Dissociative mechanism of oxygen reduction reaction (ORR) on Pd-Cu disordered binary alloy metal surfaces: A theoretical study

López-Chávez, Ernesto; Garcia-Quiroz, Alberto; González‐García, Gerardo; Peña-Castañeda, Yesica A.; Díaz-Góngora, J.A.I.; Castillo-Alvarado, Fray de Landa

doi:10.1016/j.ijhydene.2016.09.001

Cited by 19 publications

(6 citation statements)

References 29 publications

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“…Among the catalytic cathodes, all three cathodes showed noticeable multiple oxidative and reductive peak currents at different applied potentials, indicating significant catalytic activity of Cu-Sn as cathode catalyst and lattice disorder effect. 31 However, the shape and the position of non-faradaic current peaks were observed different for different loadings of the catalyst on cathode, revealing recognizable effect of concentration of catalyst on cathode overpotential. The first reduction peak for Cat-2 and Cat-3, which possibly is the first hydrogenation peak of adsorbed O (i.e.…”

Section: Resultsmentioning

confidence: 95%

Carbon Supported Cu-Sn Bimetallic Alloy as an Excellent Low-Cost Cathode Catalyst for Enhancing Oxygen Reduction Reaction in Microbial Fuel Cell

Noori

Bhowmick

Tiwari

et al. 2018

J. Electrochem. Soc.

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Cu-Sn bimetallic alloy supported on acetylene black was prepared and tested under different loadings per unit cathode surface area viz. 1 mg.cm −2 , 2 mg.cm −2 and 5 mg.cm −2 as a catalyst to improve the oxygen reduction reaction (ORR) and to enhance performance of the microbial fuel cell (MFC). Electrochemical analyses were performed to evaluate the ORR kinetics. Results of cyclic voltammetry showed multiple redox current peaks for all the loadings of Cu-Sn with positive onset potential of ∼0.25 V. Among different loadings, cathode with Cu-Sn loading of 2 mg.cm −2 proved to be the best choice for application in MFC, due to less charge transfer resistance and high redox current. Power density and coulombic efficiency of 470 mW.m −2 and 36%, respectively, were obtained from MFC using Cu-Sn catalyzed cathode with a loading of 2 mg.cm −2 , which was higher than the MFCs using cathodes with 1 and 5 mg.cm −2 of Cu-Sn loadings and it was even found slightly higher than the MFC using Pt-C catalyst on cathode. Power generation per unit cost of catalyst for MFC using Cu-Sn catalyst was found to be 11-fold higher than the MFC using Pt-C cathode, ascertaining former as low-cost cathode catalyst for harvesting more power from MFCs.

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Section: Resultsmentioning

confidence: 95%

Carbon Supported Cu-Sn Bimetallic Alloy as an Excellent Low-Cost Cathode Catalyst for Enhancing Oxygen Reduction Reaction in Microbial Fuel Cell

Noori

Bhowmick

Tiwari

et al. 2018

J. Electrochem. Soc.

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“…Constructing dual active sites (such as adjacent defective carbon) and optimizing the geometric configuration of carbon defects may be the best and most efficient strategy to realize the direct breaking of the O–O bond during the ORR process. However, the energy required for O–O cleavage to ensure a dissociative mechanism is higher than *O–OH cleavage in the associative pathway . It is still a significant challenge to design defective sites in CNMs to reduce the energy barrier of direct O–O cleavage.…”

Section: Introductionmentioning

confidence: 99%

“…However, the energy required for O−O cleavage to ensure a dissociative mechanism is higher than *O−OH cleavage in the associative pathway. 30 It is still a significant challenge to design defective sites in CNMs to reduce the energy barrier of direct O−O cleavage. Moreover, the formation of the adjacent defective carbon inevitably results in the generation of vacancy defects.…”

Section: ■ Introductionmentioning

confidence: 99%

Boosting Oxygen Reduction Reaction Kinetics by Designing Rich Vacancy Coupling Pentagons in the Defective Carbon

