Hydrogen evolution assisted electrodeposition of porous Cu-Ni alloy electrodes and their use for nitrate reduction in alkali

Mattarozzi, Luca; Cattarin, Sandro; Comisso, Nicola; Gambirasi, Arianna; Guerriero, P.; Musiani, Marco; Vázquez‐Gómez, Lourdes; Verlato, Enrico

doi:10.1016/j.electacta.2014.04.048

Cited by 94 publications

(70 citation statements)

References 46 publications

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“…XRD data for Cu and Cu-Ni, reported in [34] and [17], respectively, proved that both materials were crystalline, with a face-centred cubic lattice, and that Cu-Ni consisted of a solid solution. EDS analyses showed that Cu-Ni layers prepared under the same conditions as those used in this work contained Cu 70 at.% [18]. Surface roughness factors relevant to Cu and Cu-Ni, estimated from EIS data recorded in 1 M NaOH solutions [18,34], were 125 and 360, respectively.…”

Section: Results and Discussion Preparation And Sem Characterization mentioning

confidence: 99%

“…Deposition baths and experimental conditions were those described in previous articles by our group [16][17][18] and by others [19,20,22,23], with possible minor variations aimed at adapting the procedures to either rotating disc or screen-printed electrodes. Rh-modified Cu electrodes were obtained by modifying porous Cu electrodes through a spontaneous deposition reaction in which Rh(III) chloride complexes displaced a part of the Cu electrodeposits.…”

Section: Results and Discussion Preparation And Sem Characterization mentioning

confidence: 99%

“…Cu was deposited from solutions containing 0.40 M CuSO 4 , 1.5 M H 2 SO 4 and 0.050 M HCl [19], with a −3 A cm −2 current density for Cu RDEs and a −6 A cm −2 current density for Au-SPE. Cu-Ni was deposited from solutions containing 0.125 M CuSO 4 , 0.125 M NiSO 4 , 0.30 M Na citrate and 1.0 M (NH 4 ) 2 SO 4 , pH 4.5 [18], with a − 3 A cm −2 current density. For both Cu and Cu-Ni, the transferred charge was 40 C cm −2 , leading to the deposition of ca.…”

Section: Methodsmentioning

confidence: 99%

“…The solutions were kept at 20°C and were vigorously stirred when Cu or Cu-Ni were deposited onto Au-SPE. The surface roughness factors of Cu and Cu-Ni porous layers were determined from EIS data, by comparing the impedances of porous electrodes with those of polished electrodes of identical compositions (assumed to be ideally flat) [18].…”

Section: Methodsmentioning

confidence: 99%

“…In recent papers [16][17][18], our group has shown that electrodeposited Cu-Ni alloys are more active than Cu in the reduction of nitrates and that, when prepared with an appropriate bimodal porosity [17,18], they withstand poisoning better than compact Cu or Cu-Ni alloys. The porous Cu-Ni deposits have been prepared according to methods previously reported for other porous metals [19][20][21][22][23][24][25][26] and alloys [26][27][28], i.e., by exploiting the transient template action of hydrogen bubbles.…”

Section: Introductionmentioning

confidence: 98%

See 4 more Smart Citations

Study of Cu, Cu-Ni and Rh-modified Cu porous layers as electrode materials for the electroanalysis of nitrate and nitrite ions

Comisso¹,

Cattarin²,

Guerriero³

et al. 2015

J Solid State Electrochem

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Three porous materials (Cu, a Cu-Ni alloy with 70 at.% Cu and Rh-modified Cu) have been tested as electrodes for the electroanalysis of nitrate and nitrite ions, in either neutral or basic media, using mainly a flow injection technique. Porous Cu and Cu-Ni were prepared by electrodeposition at high current density, exploiting the transient template action of hydrogen bubbles. Rh-modified Cu electrodes were obtained from porous Cu, through a galvanic displacement reaction. All materials had a linear response for both nitrates and nitrites, at concentrations up to 10 −3 M, at least. Sensitivities, detection limits and stability were determined. Compared with Cu, used as a benchmark, (i) Rh-modified Cu had higher sensitivity for nitrates, comparable sensitivity for nitrites, lower or comparable detection limits and overall better stability; (ii) Cu-Ni had lower sensitivity, but exhibited lower detection limits and more stable performance for most analyte/medium combinations.

