Axial nitrogen-coordination engineering over Fe-Nx active species for enhancing Fenton-like reaction performance

Liu, Fenli; Ren, Yujing; Duan, Jianglin; Deng, Pengcheng; Lu, Jian‐yu; Ge, Huibin; Liu, Xin; Xia, Qixing; Qi, Haifeng; Yang, Na; Qin, Yong

doi:10.1016/j.cej.2022.140382

Cited by 13 publications

(5 citation statements)

References 52 publications

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“…[ 21 ] Despite these encouraging efforts to regulate Zn central coordinated environment, the electronic structure of Zn site is insensitive to changes in planar local microenvironment due to the fully filled 3d 10 configuration. Interestingly, recent studies found that the introduction of the axial coordination can break the electronic distribution symmetry of center metal and directly regulate the electronic property of d orbital, [ 22 , 23 ] further achieving the optimization of catalytic activity, selectivity and durability. [ 24 , 25 ] Wang and co‐workers indicated that axial Co‐O coordination was able to induce the electronic delocalization of Co center, thus optimizing the intermediate adsorption and improving ORR activity.…”

Section: Introductionmentioning

confidence: 99%

Axial Oxygen Ligands Regulating Electronic and Geometric Structure of Zn‐N‐C Sites to Boost Oxygen Reduction Reaction

et al. 2023

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Zn‐N‐C possesses the intrinsic inertia for Fenton‐like reaction and can retain robust durability in harsh circumstance, but it is often neglected in oxygen reduction reaction (ORR) because of its poor catalytic activity. Zn is of fully filled 3d104s2 configuration and is prone to evaporation, making it difficult to regulate the electronic and geometric structure of Zn center. Here, guided by theoretical calculations, five‐fold coordinated single‐atom Zn sites with four in‐plane N ligands is constructed and one axial O ligand (Zn‐N4‐O) by ionic liquid‐assisted molten salt template method. Additional axial O not only triggers a geometry transformation from the planar structure of Zn‐N4 to the non‐planar structure of Zn‐N4‐O, but also induces the electron transfer from Zn center to neighboring atoms and lower the d‐band center of Zn atom, which weakens the adsorption strength of *OH and decreases the energy barrier of rate determining step of ORR. Consequently, the Zn‐N4‐O sites exhibit improved ORR activity and excellent methanol tolerance with long‐term durability. The Zn‐air battery assembled by Zn‐N4‐O presents a maximum power density of 182 mW cm−2 and can operate continuously for over 160 h. This work provides new insights into the design of Zn‐based single atom catalysts through axial coordination engineering.

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Section: Introductionmentioning

confidence: 99%

Axial Oxygen Ligands Regulating Electronic and Geometric Structure of Zn‐N‐C Sites to Boost Oxygen Reduction Reaction

et al. 2023

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“…Furthermore, the axially coordinated single‐atom strategy has demonstrated its effectiveness in various catalytic fields beyond ORR. [ 176,177 ] For example, due to the optimized electronic structure of metal active sites, SACMs with axial coordination of metal atoms exhibit high activity and stable OER performance. [ 178 ] Moreover, the reduction efficiency of CO 2 can be significantly enhanced by introducing axially coordination structure, thereby promoting progress in environmental protection, energy transition, and sustainable development.…”

Section: Modification Of Single‐atom Active Sitesmentioning

confidence: 99%

Precise Design and Modification Engineering of Single‐Atom Catalytic Materials for Oxygen Reduction

Zhang,

Liu,

Liu

et al. 2023

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Due to their unique electronic and structural properties, single‐atom catalytic materials (SACMs) hold great promise for the oxygen reduction reaction (ORR). Coordinating environmental and engineering strategies is the key to improving the ORR performance of SACMs. This review summarizes the latest research progress and breakthroughs of SACMs in the field of ORR catalysis. First, the research progress on the catalytic mechanism of SACMs acting on ORR is reviewed, including the latest research results on the origin of SACMs activity and the analysis of pre‐adsorption mechanism. The study of the pre‐adsorption mechanism is an important breakthrough direction to explore the origin of the high activity of SACMs and the practical and theoretical understanding of the catalytic process. Precise coordination environment modification, including in‐plane, axial, and adjacent site modifications, can enhance the intrinsic catalytic activity of SACMs and promote the ORR process. Additionally, several engineering strategies are discussed, including multiple SACMs, high loading, and atomic site confinement. Multiple SACMs synergistically enhance catalytic activity and selectivity, while high loading can provide more active sites for catalytic reactions. Overall, this review provides important insights into the design of advanced catalysts for ORR.

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“…And according to the literature, the last N species at around 399.8 eV is attributed to M-N species. 7,9,15 On this basis, the N (M-N) to Mn atomic ratio was calculated (details are given in the ESI †). From Table S4 (ESI †), it can be clearly seen that the N (Mn-N) /Mn ratio is about 4, suggesting the possibility of an Mn 1 -N 4 active structure in the Mn 1 /ND catalyst.…”

Section: Preparation and Characterizationmentioning

confidence: 99%

“…In Table S7 (ESI †), the adsorption energy for H 2 O 2 over the Mn 1 -N 4 site is calculated as À2.8 eV, which suggests that the H 2 O 2 molecule strongly interacts at the Mn 1 -N 4 site compared to that at the M 1 -N 4 site (M = Fe, Co, Ni, Cu). [30][31][32] Hence, the Mn 1 -N 4 site exhibits an excellent OH generation rate for achieving high TMB oxidation activity.…”

Section: Catalytic Performance and Mechanismmentioning

confidence: 99%

“…6,7 In recent years, many studies demonstrated that the catalytic mechanism of the Fenton-like process is actually the redox process over variable valency transition-metal sites, in which oxidation of the metal site accompanied by electron donation to H 2 O 2 directly induces OH generation. [8][9][10] On this basis, one can see that, by rationally constructing active sites with rapid electron donation and acceptance capabilities, a high-performance heterogeneous catalyst for OH production can be achieved.…”

Section: Introductionmentioning

confidence: 99%

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Highly efficient ˙OH generation in Fenton-like reactions over a bioinspired manganese single-atom site

Yang¹,

Ren²

2023

New J. Chem.

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Axial nitrogen-coordination engineering over Fe-Nx active species for enhancing Fenton-like reaction performance

Cited by 13 publications

References 52 publications

Axial Oxygen Ligands Regulating Electronic and Geometric Structure of Zn‐N‐C Sites to Boost Oxygen Reduction Reaction

Axial Oxygen Ligands Regulating Electronic and Geometric Structure of Zn‐N‐C Sites to Boost Oxygen Reduction Reaction

Precise Design and Modification Engineering of Single‐Atom Catalytic Materials for Oxygen Reduction

Highly efficient ˙OH generation in Fenton-like reactions over a bioinspired manganese single-atom site

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