Mechanistic insights into the pseudocapacitive performance of bronze-type vanadium dioxide with mono/multi-valent cations intercalation

Zeng, Ying; Hu, Jian Zhi; Jian, Yang; Tang, Pei Song; Fu, Qingfeng; Zhou, Wang; Peng, Yufan; Xiao, Peitao; Chen, Shi; Guo, Kunkun; Gao, Peng; Dong, Hongliang; Liu, Jilei

doi:10.1039/d2ta00760f

Cited by 20 publications

(11 citation statements)

References 69 publications

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“…Further investigations for the charge transfer process between Co and N 2 were conducted with electronic density difference calculation based on the equation Δρ = ρ AB – ρ A – ρ B , where ρ AB is the total charge density of the catalyst with the absorbed N 2 molecule and ρ A and ρ B represent the charge density of the isolated catalyst and N 2 molecule. The cloud with blue/yellow represents gaining/losing electrons, respectively . Alternating blue and yellow electronic clouds along the NN bonds mean that the catalysts could polarize the nonpolar triple bond.…”

Section: Resultsmentioning

confidence: 99%

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Bifunctional OER/NRR Catalysts Based on a Thin-Layered Co₃O_4–x/GO Sandwich Structure

Sun

Qiao

Liu

2022

ACS Appl. Mater. Interfaces

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Due to ample low-coordinated surface atoms, a distorted lattice endows thin-layered transition metal oxides with a flexible electronic structure, making them the ideal candidates for overall ammonia synthesis. This work proposes a novel and facile method for the controllable synthesis of thin-layered Co3O4 catalysts with graphene as a conductive matrix to further enhance the overall N2 fixation performance. X-ray photoelectron spectroscopy (XPS) and synchrotron radiation X-ray absorption spectroscopy (XAS) demonstrate that the sandwiched Co3O4–x /GO catalysts enable exposure of more coordination unsaturated active sites, resulting in numerous oxygen vacancies. With a higher conductivity and distorted crystalline structure, excellent electrochemical NRR activity is realized with a NH3 production rate of 5.19 mmol g–1 h–1 and a Faradaic efficiency of 10.68% at −0.4 V vs reversible hydrogen electrode (RHE). The density functional theory (DFT) calculation demonstrates that introducing oxygen vacancies in thin-layered cobalt oxides could result in an increased density of states (DOS) near the Fermi level, which would accelerate the NRR rate-determining step. Charge transfer could be accelerated through a weak Co 3d–N 2p σ hybrid bond with a lower energy level. No obvious performance decay could be found after six cycles. Furthermore, the sandwiched Co3O4–x /GO catalyst exhibits a low overpotential of 280 mV@10 mA cm–2 and an outstanding durability for the anode OER, even better than those of the benchmark RuO2. Such an inexpensive sandwiched transition metal oxide catalyst shows great potential in the field of overall N2 fixation.

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Section: Resultsmentioning

confidence: 99%

“…The cloud with blue/yellow represents gaining/losing electrons, respectively. 44 Alternating blue and yellow electronic clouds along the N�N bonds mean that the catalysts could polarize the nonpolar triple bond. Note that a larger scale charge transfer (in black circle) could be found in l-Co 3 O 4 .…”

Section: Resultsmentioning

confidence: 99%

Bifunctional OER/NRR Catalysts Based on a Thin-Layered Co₃O_4–x/GO Sandwich Structure

Sun

Qiao

Liu

2022

ACS Appl. Mater. Interfaces

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“…Both Mn 3 O 4 and CoMn 2 O 4 exhibit type IV-like isotherms with distinct H3type hysteresis loops, demonstrating the presence of meso-and macropores based on IUPAC classification. 30 The ZnMn 2 O 4 exhibits a type IV-like isotherm with an H2-hysteresis loop, demonstrating its mesoporous structure. 6 Their different pore structures were also confirmed by the pore size distributions, as shown in Figure S2 The crystal structures and phases of as-synthesized samples were characterized by XRD.…”

Section: Microstructure Characterizations Of Spinel-typementioning

confidence: 94%

Unraveling the Critical Role of Octahedrally Coordinated Mn in Spinel Manganites toward Enhanced Electrochemical Charge Storage

Gong,

Zi,

Yang

et al. 2023

ACS Sustainable Chem. Eng.