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Section: Results and Discussion Preparation And Sem Characterization mentioning

confidence: 99%

Section: Results and Discussion Preparation And Sem Characterization mentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

See 3 more Smart Citations

Study of Cu, Cu-Ni and Rh-modified Cu porous layers as electrode materials for the electroanalysis of nitrate and nitrite ions

Comisso¹,

Cattarin²,

Guerriero³

et al. 2015

J Solid State Electrochem

Self Cite

View full text Add to dashboard Cite

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Theoretical Insights into the Mechanism of Selective Nitrate‐to‐Ammonia Electroreduction on Single‐Atom Catalysts

Niu

Zhang

Wang

et al. 2020

Adv Funct Materials

343

287

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Selective nitrate‐to‐ammonia electrochemical conversion is an efficient pathway to solve the pollution of nitrate and an attractive strategy for low‐temperature ammonia synthesis. However, current studies for nitrate electroreduction (NO3RR) mainly focus on metal‐based catalysts, which remains challenging because of the poor understanding of the catalytic mechanism. Herein, taking single transition metal atom supported on graphitic carbon nitrides (g‐CN) as an example, the NO3RR feasibility of single‐atom catalysts (SACs) is first demonstrated by using density functional theory calculations. The results reveal that highly efficient NO3RR toward NH3 can be achieved on Ti/g‐CN and Zr/g‐CN with low limiting potentials of −0.39 and −0.41 V, respectively. Furthermore, the considerable energy barriers are observed during the formation of byproducts NO2, NO, N2O, and N2 on Ti/g‐CN and Zr/g‐CN, guaranteeing their high selectivity. This work provides a new route for the application of SACs and paves the way to the development of NO3RR.

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Direct Synthesis of Ammonia from Nitrate on Amorphous Graphene with Near 100% Efficiency

Huang

Cheng

et al. 2023

Advanced Materials

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Ammonia is an indispensable commodity in the agricultural and pharmaceutical industries. Direct nitrate‐to‐ammonia electroreduction is a decentralized route yet challenged by competing side reactions. Most catalysts are metal‐based, and metal‐free catalysts with high nitrate‐to‐ammonia conversion activity are rarely reported. Herein, it is shown that amorphous graphene synthesized by laser induction and comprising strained and disordered pentagons, hexagons, and heptagons can electrocatalyze the eight‐electron reduction of NO3− to NH3 with a Faradaic efficiency of ≈100% and an ammonia production rate of 2859 µg cm−2 h−1 at −0.93 V versus reversible hydrogen electrode. X‐ray pair‐distribution function analysis and electron microscopy reveal the unique molecular features of amorphous graphene that facilitate NO3− reduction. In situ Fourier transform infrared spectroscopy and theoretical calculations establish the critical role of these features in stabilizing the reaction intermediates via structural relaxation. The enhanced catalytic activity enables the implementation of flow electrolysis for the on‐demand synthesis and release of ammonia with >70% selectivity, resulting in significantly increased yields and survival rates when applied to plant cultivation. The results of this study show significant promise for remediating nitrate‐polluted water and completing the NOx cycle.

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Hydrogen evolution assisted electrodeposition of porous Cu-Ni alloy electrodes and their use for nitrate reduction in alkali

Cited by 94 publications

References 46 publications

Study of Cu, Cu-Ni and Rh-modified Cu porous layers as electrode materials for the electroanalysis of nitrate and nitrite ions

Study of Cu, Cu-Ni and Rh-modified Cu porous layers as electrode materials for the electroanalysis of nitrate and nitrite ions

Theoretical Insights into the Mechanism of Selective Nitrate‐to‐Ammonia Electroreduction on Single‐Atom Catalysts

Direct Synthesis of Ammonia from Nitrate on Amorphous Graphene with Near 100% Efficiency

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