Designing superior bifunctional electrocatalyst with high-purity pyrrole-type CoN4 and adjacent metallic cobalt sites for rechargeable Zn-air batteries

Yang, Huan; Gao, Shuai; Rao, Dewei; Yan, Xiaohong

doi:10.1016/j.ensm.2022.01.040

Cited by 104 publications

(69 citation statements)

References 55 publications

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Section: Resultsmentioning

confidence: 99%

“…[11b] These results indicated that the coordination bridging effect between Co(II) and PANI can induce the formation of more pyridinic N and graphitic N species, which can potentially promote the electron transfer and enhance the catalytic activity. [18,48] Synchrotron X-ray absorption spectroscopy (XAS) was performed to investigate the coordination environment and local electronic structure around the Co atoms in Co-CoN 4 @NCNs and the reference samples (Co foil, CoPc, and CoO). The Co K-edge X-ray absorption near-edge structure (XANES) spectra shown in Figure 3e exhibit a pre-edge feature at 7712 eV for Co-CoN 4 @NCNs, which can be attributed to the 1s→3d electron transition of Co. Additionally, the peak intensity observed for Co-CoN 4 @NCNs (1s→4p + LMCT) was higher than that of Co foil and was similar to CoPc.…”

Section: Fabrication and Characterization Of The Co-con4@ncns Catalystmentioning

confidence: 99%

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Robust Electronic Correlation of Co‐CoN₄ Hybrid Active Sites for Durable Rechargeable Zn‐Air Batteries

Ding

Luo

et al. 2022

Adv Funct Materials

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The rational design of bifunctional catalysts with excellent activity and stability toward the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is essential for rechargeable Zn-air batteries (ZABs). In this study, a facile coordination bridging strategy is proposed to construct bifunctional Co-CoN 4 hybrid active sites embedded in porous N-rich carbon nanolamellas (denoted as Co-CoN 4 @NCNs) for both the ORR and OER. Synchrotron X-ray absorption spectroscopy and density functional theory calculations reveal that the increased intrinsic ORR/OER activities can be attributed to the efficient interfacial charge transfer between the atomic CoN sites and metallic Co sites due to their robust electronic correlation. In situ Raman spectroscopy confirms that the OER activity depends on the CoOOH intermediates formed during the reaction. Co-CoN 4 @NCNs exhibits superior bifunctional catalytic performance for the ORR (E 1/2 = 0.83 V) and OER (η = 310 mV at 10 mA cm −2 ) conducted in alkaline media. The assembled rechargeable Co-CoN 4 @NCNs-based ZAB displays an open-circuit voltage of 1.47 V, peak power density of 118.8 mW cm −2 , specific capacity of 776.7 mAh g −1 , and outstanding cycling stability over 1500 cycles. The regulation of the interfacial electronic properties can contribute to the rational design of bifunctional electrocatalysts used in rechargeable metal-air batteries.

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Section: Resultsmentioning

confidence: 99%

Section: Fabrication and Characterization Of The Co-con4@ncns Catalystmentioning

confidence: 99%

Robust Electronic Correlation of Co‐CoN₄ Hybrid Active Sites for Durable Rechargeable Zn‐Air Batteries

Ding

Luo

et al. 2022

Adv Funct Materials

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“…Generally, a smaller value of ΔE means better bifunctional properties associated with oxygen. As shown in Figure a, MS-Co SA -N-C-800°C shows the ΔE value of 0.76 V, with is smaller than those of MS-CoNC-900°C (0.8 V), MS-CoNC-1000°C (0.91 V), Co@NC-700°C (0.97 V), Co@NC-800°C (1.05 V), and Co@NC-900°C (0.96 V) and the major results of recent reports (Table S6), ,− ,,− implying the excellent bifunctional electrocatalytic performance of MS-Co SA -N-C-800°C. To evaluate the practical application of the MS-Co SA -N-C-800°C electrocatalyst in energy conversion storage devices, a primary Zn-air battery was assembled utilizing MS-Co SA -N-C-800°C loaded nickel foam on a gas diffusion layer serving as an air cathode, together with a Zn plate as anode and 6.0 M KOH as electrolyte, respectively (Figure c).…”

Section: Resultsmentioning

confidence: 61%

Modulation of Ligand Fields in a Single-Atom Site by the Molten Salt Strategy for Enhanced Oxygen Bifunctional Activity for Zinc-Air Batteries

