Oxidation of Cu3N thin films obtained from Cu annealed under NH3:O2 flow: A Raman and N-K-edge NEXAFS study

Mavridou, Kalliopi; Zervos, Matthew; Pinakidou, F.; Brzhezinskaya, Maria; Katsikini, M.

doi:10.1016/j.jallcom.2022.165293

Cited by 9 publications

(2 citation statements)

References 43 publications

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“…1j and Supplementary Fig. 5 ) illustrates the sequential diminishment and ultimate disappearance of the Cu 3 N Raman peak, implying the formation of metallic Cu 31 – 33 . Building upon these analyses, XPS results for the V-Cu NAE showed that the Cu 2 p 3/2 and Cu 2 p 1/2 peaks shifted by 0.13 eV and 0.17 eV, respectively, when compared to those of Cu NWs (Supplementary Fig.…”

Section: Resultsmentioning

confidence: 96%

Defect-induced triple synergistic modulation in copper for superior electrochemical ammonia production across broad nitrate concentrations

Zhang,

Dai,

Chen

et al. 2024

Nat Commun

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Nitrate can be electrochemically degraded to produce ammonia while treating sewage while it remains grand challenge to simultaneously realize high Faradaic efficiency and production rate over wide-range concentrations in real wastewater. Herein, we report the defect-rich Cu nanowire array electrode generated by in-situ electrochemical reduction, exhibiting superior performance in the electrochemical nitrate reduction reaction benefitting from the triple synergistic modulation. Notably, the defect-rich Cu nanowire array electrode delivers current density ranging from 50 to 1100 mA cm−2 across wide nitrate concentrations (1–100 mM) with Faradaic efficiency over 90%. Operando Synchrotron radiation Fourier Transform Infrared Spectroscopy and theoretical calculations revealed that the defective Cu sites can simultaneously enhance nitrate adsorption, promote water dissociation and suppress hydrogen evolution. A two-electrode system integrating nitrate reduction reaction in industrial wastewater with glycerol oxidation reaction achieves current density of 550 mA cm−2 at −1.4 V with 99.9% ammonia selectivity and 99.9% nitrate conversion with 100 h stability, demonstrating outstanding practicability.

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Section: Resultsmentioning

confidence: 96%

Defect-induced triple synergistic modulation in copper for superior electrochemical ammonia production across broad nitrate concentrations

Zhang,

Dai,

Chen

et al. 2024

Nat Commun

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“…The results showed that the synergistic effect of the bimetallic effect increased the degree of Cu-NC has two characteristic peaks at 142 and 609 cm −1 attributed to an oxide layer of Cu 2 O (Figure 2d). 28,29 The Raman signal of 0.1CuCo-Nc had five characteristic peaks, followed by the shear vibration of F 2g (191 cm −1 ) of Co-O and the symmetric tensile vibration of E g (468 cm −1 ), 2F 2g (525 and 610 cm −1 ), and A 1g (675 cm −1 ). 30,31 Due to the low content of Cu, no obvious Cu characteristic peaks were observed in the Raman spectra of 0.1CuCo-NC.…”

Section: Resultsmentioning

confidence: 99%

Cu Regulating the Bifunctional Activity of Co-O Sites for the High-Performance Rechargeable Zinc-Air Battery

Niu,

Yue,

Wang

et al. 2024

ACS Appl. Mater. Interfaces

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The rational design of cost-effective and highly active electrocatalysts becomes the crucial energy storage technology to boost the kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), which hinders the large-scale application of metal-air batteries under the situation of increasingly pressing energy anxiety. Herein, the Co-based ZIF introduced the moderate amount of Cu 2+ -derived Cu/Co metal nanoparticles (NPs) embedded in carbon frameworks after hightemperature calcination. The Co-O bond on the surface of Co nanoparticles is modulated by adjacent Cu nanoparticles with the surface Cu-O bonds. The resulted increase of the Co 2+ /Co 3+ ratio in 0.1CuCo-NC enhances the ORR/OER bifunctional catalytic kinetics along with the ΔE of 0.639 V. In situ Raman spectra of the catalyst on the three-electrode system as well as in the driven zinc-air battery (ZAB) show that the Co-O active sites regulated by Cu nanoparticles with Cu-O bonds maintain a periodic lattice expansion and compression during discharging and charging. The zinc-air battery based on 0.1CuCo-NC has a peak power density of up to 198.3 mW cm −2 , a mass-specific capacity of 798.2 mAh g −1 , and a cycling stability of 923 h at room temperature. This work makes up the research gap of a Co-based metal−organic framework (MOF)-derived catalyst regulated by a transition metal.

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Modulating Metal‐Nitrogen Coupling in Anti‐Perovskite Nitride via Cation Doping for Efficient Reduction of Nitrate to Ammonia

Gong,

Xiang,

Zhong

et al. 2023

Angewandte Chemie

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The complexes of metal center and nitrogen ligands are the most representative systems for catalyzing hydrogenation reactions in small molecule conversion. Developing heterogeneous catalysts with similar active metal‐nitrogen functional centers, nevertheless, still remains challenging. In this work, we demonstrate that the metal‐nitrogen coupling in anti‐perovskite Co4N can be effective modulated by Cu doping to form Co3CuN, leading to strongly promoted hydrogenation process during electrochemical reduction of nitrate (NO3−RR) to ammonia. The combination of advanced spectroscopic techniques and density functional theory calculations reveal that Cu dopants strengthen the Co−N bond and upshifted the metal d‐band towards the Fermi level, promoting the adsorption of NO3− and *H and facilitating the transition from *NO2/*NO to *NO2H/*NOH. Consequently, the Co3CuN delivers noticeably better NO3−RR activity than the pristine Co4N, with optimal Faradaic efficiency of 97 % and ammonia yield of 455.3 mmol h−1 cm−2 at −0.3 V vs. RHE. This work provides an effective strategy for developing high‐performance heterogeneous catalyst for electrochemical synthesis.

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Oxidation of Cu3N thin films obtained from Cu annealed under NH3:O2 flow: A Raman and N-K-edge NEXAFS study

Cited by 9 publications

References 43 publications

Defect-induced triple synergistic modulation in copper for superior electrochemical ammonia production across broad nitrate concentrations

Defect-induced triple synergistic modulation in copper for superior electrochemical ammonia production across broad nitrate concentrations

Cu Regulating the Bifunctional Activity of Co-O Sites for the High-Performance Rechargeable Zinc-Air Battery

Modulating Metal‐Nitrogen Coupling in Anti‐Perovskite Nitride via Cation Doping for Efficient Reduction of Nitrate to Ammonia

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