Redistribution of d-orbital in Fe-N4 active sites optimizing redox kinetics of the sulfur cathode

Cao, Guiqiang; Li, Xifei; Duan, Ruixian; Xu, Ke; Zhang, Kun; Chen, Liping; Jiang, Qinting; Li, Jun; Wang, Jingjing; Li, Ming; Wang, Ni; Wang, Jing; Xie, Chong; Li, Wenbin

doi:10.1016/j.nanoen.2023.108755

Cited by 30 publications

(13 citation statements)

References 39 publications

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“…As a result, SDS successfully regulated the coordination environment of FNS, thereby increasing the oxidation state of Fe and decreasing that of Ni. [1,9] According to some studies, [8,10] the regulation of the coordination environment of Fe atoms is of great significance for achieving rapid reconstruction reactions. This can effectively modulate the hybridization between the Fe 3d orbitals and the O 2p orbitals, optimizing the reconstruction rate before the occurrence of OER.…”

Section: Resultsmentioning

confidence: 99%

Rapid Surface Reconstruction of Pentlandite by High‐Spin State Iron for Efficient Oxygen Evolution Reaction

Du,

Meng,

Gong

et al. 2024

Angewandte Chemie

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Triggering rapid reconstruction reactions holds the potential to approach the theoretical limits of the oxygen evolution reaction (OER), and spin state manipulation has shown great promise in this regard. In this study, the transition of Fe spin states from low to high was successfully achieved by adjusting the surface electronic structure of pentlandite. In‐situ characterization and kinetic simulations confirmed that the high‐spin state of Fe promoted the accumulation of OH− on the surface and accelerated electron transfer, thereby enhancing the kinetics of the reconstruction reaction. Furthermore, theoretical calculations revealed that the lower d‐band center of high‐spin Fe optimized the adsorption of active intermediates, thereby enhancing the reconstruction kinetics. Remarkably, pentlandites with high‐spin Fe exhibited ultra‐low overpotential (245 mV @ 10 mA cm−2) and excellent stability. These findings provided new insights for the design and fabrication of highly active OER electrocatalysts.

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Section: Resultsmentioning

confidence: 99%

Rapid Surface Reconstruction of Pentlandite by High‐Spin State Iron for Efficient Oxygen Evolution Reaction

Du,

Meng,

Gong

et al. 2024

Angewandte Chemie

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“…In addition, the projected density of state (PDOS) analysis (d-orbital) is further investigated to probe the electronic interaction between the H adsorbate and the Ni site of nickel sulfide before and after the Pt loading as well as the phase change. [70,71] As depicted in Figure S25 (Supporting Information), the d-band center (E d ) relative to Fermi level (E f ) is calculated. And Pt-NiS exhibits a deeper E d of −1.94 eV at the Ni site closed to Pt nanoparticles than barNiS (−1.83 eV), which is also revealed from the calculated E d of Pt-Ni 3 S 2 (−1.67 eV) and Ni 3 S 2 (−1.49 eV).…”

Section: Hydrogen Evolution Reaction (Her)mentioning

confidence: 99%

Significantly Enhanced Energy‐Saving H₂ Production Coupled with Urea Oxidation by Low‐ and Non‐Pt Anchored on NiS‐Based Conductive Nanofibers

Zhong,

Yang,

et al. 2023

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Rational designing electrocatalysts is of great significance for realizing high‐efficiency H2 production in the water splitting process. Generally, reducing the usage of precious metals and developing low‐potential nucleophiles oxidation reaction to replace anodic oxygen evolution reaction (OER) are efficient strategies to promote H2 generation. Here, NiS‐coated nickel–carbon nanofibers (NiS@Ni‐CNFs) are prepared for low‐content Pt deposition (Pt‐NiS@Ni‐CNFs) to attain the alkaline HER catalyst. Due to the reconfiguration of NiS phase and synergistic effect between Pt and nickel sulfides, the Pt‐NiS@Ni‐CNFs catalyst shows a high mass activity of 2.74‐fold of benchmark Pt/C sample. In addition, the NiS@Ni‐CNFs catalyst performs a superior urea oxidation reaction (UOR) activity with the potential of 1.366 V versus reversible hydrogen electrode (RHE) at 10 mA cm−2, which demonstrates the great potential in the replacement of OER. Thus, a urea‐assisted water splitting electrolyzer of Pt‐NiS@Ni‐CNFs (cathode)||NiS@Ni‐CNFs (anode) is constructed to exhibit small voltages of 1.44 and 1.65 V to reach 10 and 100 mA cm−2, which is much lower than its overall water splitting process, and presents a 6.5‐fold hydrogen production rate enhancement. This work offers great opportunity to design new catalysts toward urea‐assisted water splitting with significantly promoted hydrogen productivity and reduced energy consumption.

