Enhancing proton storage in the zinc-ion battery cathode material of MnO holds promise in promoting its electrochemical performance by mitigating the intense Coulombic interaction between divalent zinc ions and the host structure. However, challenges persist in addressing the structural instability caused by Jahn-Teller effects and accurately modulating H intercalation in MnO. Herein, the doping of high-electronegativity Sb with fully occupied d-orbital in MnO is reported. The Sb doping strategy engenders the formation of Mn-O-Sb path in the structure with a strong dipole polarization field, which facilitates the delocalization of e orbital electron in Mn and thus mitigates the Jahn-Teller effects. Simultaneously, adjusting the level of Sb doping in MnO leads to modulation of the p-band center of O, optimizing its interaction with hydrogen and thereby enhancing proton storage. Consequently, MnO doped with 6% Sb exhibits commendable performance in both rate capability and cycling endurance, delivering 113 mAh g at 2 A g after 2000 cycles. This investigation underscores the crucial role of electronic structural engineering in elevating the electrochemical performance of cathode materials for zinc-ion batteries.
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http://dx.doi.org/10.1021/acsnano.4c06672 | DOI Listing |
ACS Appl Mater Interfaces
January 2025
TCS Research, Sahyadri Park 2, Rajiv Gandhi Infotech Park, Hinjewadi Phase 3, Pune 411057, India.
Realization of a sustainable hydrogen economy in the future requires the development of efficient and cost-effective catalysts for its production at scale. MXenes (MX) are a class of 2D materials with 'n' layers of carbon or nitrogen (X) interleaved by 'n+1' layers of transition metal (M) and have emerged as promising materials for various applications including catalysts for hydrogen evolution reaction (HER). Their properties are intimately related to both their composition and their atomic structure.
View Article and Find Full Text PDFAdv Sci (Weinh)
December 2024
Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials, Jiangxi Normal University, Nanchang, 330022, China.
Oxygen evolution reaction (OER) is an indispensable anode reaction for sustainable hydrogen production from water electrolysis, yet overreliance on metal-based catalysts featured with vibrant d-electrons. It still has notable gap between metal-free and metal-based electrocatalysts, due to lacking accurate and efficient p-band regulation methods on non-metal atoms. Herein, a molecular modularization strategy is proposed for fine-tuning the p-orbital states of series metal-free covalent organic frameworks (COFs) for realizing OER performance beyond benchmark precious metal catalysts.
View Article and Find Full Text PDFInorg Chem
December 2024
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China.
To systematically investigate the influence of the number of [AO] layers in the unit cell of hexagonal perovskite oxide on the oxygen evolution reaction performance, we successfully synthesized the three new hexagonal perovskite oxides 2H-BaCoRuO, 6H-BaCoRuO, and 10H-BaCoRuO with the same element composition but different [BaO] layers via the sol-gel method. Here, 2H, 6H, and 10H refer to the number of [BaO] layers contained in the unit cell of the BaCoRuO system. Experimentally, 10H-BaCoRuO, featuring ten layers of [BaO], exhibits optimal electrochemical activity among the three oxide catalysts, and in situ Raman results under various bias voltages confirm its ability to maintain a high surface crystal structural stability.
View Article and Find Full Text PDFSmall
November 2024
Key Laboratory of Heavy Oil Processing, China University of Petroleum Beijing, No. 18 Fuxue RD, Beijing, 102249, China.
Rational design of defect engineering and interfacial built-in electric fields of photocatalysts is imperative for renewable energy conversion. Herein, a multi-strategy involving the introduction of Ni vacancies, the adjustment of the Se/S ratio, and the construction of dual junctions are employed to simultaneously realize NiSSe/phase junction CdS (HCC) an excellent photocatalytic activity and broad light absorption. With the help of V and the regulation of S/Se, the local electrons are redistributed to occupy more antibonding orbitals and adjust the p-band center, thus optimizing the H adsorption energy of the catalyst to accelerate the photocatalytic reaction kinetics.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Hefei National Research Center for Physical Sciences at the Microscale, CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
The sulfion oxidation reaction (SOR) could offer an energy-efficient and tech-economically favorable alternative to the oxygen evolution reaction (OER) for H production. Transition metal (TM) based catalysts have been considered promising candidates for SOR but suffer from limited activity due to the excessive bond strength from TM-S d-p orbit coupling. Herein, we propose a feasible strategy of screening direct d-p orbit hybridization between TM and S by constructing the Turing structure composed of lamellar stacking carbon-confined nickel nanosheets.
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