Nitrate Adsorption and Reduction on Cu(100) in Acidic Solution

Bae, Sang-Eun; Stewart, Karen L.; Gewirth, Andrew A.

doi:10.1021/ja071330n

Cited by 207 publications

(191 citation statements)

References 53 publications

(83 reference statements)

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“…In the present case, the (moderate) increase in sensitivity combined with a significantly lowering of the background noise is anyhow effective in achieving a significant decrease in detection limits. Note that LOD values here obtained with CuWNEEs are among the lowest reported in the literature for nitrate electroanalyses, where previous values were in the 6-12.5 M range [10,12,36,37], with the only exception of Hazefi et al [38], who reported a LOD of 0.59 M, however, operating under hydrodynamic flow conditions.…”

Section: Electrochemical Reduction Of Nitrate At Cuwneesmentioning

confidence: 46%

Arrays of copper nanowire electrodes: Preparation, characterization and application as nitrate sensor

Stortini

Moretto

Mardegan

et al. 2015

Sensors and Actuators B: Chemical

105

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a b s t r a c tEnsembles of copper nanowire electrodes (CuWNEEs) are prepared via electrodeposition in track-etched polycarbonate membranes. Three different preparation methods are compared showing that the better results in terms of sensor durability and reproducibility are achieved by pre-sputtering a thin gold film on the templating membrane and attaching it to a supporting electrode by exploiting the adhesion property and ionic conductivity of a thin Nafion interlayer. SEM-EDS analyses together with double layer charging currents measurements indicate that these arrays are formed by copper nanowires with 400 nm diameter, 10 m length distributed with a spatial density of 1 × 10 8 nanowires/cm 2 . The voltammetric reduction of nitrate at CuWNEEs is characterized by a well-resolved cathodic peak at approximately −0.680 V vs Ag/AgCl, whose current scales linearly with the nitrate concentration in the 10-400 M range. The limit of detection (LOD) achieved by simple linear sweep voltammetry is in the 1.7-3.0 M range, depending on the CuWNEE preparation method, such LOD values being among the lowest reported up to now in the literature. The possibility to use CuWNEEs in chloride and nitrite containing water samples is demonstrated.

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Section: Electrochemical Reduction Of Nitrate At Cuwneesmentioning

confidence: 46%

Arrays of copper nanowire electrodes: Preparation, characterization and application as nitrate sensor

Stortini

Moretto

Mardegan

et al. 2015

Sensors and Actuators B: Chemical

105

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“…This peak is attributed to NO 3 -reduction to NO 2 -through a 2 e -reduction, as reported previously. [16] The onset for nitrate reduction on Cu(100) is around -0.2 V. We also note the difference in voltammetric behavior between the Cu(100) and Cu(111) surfaces, as Cu (100) demonstrates a more negative potential onset reduction than Cu(111). Using the same potential range, 0 V to -0.8 V, SHINERS spectra were collected for each surface during cathodic polarization to investigate the nature of adsorbed intermediates during nitrate reduction.…”

Section: + H 2 O (4)mentioning

confidence: 66%

Nitrate reduction pathways on Cu single crystal surfaces: Effect of oxide and Cl−

2016

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The origin of different nitrate reduction activity between the (100), (111), and (110) faces of Cu is examined using vibrational spectroscopy and calculations. Shell isolated nanoparticle enhanced Raman spectroscopy (SHINERS) reveals a suite of intermediates from the nitrate reduction process on Cu(100), Cu(111), and Cu(110) including NO 2 -and HNO. All three faces show similar intermediates, suggesting the same mechanism is operative on all of them. Critical to the reduction pathway on the bare Cu surfaces is the reduction of nitrate to nitrite concomitant with partial oxidation of the Cu surface. This priming action facilitates nitrate reduction and reduces overpotentials, particularly on the Cu(111) and Cu(110) faces, which are more susceptible to oxidation. Decoration of the surfaces with Cl -suppresses nitrate reduction, resulting in higher overpotentials and lower current density. NH 3 is observed by SHINERS as a direct nitrate reduction product in the presence of Cl -, rather than NO x species observed on the bare Cu surfaces, indicating a reaction pathway unique from the bare, undecorated surface. Graphical Abstract

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“…Each sample was charged, washed in diethyl carbonate, and then immediately taken to the SEM. Raman experiments were carried out using instrumentation previously described [ 46 ] . An in-situ spectroelectrochemical cell was used to acquire Raman spectra while potentiostatically cycling the silicon.…”

Section: Characterizationmentioning

confidence: 99%

Strain Anisotropies and Self‐Limiting Capacities in Single‐Crystalline 3D Silicon Microstructures: Models for High Energy Density Lithium‐Ion Battery Anodes

Goldman

Long

Gewirth

et al. 2011

Adv Funct Materials

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188

179

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This study examines the crystallographic anisotropy of strain evolution in model, single-crystalline silicon anode microstructures on electrochemical intercalation of lithium atoms. The 3D hierarchically patterned singlecrystalline silicon microstructures used as model anodes were prepared using combined methods of photolithography and anisotropic dry and wet chemical etching. Silicon anodes, which possesses theoretically ten times the energy density by weight compared to conventional carbon anodes, reveal highly anisotropic but more importantly, variably recoverable crystallographic strains during cycling. Model strain-limiting silicon anode architectures that mitigate these impacts are highlighted. By selecting a specifi c design for the silicon anode microstructure, and exploiting the crystallographic anisotropy of strain evolution upon lithium intercalation to control the direction of volumetric expansion, the volume available for expansion and thus the charging capacity of these structures can be broadly varied. We highlight exemplary design rules for this self-strain-limited charging in which an anode can be variably optimized between capacity and stability. Strain-limited capacities ranging from 677 mAhg − 1 to 2833 mAhg − 1 were achieved by constraining the area available for volumetric expansion via the design rules of the microstructures.

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Nitrate Adsorption and Reduction on Cu(100) in Acidic Solution

Cited by 207 publications

References 53 publications

Arrays of copper nanowire electrodes: Preparation, characterization and application as nitrate sensor

Arrays of copper nanowire electrodes: Preparation, characterization and application as nitrate sensor

Nitrate reduction pathways on Cu single crystal surfaces: Effect of oxide and Cl−

Strain Anisotropies and Self‐Limiting Capacities in Single‐Crystalline 3D Silicon Microstructures: Models for High Energy Density Lithium‐Ion Battery Anodes

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