Issue

Vol. 15 (2023)

Mutual Self-Regulation of d-Electrons of Single Atoms and Adjacent Nanoparticles for Bifunctional Oxygen Electrocatalysis and Rechargeable Zinc-Air Batteries

https://doi.org/10.1007/s40820-023-01022-8
Sundaram Chandrasekaran
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Rong Hu
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Lei Yao
Shenzhen Key Laboratory of Special Functional Materials, Shenzhen Engineering Laboratory for Advanced Technology of Ceramics, College of Materials Science and Engineering, Guangdong Research Center for Interfacial Engineering of Functional Materials, Shenzhen University, Shenzhen 518060, People’s Republic of China
Lijun Sui
Shanghai Key Laboratory for R&D and Application of Metallic Functional Materials, Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai 201804, People’s Republic of China
Yongping Liu
College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, People’s Republic of China
Amor Abdelkader
Department of Design and Engineering, Faculty of Science & Technology, Bournemouth University, Poole BH12 5BB, Dorset, UK
Yongliang Li
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Xiangzhong Ren
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Libo Deng
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China

Corresponding Author: Libo Deng

Denglb@szu.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 48

Abstract

Rechargeable zinc-air batteries (ZABs) are a promising energy conversion device, which rely critically on electrocatalysts to accelerate their rate-determining reactions such as oxygen reduction (ORR) and oxygen evolution reactions (OER). Herein, we fabricate a range of bifunctional M–N–C (metal-nitrogen-carbon) catalysts containing M–Nx coordination sites and M/MxC nanoparticles (M = Co, Fe, and Cu) using a new class of γ-cyclodextrin (CD) based metal–organic framework as the precursor. With the two types of active sites interacting with each other in the catalysts, the obtained Fe@C-FeNC and Co@C-CoNC display superior alkaline ORR activity in terms of low half-wave (E1/2) potential (~ 0.917 and 0.906 V, respectively), which are higher than Cu@C-CuNC (~ 0.829 V) and the commercial Pt/C (~ 0.861 V). As a bifunctional electrocatalyst, the Co@C-CoNC exhibits the best performance, showing a bifunctional ORR/OER overpotential (ΔE) of ~ 0.732 V, which is much lower than that of Fe@C-FeNC (~ 0.831 V) and Cu@C-CuNC (~ 1.411 V), as well as most of the robust bifunctional electrocatalysts reported to date. Synchrotron X-ray absorption spectroscopy and density functional theory simulations reveal that the strong electronic correlation between metallic Co nanoparticles and the atomic Co-N4 sites in the Co@C-CoNC catalyst can increase the d-electron density near the Fermi level and thus effectively optimize the adsorption/desorption of intermediates in ORR/OER, resulting in an enhanced bifunctional electrocatalytic performance. The Co@C-CoNC-based rechargeable ZAB exhibited a maximum power density of 162.80 mW cm−2 at 270.30 mA cm−2, higher than the combination of commercial Pt/C + RuO2 (~ 158.90 mW cm−2 at 265.80 mA cm−2) catalysts. During the galvanostatic discharge at 10 mA cm−2, the ZAB delivered an almost stable discharge voltage of 1.2 V for ~ 140 h, signifying the virtue of excellent bifunctional ORR/OER electrocatalytic activity.


Highlights:


1 A new class of γ-cyclodextrin based metal–organic framework -derived strategy was used to fabricate highly active M–N-C catalysts containing both single-atom sites and nanoparticles.
2 The obtained Co@C-CoNC exhibits remarkable bifunctional oxygen reduction (ORR)/oxygen evolution reactions (OER) performance, which further delivered a high power density and excellent cyclic stability in rechargeable zinc-air batteries.
3 Density functional theory calculation suggests that the mutual self-regulation of d-electron density of both Co NP and Co SAC conjointly reduce the reaction energy barriers and thus boost the ORR/OER kinetics through their fast adsorption/desorption ability of reaction intermediates.

Keywords

Cyclodextrin CD-MOF Single-atom catalyst ORR/OER Zinc-air battery
Chandrasekaran, Sundaram, Rong Hu, Lei Yao, Lijun Sui, Yongping Liu, Amor Abdelkader, Yongliang Li, Xiangzhong Ren, and Libo Deng. 2023. “Mutual Self-Regulation of D-Electrons of Single Atoms and Adjacent Nanoparticles for Bifunctional Oxygen Electrocatalysis and Rechargeable Zinc-Air Batteries”. Nano-Micro Letters 15 (February):48. https://doi.org/10.1007/s40820-023-01022-8.
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