Improved Electronic Structure from Spin-State Reconstruction of a Heteronuclear Fe–Co Diatomic Pair to Boost the Fenton-like Reaction

Zhao, Zhendong; Hu, Mingzhu; Nie, Tiantian; Zhou, Wenjun; Pan, Bingcai; Xing, Baoshan; Zhu, Lizhong

doi:10.1021/acs.est.2c09336

Cited by 79 publications

(27 citation statements)

References 58 publications

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“…Single-atom catalysts (SACs) achieve maximum contact between metal atoms and support in heterogeneous catalysis and further generate highly active sites so they are considered an ideal model for studying the strong interaction between metal and support. – The first-shell coordination atoms around metal center atoms profoundly impact electron structure, surface nature, and even reaction routes due to the direct covalent bonding . Thus, optimizing the local atomic environment of SACs is imperative to achieve excellent catalytic performance. – Transition metal-based SACs demonstrate immense advantages in PMS-AOPs with high catalytic activity and stability, tunable coordination environments, and superior selectivity as compared to nanoparticle-based catalysts. – Significant progress has been made in the field of single-atom catalysis in the past decade, but a profound understanding of the structure–property correlation of SACs at the atomic scale remains a challenging task. Nitrogen-doped carbon-supported (NC) SACs have been extensively used to convert PMS into 1 O 2 to efficiently degrade organic pollutants. – The pyrolysis strategy remains the most commonly used method for preparing carbon-supported SACs.…”

Section: Introductionmentioning

confidence: 99%

Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification

Wu,

Huang,

Wang

et al. 2023

Environ. Sci. Technol.

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Precisely identifying the atomic structures in single-atom sites and establishing authentic structure–activity relationships for single-atom catalyst (SAC) coordination are significant challenges. Here, theoretical calculations first predicted the underlying catalytic activity of Fe–N x C4–x sites with diverse first-shell coordination environments. Substituting N with C to coordinate with the central Fe atom induces an inferior Fenton-like catalytic efficiency. Then, Fe-SACs carrying three configurations (Fe–N2C2, Fe–N3C1, and Fe–N4) fabricate facilely and demonstrate that optimized coordination environments of Fe–N x C4–x significantly promote the Fenton-like catalytic activity. Specifically, the reaction rate constant increases from 0.064 to 0.318 min–1 as the coordination number of Fe–N increases from 2 to 4, slightly influencing the nonradical reaction mechanism dominated by 1O2. In-depth theoretical calculations unveil that the modulated coordination environments of Fe-SACs from Fe–N2C2 to Fe–N4 optimize the d-band electronic structures and regulate the binding strength of peroxymonosulfate on Fe–N x C4–x sites, resulting in a reduced energy barrier and enhanced Fenton-like catalytic activity. The catalytic stability and the actual hospital sewage treatment capacity also showed strong coordination dependency. This strategy of local coordination engineering offers a vivid example of modulating SACs with well-regulated coordination environments, ultimately maximizing their catalytic efficiency.

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Section: Introductionmentioning

confidence: 99%

Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification

Wu,

Huang,

Wang

et al. 2023

Environ. Sci. Technol.

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“…Quenching tests were conducted to investigate the production of various ROSs in the 2,4-D degradation process. Methanol (MeOH), isopropanol (IPA), l -histidine, and nitrogen (N 2 ) were chosen as scavengers of SO 4 •– , • OH, 1 O 2 , and O 2 •– , respectively. As exhibited in Figure a, the 2,4-D degradation efficiency was decreased from 100% to 72% and 35% with addition of MeOH and IPA, respectively, implying that SO 4 •– and • OH might play an important role in the FeSe 2 @MoO 3 -8/PMS system.…”

Section: Resultsmentioning

confidence: 99%

The Pivotal Role of Selenium Vacancies in Defective FeSe₂@MoO₃ for Efficient Peroxymonosulfate Activation: Experimental and DFT Calculation

