desorb the components on the AuNPs/GCE for regenerating the cytosensor. These results have demonstrated that the electrochemical cytosensor has the potential to be a feasible tool for cost-effective cancer cell detection in early cancer diagnosis. Copyright © 2015 Elsevier B.V. All rights reserved.

Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

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

Gupta, Sanju, E-mail: sanju.gupta@wku.edu; Price, Carson

2015-10-15

Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO){sub 1}, (PPy/ErGO){sub 1}, (PAni/GO){sub 1} and (PPy/GO){sub 1}. The rationale design is to create thin films that possess interconnectedmore » graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, C{sub s}, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent C{sub s} of ≥350 F g{sup −1} as compared with constituents (∼70 F g{sup −1}) at discharge current density of 0.3 A g{sup −1} that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine electrochemical (re)activity of surface ion adsorption sites density at solid/liquid interface.« less

Electrochemical Induced Calcium Phosphate Precipitation: Importance of Local pH

PubMed Central

2017-01-01

Phosphorus (P) is an essential nutrient for living organisms and cannot be replaced or substituted. In this paper, we present a simple yet efficient membrane free electrochemical system for P removal and recovery as calcium phosphate (CaP). This method relies on in situ formation of hydroxide ions by electro mediated water reduction at a titanium cathode surface. The in situ raised pH at the cathode provides a local environment where CaP will become highly supersaturated. Therefore, homogeneous and heterogeneous nucleation of CaP occurs near and at the cathode surface. Because of the local high pH, the P removal behavior is not sensitive to bulk solution pH and therefore, efficient P removal was observed in three studied bulk solutions with pH of 4.0 (56.1%), 8.2 (57.4%), and 10.0 (48.4%) after 24 h of reaction time. While P removal efficiencies are not generally affected by bulk solution pH, the chemical-physical properties of CaP solids collected on the cathode are still related to bulk solution pH, as confirmed by structure characterizations. High initial solution pH promotes the formation of more crystalline products with relatively high Ca/P molar ratio. The Ca/P molar ratio increases from 1.30 (pH 4.0) to 1.38 (pH 8.2) and further increases to 1.55 (pH 10.0). The formation of CaP precipitates was a typical crystallization process, with an amorphous phase formed at the initial stage which then transforms to the most stable crystal phase, hydroxyapatite, which is inferred from the increased Ca/P molar ratio from 1.38 (day 1) to the theoretical 1.76 (day 11) and by the formation of needle-like crystals. Finally, we demonstrated the efficiency of this system for real wastewater. This, together with the fact that the electrochemical method can work at low bulk pH, without dosing chemicals and a need for a separation process, highlights the potential application of the electrochemical method for P removal and recovery. PMID:28872838

Design of a Sensitive and Selective Electrochemical Aptasensor for the Determination of the Complementary cDNA of miRNA-145 Based on the Intercalation and Electrochemical Reduction of Doxorubicin.

PubMed

Mohamadi, Maryam; Mostafavi, Ali; Torkzadeh-Mahani, Masoud

2017-11-01

The aim of this research was the determination of a microRNA (miRNA) using a DNA electrochemical aptasensor. In this biosensor, the complementary complementary DNA (cDNA) of miRNA-145 (a sense RNA transcript) was the target strand and the cDNA of miRNA-145 was the probe strand. Both cDNAs can be the product of the reverse transcriptase-polymerase chain reaction of miRNA. The proposed aptasensor's function was based on the hybridization of target strands with probes immobilized on the surface of a working electrode and the subsequent intercalation of doxorubicin (DOX) molecules functioning as the electroactive indicators of any double strands that formed. Electrochemical transduction was performed by measuring the cathodic current resulting from the electrochemical reduction of the intercalated molecules at the electrode surface. In the experiment, because many DOX molecules accumulated on each target strand on the electrode surface, amplification was inherently easy, without a need for enzymatic or complicated amplification strategies. The proposed aptasensor also had the excellent ability to regenerate as a result of the melting of the DNA duplex. Moreover, the use of DNA probe strands obviated the challenges of working with an RNA probe, such as sensitivity to RNase enzyme. In addition to the linear relationship between the electrochemical signal and the concentration of the target strands that ranged from 2.0 to 80.0 nM with an LOD of 0.27 nM, the proposed biosensor was clearly capable of distinguishing between complementary (target strand) and noncomplementary sequences. The presented biosensor was successfully applied for the quantification of DNA strands corresponding to miRNA-145 in human serum samples.