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Spinel manganite is considered as the most promising pseudocapacitive material due to its typical battery-type electrochemical behavior and high theoretical capacitance; however, understanding its structure−property relationship at the atomic level is still vague. In this study, the substitutional cation-related and geometrical site-dependent charge storage properties in the alkaline electrolyte have been systematically investigated by replacing the Mn with Co and Zn. Structure characterizations and electrochemical analysis clearly revealed the critically important role of octahedrally coordinated Mn in improving the electrode's charge storage capability. The Zn substitution results in dominant occupation of Mn in octahedral interstices and 3.5× enhanced specific capacitance at a current density of 1 A/g, whereas the Co ions occupy both octahedral and tetrahedral interstices with slight increment (18%) of the specific capacitance. However, the bimetallic compositional feature of CoMn 2 O 4 enables better capacitance retention rate and excellent cycling performance; in contrast, the Zn incorporation may lead to a distorted local structure and affect ion diffusion. Therefore, choosing substitutional cations with appropriate size and strong affinity to tetrahedral sites would be beneficial to improve the electrode's electrochemical charge storage properties. In general, our work not only provides a fundamental understanding of the geometrical site-dependent activity in spinel manganites but also summarizes the general principle in optimizing the electrode's charge transfer and ion diffusion processes, which can guide the synthesis of more spinel oxides with improved charge storage capability.

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“…2 Conventional SCs include electric double layer capacitors and pseudocapacitors. [3][4][5] Whatever their type, developing safe, high-power-output, and nontoxic SCs that operate in high-temperature environments presents huge challenges.…”

Section: Introductionmentioning

confidence: 99%

Vacancy-modified few-layered GaN crystal for novel high-temperature energy storage

Wang

et al. 2022

J. Mater. Chem. A

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Mechanistic insights into the pseudocapacitive performance of bronze-type vanadium dioxide with mono/multi-valent cations intercalation

Abstract: Bronze-type vanadium dioxide (VO2(B)) is a promising intercalation pseudocapacitive material due to its special corner and edge-sharing structure. Meanwhile, the utilization of multivalent cations as charge carriers has been considered...

Cited by 20 publications

References 69 publications

Bifunctional OER/NRR Catalysts Based on a Thin-Layered Co₃O_4–x/GO Sandwich Structure

Bifunctional OER/NRR Catalysts Based on a Thin-Layered Co₃O_4–x/GO Sandwich Structure

Unraveling the Critical Role of Octahedrally Coordinated Mn in Spinel Manganites toward Enhanced Electrochemical Charge Storage

Vacancy-modified few-layered GaN crystal for novel high-temperature energy storage

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Mechanistic insights into the pseudocapacitive performance of bronze-type vanadium dioxide with mono/multi-valent cations intercalation

Abstract: Bronze-type vanadium dioxide (VO2(B)) is a promising intercalation pseudocapacitive material due to its special corner and edge-sharing structure. Meanwhile, the utilization of multivalent cations as charge carriers has been considered...

Cited by 20 publications

References 69 publications

Bifunctional OER/NRR Catalysts Based on a Thin-Layered Co3O4–x/GO Sandwich Structure

Bifunctional OER/NRR Catalysts Based on a Thin-Layered Co3O4–x/GO Sandwich Structure

Unraveling the Critical Role of Octahedrally Coordinated Mn in Spinel Manganites toward Enhanced Electrochemical Charge Storage

Vacancy-modified few-layered GaN crystal for novel high-temperature energy storage

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Resources

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Bifunctional OER/NRR Catalysts Based on a Thin-Layered Co₃O_4–x/GO Sandwich Structure

Bifunctional OER/NRR Catalysts Based on a Thin-Layered Co₃O_4–x/GO Sandwich Structure