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“…Recently, tremendous research has focused on modifying carbon materials by doping polar heteroatoms (Fe, B, N, O, or S) to improve the electrostatic attraction (Li bond) between the LPSs and doped carbon materials, which can effectively restrain the shuttling of LPSs. − Even so, the easy aggregation of S nanoparticles still easily leads to their migration and aggregation on nonpolar carbon surfaces, making it difficult to balance the high loading specific capacity and easy aggregation of S. Therefore, the effective limitation and simultaneous highly efficient conversion of sulfur species is a serious challenge for LSBs. As an alternative strategy to suppress the shuttling effect of LPSs, polar compounds or composites such as metal oxides, sulfides, , phosphides, , etc.…”

Section: Introductionmentioning

confidence: 99%

Hybrid Ascharite/Reduced Graphene Oxide with Polysulfide Adsorption Host for Advanced Lithium–Sulfur Batteries

Zhao,

Dang,

et al. 2024

Inorg. Chem.

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Balancing the adsorption of lithium-polysulfide intermediates on polar host material surfaces and the effect of their electronic conductivity in the subsequent oxidation and reduction kinetics of electrochemical reactions is necessary and remains a challenge. Herein, we have evaluated the role of polarity and conductivity in preparing a series of ascharite/reduced graphene oxide (RGO) aerogels by dispersing strong polar ascharite nanowires of varying mass into the conductive RGO matrix. When severed as Li–S battery cathodes, the optimized S@ascharite/RGO cathode with a sulfur content of 73.8 wt % demonstrates excellent rate performance and cycle stability accompanied by a high-capacity retention for 500 cycles at 1.0 C. Interesting advantages including the enhanced adsorption ability by the formation of the Mg–S and Li bonds, the continuous and quick electron/ion transportations assembled conductive RGO framework, and the effective deposition of Li2S are combined in the ascharite/RGO aerogel hosts. The electrochemical results further demonstrate that the polarity of ascharite components for the S cathode plays a dominant role in the improvement of electrochemical performance, but the absence of a conductive substrate leads to serious capacity attenuation, especially the rate performance. The balanced design protocol provides a universal method for the synthesis of multiple S hosts for high-performance LSBs.

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Redistribution of d-orbital in Fe-N4 active sites optimizing redox kinetics of the sulfur cathode

Cited by 30 publications

References 39 publications

Rapid Surface Reconstruction of Pentlandite by High‐Spin State Iron for Efficient Oxygen Evolution Reaction

Rapid Surface Reconstruction of Pentlandite by High‐Spin State Iron for Efficient Oxygen Evolution Reaction

Significantly Enhanced Energy‐Saving H₂ Production Coupled with Urea Oxidation by Low‐ and Non‐Pt Anchored on NiS‐Based Conductive Nanofibers

Hybrid Ascharite/Reduced Graphene Oxide with Polysulfide Adsorption Host for Advanced Lithium–Sulfur Batteries

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Redistribution of d-orbital in Fe-N4 active sites optimizing redox kinetics of the sulfur cathode

Cited by 30 publications

References 39 publications

Rapid Surface Reconstruction of Pentlandite by High‐Spin State Iron for Efficient Oxygen Evolution Reaction

Rapid Surface Reconstruction of Pentlandite by High‐Spin State Iron for Efficient Oxygen Evolution Reaction

Significantly Enhanced Energy‐Saving H2 Production Coupled with Urea Oxidation by Low‐ and Non‐Pt Anchored on NiS‐Based Conductive Nanofibers

Hybrid Ascharite/Reduced Graphene Oxide with Polysulfide Adsorption Host for Advanced Lithium–Sulfur Batteries

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Product

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Significantly Enhanced Energy‐Saving H₂ Production Coupled with Urea Oxidation by Low‐ and Non‐Pt Anchored on NiS‐Based Conductive Nanofibers