et al. 2023

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The presence of selenium vacancies (V Se ) in metal selenides enables the activation of peroxymonosulfate (PMS) for efficient water purification. However, the mechanisms of interactions of V Se with PMS and organic pollutant removal are unclear. Hence, we precisely prepared a series of FeSe 2 @MoO 3 composites with V Se for effective activation of PMS for the removal of various organic pollutants. The roles of V Se are explored via density functional theory (DFT) calculations: (i) regulating the electron distribution of Fe and Mo orbitals in FeSe 2 @MoO 3 for enhancing the PMS adsorption and (ii) promoting the conversion of transition metallic redox pairs (Fe 3+ /Fe 2+ and Mo 6+ /Mo 5+ / Mo 4+ ). The as-prepared FeSe 2 @MoO 3 -8 exhibits excellent catalytic performance via PMS activation in which nearly 100% removal efficiencies of various organic pollutants are achieved within 2−10 min. The quenching experiments, electronic spin resonance (ESR), and probe tests demonstrated that the multiple reactive species like SO 4•− , O 2 •− , • OH, and 1 O 2 contributed to the removal of 2,4-D. Finally, FeSe 2 @MoO 3 -8 was attached to the polyvinylidene difluoride (PVDF) membrane for continuous and efficient removal of 2,4-D, in which the removal efficiency and total organic carbon removal efficiency of 2,4-D were > 90% and >70% within 12 h of operation.

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“…(c) The d-band center of Co–N/C, Fe–N/C, and FeCo–N/C before and after PMS adsorption and corresponding adsorption energies; CDD diagrams and Bader charges of PMS adsorbed on different sites on FeCo–N/C models. Adapted with permission from ref . Copyright 2023 American Chemical Society.…”

Section: Theoretical Calculation Of Pms-aops Involving Cobalt-based H...mentioning

confidence: 99%

“…(d) Reaction pathway and free energy profiles of PMS activation on FeCo–N/C for the generation of high-valent species and optimized configurations of the proposed intermediate. Adapted with permission from ref . Copyright 2023 American Chemical Society.…”

Section: Theoretical Calculation Of Pms-aops Involving Cobalt-based H...mentioning

confidence: 99%

Current Mechanism of Peroxymonosulfate Activation by Cobalt-Based Heterogeneous Catalysts in Degrading Organic Compounds

et al. 2023

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Persulfate based advanced oxidation processes (PS-AOPs) have been regarded as a mainstream degradation technology of organic compounds due to their high efficiency in wastewater treatment. In particular, peroxymonosulfate (PMS) has a unique structure and chemical properties, which can be efficiently activated by Co-based catalysts to produce active species with a high oxidation potential. These active species usually determine the subsequent degradation of organic compounds in an efficient process, while the intrinsic reaction mechanism behind this complex process remains unclear and therefore impedes the continual development in this scientific community. Recently, density functional theory (DFT) calculations have emerged as a powerful means to identify the electronic properties and distinguish energy changes in the PMS activation system. With the assistance of this quantum calculation, increasing investigations have been conducted focusing on explaining the phenomenon that occurred in experiments. However, these calculations mainly contributed in part to the reaction mechanism of PMS activation by Co-based catalysts and sometimes even differ from each other, lacking a comprehensive summary based on DFT calculation results. In this review, we introduce the main uses of DFT in the catalytic activation of PMS, provide recent application of calculation examples of Co-based heterogeneous catalysts with different structures, and then discuss the mechanism of PMS activation in detail. Finally, the research results of the DFT method in this field are summarized, and the future research focus and challenges are put forward, which is conducive to guiding the practical design of Co-based catalysts and further application of PS-AOPs in creating value products.

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Improved Electronic Structure from Spin-State Reconstruction of a Heteronuclear Fe–Co Diatomic Pair to Boost the Fenton-like Reaction

Cited by 79 publications

References 58 publications

Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification

Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification

The Pivotal Role of Selenium Vacancies in Defective FeSe₂@MoO₃ for Efficient Peroxymonosulfate Activation: Experimental and DFT Calculation

Current Mechanism of Peroxymonosulfate Activation by Cobalt-Based Heterogeneous Catalysts in Degrading Organic Compounds

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Improved Electronic Structure from Spin-State Reconstruction of a Heteronuclear Fe–Co Diatomic Pair to Boost the Fenton-like Reaction

Cited by 79 publications

References 58 publications

Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification

Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification

The Pivotal Role of Selenium Vacancies in Defective FeSe2@MoO3 for Efficient Peroxymonosulfate Activation: Experimental and DFT Calculation

Current Mechanism of Peroxymonosulfate Activation by Cobalt-Based Heterogeneous Catalysts in Degrading Organic Compounds

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The Pivotal Role of Selenium Vacancies in Defective FeSe₂@MoO₃ for Efficient Peroxymonosulfate Activation: Experimental and DFT Calculation