Xia,

Pang,

Dong

et al. 2023

J. Am. Chem. Soc.

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In the energy conversion context, the design and synthesis of high-performance metal-free carbon nanomaterials with topological defects for the oxygen reduction reaction (ORR) are essential. Herein, we first report a template-assisted strategy to fabricate carbon defect electrocatalysts with rich vacancy coupling pentagons (VP) as active sites in two-dimensional (2D) carbon nanosheets (VP/CNs). Experimental characterizations verify the presence of abundant VP active sites in the VP/CNs electrocatalyst, and the ORR activity is linearly related to the amounts of VP active sites. In situ spectroscopic results identify that the VP/CNs can catalyze direct O–O bond cleavage, bypassing the formation of traditional *OOH intermediates, resulting in the fast kinetics of ORR via a dissociative pathway. The as-prepared VP/CNs show outstanding intrinsic activity for alkaline ORR (half-wave potential of 0.86 V vs reversible hydrogen electrode) with an almost 99% efficiency for four-electron selectivity, outperforming that using the benchmark of Pt/C. Density functional theory calculations further reveal that the cooperative effect between carbon vacancy and adjacent pentagons significantly increases the charge transfer and achieves a lower ORR reaction energy barrier compared with the counterpart of adjacent pentagons or single pentagon. The well-designed carbon defects pave a new avenue for the rational design of metal-free electrocatalysts with high efficiency.

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“…For this purpose, pulsed electrocatalysis has emerged as an interesting candidate to effectively improve reaction kinetics and tailor product selectivity. 1−15 By introducing the additional pulsed E rest and T rest factors, a series of evolution steps can be aroused at the electrocatalyst active sites 1−5 and the electric double layer (EDL) at the interface, 6−8 which rely on the potential dependence 16,17 and the non-Faraday process caused by the transient potential change. At present, it has been proven that the introduction of pulsed electrocatalysis could dynamically reconstruct the valence states and morphology of metal-based electrocatalysts (such as Cu) [1][2][3][4]18 and exert in situ stabilization and activation effects on the carboxyl groups and defect sites of O-doped carbon-based materials.…”

mentioning

confidence: 99%

“…Nevertheless, in the typical heterogeneous cathodic reduction reaction, such as the O 2 reduction reaction (ORR), the CO 2 reduction reaction (CO 2 RR), and the H 2 evolution reaction (HER), there still remain ongoing challenges such as regulating the intermediate existence state and balancing the inconsistency between mass transfer and surface reaction. For this purpose, pulsed electrocatalysis has emerged as an interesting candidate to effectively improve reaction kinetics and tailor product selectivity. − By introducing the additional pulsed E rest and T rest factors, a series of evolution steps can be aroused at the electrocatalyst active sites − and the electric double layer (EDL) at the interface, − which rely on the potential dependence , and the non-Faraday process caused by the transient potential change. At present, it has been proven that the introduction of pulsed electrocatalysis could dynamically reconstruct the valence states and morphology of metal-based electrocatalysts (such as Cu) − , and exert in situ stabilization and activation effects on the carboxyl groups and defect sites of O-doped carbon-based materials …”

mentioning

confidence: 99%

Revealing the In Situ Dynamic Regulation of the Interfacial Microenvironment Induced by Pulsed Electrocatalysis in the Oxygen Reduction Reaction

Ding

Zhou

et al. 2023

ACS Energy Lett.

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Pulsed electrocatalysis has emerged as a promising technology to effectively improve reaction kinetics and tailor product selectivity. While most research focuses on the evolution of electrocatalyst active sites, the dynamic response of the interfacial microenvironment during pulsed electrocatalysis still remains unknown. Here, we reveal the in situ dynamic regulation of the interfacial microenvironment induced by pulsed electrocatalysis in the oxygen reduction reaction process, from the interface reactant delivery to intermediate formation dynamics. At the diffusion layer, the coupling of pulsed electrocatalysis and hierarchical pore structure was proven to break the limitation of proton transfer, resulting in favorable H2O2 production kinetics. At the electrode/electrolyte interface, the pulsed electric field would stimulate the cation effect to activate C–*OOH and reduced the reaction energy barrier, giving rise to more favorable *OOH formation thermodynamics. This work provides new insights into exploring in situ regulation of the interfacial microenvironment, which is expected to be extended to different electrochemical processes.

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Dissociative mechanism of oxygen reduction reaction (ORR) on Pd-Cu disordered binary alloy metal surfaces: A theoretical study

Cited by 19 publications

References 29 publications

Carbon Supported Cu-Sn Bimetallic Alloy as an Excellent Low-Cost Cathode Catalyst for Enhancing Oxygen Reduction Reaction in Microbial Fuel Cell

Carbon Supported Cu-Sn Bimetallic Alloy as an Excellent Low-Cost Cathode Catalyst for Enhancing Oxygen Reduction Reaction in Microbial Fuel Cell

Boosting Oxygen Reduction Reaction Kinetics by Designing Rich Vacancy Coupling Pentagons in the Defective Carbon

Revealing the In Situ Dynamic Regulation of the Interfacial Microenvironment Induced by Pulsed Electrocatalysis in the Oxygen Reduction Reaction

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