Wang

Jing

et al. 2022

ACS Nano

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Achieving full utilization of active sites and optimization of the electronic structure of metal centers is the key to improving the intrinsic activity of single-atom catalysts (SACs) but still remains a challenge to date. Herein, a versatile molten saltassisted pyrolysis strategy was developed to construct ultrathin, porous carbon nanosheets supported Co SACs. Molten salts are capable of inducing the formation of a Co singleatom and porous graphene-like carbon, which facilitates full exposure of the active center and simultaneously endows the Co SACs with abundant defective Co-N 4 configurations. The reported Co SACs deliver an excellent bifunctional activity and good stability for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Moreover, metal-air batteries (MABs) assembled with the Co SACs as air electrode also deliver excellent performance with high power densities of 160 mW•cm −2 , large capacities of 760 mAh•g −1 , and superior long-term charge/discharge stability, outperforming those of commercial Pt/C+RuO 2 . DFT theoretical calculation results show that the defects in the second coordination shell (CS) of Co SACs promote desorption of the OH* intermediate for the ORR and facilitate deprotonation of OH* for the OER, which can serve as the favorable active site for oxygen bifunctional catalysts. Our work provides an efficient strategy for the preparation of SACs with fully exposed active centers and optimized electronic structures.

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“…synthesized four pyrrolic‐ N ‐coordinated single cobalt atoms (Co‐N 4 ) and adjacent metallic cobalt nanoparticles in porous carbon by pyrolyzing the precursor of polydopamine‐coated Co hydroxides. [ 12 ] Yang et al. proposed a bimetallic‐ion exchange strategy using metal–organic frameworks (MOFs) as self‐templates to prepare NiCo nanoalloy modified atomically dispersed Co‐N 4 doped hierarchical porous carbon nanomaterials.…”

Section: Introductionmentioning

confidence: 99%

Carbon‐Nanotube‐Bridging Strategy for Integrating Single Fe Atoms and NiCo Nanoparticles in a Bifunctional Oxygen Electrocatalyst toward High‐Efficiency and Long‐Life Rechargeable Zinc–Air Batteries

Ding

Fang

et al. 2022

Advanced Energy Materials

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The development of highly efficient and robust bifunctional electrocatalysts for oxygen reduction (ORR) and evolution reactions (OER) is the key issue for realizing high‐performance and long‐life rechargeable zinc–air batteries (ZABs). However, it is still a great challenge to integrate independent ORR and OER sites in a catalyst with high activity. Here, a carbon nanotube‐bridging strategy is proposed to synthesize such a bifunctional oxygen electrocatalyst enriched with highly active single‐atom Fe sites for the ORR and high‐performance nanosized NiCo hydroxides for the OER. Consequently, the developed catalyst shows a small overpotential difference of 0.686 V. When used as an oxygen electrode catalyst, the corresponding ZAB exhibits a large power density of 219.5 mW cm−2, a small charge–discharge voltage gap of 0.72 V at 10 mA cm−2, and outstanding discharge–charge durability without attenuation after more than 700 cycles. This work proposes a new idea to realize multifunctional catalysts and drives the practical application of ZABs.

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Designing superior bifunctional electrocatalyst with high-purity pyrrole-type CoN4 and adjacent metallic cobalt sites for rechargeable Zn-air batteries

Cited by 104 publications

References 55 publications

Robust Electronic Correlation of Co‐CoN₄ Hybrid Active Sites for Durable Rechargeable Zn‐Air Batteries

Robust Electronic Correlation of Co‐CoN₄ Hybrid Active Sites for Durable Rechargeable Zn‐Air Batteries

Modulation of Ligand Fields in a Single-Atom Site by the Molten Salt Strategy for Enhanced Oxygen Bifunctional Activity for Zinc-Air Batteries

Carbon‐Nanotube‐Bridging Strategy for Integrating Single Fe Atoms and NiCo Nanoparticles in a Bifunctional Oxygen Electrocatalyst toward High‐Efficiency and Long‐Life Rechargeable Zinc–Air Batteries

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Designing superior bifunctional electrocatalyst with high-purity pyrrole-type CoN4 and adjacent metallic cobalt sites for rechargeable Zn-air batteries

Cited by 104 publications

References 55 publications

Robust Electronic Correlation of Co‐CoN4 Hybrid Active Sites for Durable Rechargeable Zn‐Air Batteries

Robust Electronic Correlation of Co‐CoN4 Hybrid Active Sites for Durable Rechargeable Zn‐Air Batteries

Modulation of Ligand Fields in a Single-Atom Site by the Molten Salt Strategy for Enhanced Oxygen Bifunctional Activity for Zinc-Air Batteries

Carbon‐Nanotube‐Bridging Strategy for Integrating Single Fe Atoms and NiCo Nanoparticles in a Bifunctional Oxygen Electrocatalyst toward High‐Efficiency and Long‐Life Rechargeable Zinc–Air Batteries

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Robust Electronic Correlation of Co‐CoN₄ Hybrid Active Sites for Durable Rechargeable Zn‐Air Batteries

Robust Electronic Correlation of Co‐CoN₄ Hybrid Active Sites for Durable Rechargeable Zn‐Air Batteries