Spin-State-Dependent Peroxymonosulfate Activation of Single-Atom M–N Moieties via a Radical-Free Pathway

Miao, Jie; Zhu, Yuanyuan; Lang, Junyu; Zhang, Jingzhen; Cheng, Si; Zhou, Baoxue; Zhang, Lizhi; Alvarez, Pedro J. J.; Long, Mingce

doi:10.1021/acscatal.1c02031

Cited by 215 publications

(149 citation statements)

References 45 publications

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“…The process of electron transfer could be confirmed by the obviously increased cathodic current densities for the p‐CoSi 1 N 3 @D electrode with the addition of PMS in the LSV analysis (Figure S41, Supporting Information). [ 18,58 ] In this case, PMS is decomposed to be SO 5 •− and to subsequently form 1 O 2 (Equations (1) and (2)), which agreed well with the EPR and scavenging experiment results [ 61,62 ]

\begin{matrix} {HSO}_{5}^{-} - {normale}^{-} \to {SO}_{5}^{• -} + {normalH}^{+} \end{matrix}

\begin{matrix} {SO}_{5}^{• -} + {SO}_{5}^{• -} \to 2 {SO}_{4}^{2 -} +^{1} {normalO}_{2} \end{matrix}

…”

Section: Resultssupporting

confidence: 80%

“…Distinct from the findings in previous studies, the peaks centered at around 830 and 1135 cm −1 did not detected after mixing with PMS, which could be ascribed to the absence of metastable and highly reactive peroxo species (labeled as Co‐PMS*) during PMS activation (Figure S40, Supporting Information). [ 58–60 ] As for p‐CoSi 1 N 3 @D/PMS oxidation system, the direct electron‐transfer pathway might play the significant role rather than the generation of Co‐PMS*. The process of electron transfer could be confirmed by the obviously increased cathodic current densities for the p‐CoSi 1 N 3 @D electrode with the addition of PMS in the LSV analysis (Figure S41, Supporting Information).…”

Section: Resultsmentioning

confidence: 88%

“…The process of electron transfer could be confirmed by the obviously increased cathodic current densities for the p-CoSi 1 N 3 @D electrode with the addition of PMS in the LSV analysis (Figure S41, Supporting Information). [18,58] In this case, PMS is decomposed to be SO 5…”

Section: Radical (Somentioning

confidence: 99%

See 2 more Smart Citations

Mineral Modulated Single Atom Catalyst for Effective Water Treatment

Dong

Chen

Tang

et al. 2022

Adv Funct Materials

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Single atom catalysts (SACs) have been growing as an emerging "hot" topic in environmental remediation. Their performance can be rationally optimized via modulating spatial coordination configuration and the porous structure of SACs, which is still challenging. Herein, a novel Si, N co-coordinated cobalt SAC (p-CoSi 1 N 3 @D) with 3D free standing architecture is tailored via employing natural mineral (diatomite) as a Si source and porous template. Theoretical calculations and experimental analysis reveal that the substitution of N by Si dramatically accelerates the interaction and electron transfer between peroxymonosulfate and the Co single atom center. Moreover, p-CoSi 1 N 3 @D inherits the hierarchically porous architecture of diatomite, providing more accessible cobalt sites and open diffusion channels for peroxymonosulfate and contaminants in water treatment applications. Thanks to optimal coordination structure and porous architecture, p-CoSi 1 N 3 @D can serve as a highly active catalyst for peroxymonosulfate activation, with a turnover frequency of 299.8 min −1 for bisphenol A degradation, surpassing those of catalysts with transition metal SACs or oxides in the disclosed literature. This work provides a novel strategy for the development of SACs for wastewater reclamation, and deepens the understanding of the significant role of templates in spatial coordination configuration of SACs.

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\begin{matrix} {HSO}_{5}^{-} - {normale}^{-} \to {SO}_{5}^{• -} + {normalH}^{+} \end{matrix}

\begin{matrix} {SO}_{5}^{• -} + {SO}_{5}^{• -} \to 2 {SO}_{4}^{2 -} +^{1} {normalO}_{2} \end{matrix}

…”

Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 88%

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Mineral Modulated Single Atom Catalyst for Effective Water Treatment

Dong

Chen

Tang

et al. 2022

Adv Funct Materials

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“…[224] N-coordinated metal (M-N x ) SACs (such as g-C 3 N 4 and N-doped carbon-based SACs) have atomically dispersed metal active sites with tunable coordination structures and easily increased atom density, which can efficiently catalyze the activation of persulfate. [225] By adjusting coordination structures and active site densities of SACs, it is expected to realize the nonfree radical persulfate activation, which lays a structural foundation for studying the intrinsic activity and simplifying descriptors of catalysts (see Figure 23 and Table 5 for details). [226][227][228][229][230][231] Generally, in advanced oxidation processes (AOPs), inexpensive and high-abundance Fe-based catalysts show the persulfate activation mechanism dominated by free radicals.…”

Section: Brief Summary Of Afcs On Electrocatalysismentioning

confidence: 99%

“…Although SACs are thermodynamically stable on related supports, their structural dynamic changes in the catalytic reaction process are likely to bring underlying instability, while the dynamic stability of SACs in the catalytic process is still ignored for a long time. [ 257 ] In the dense distribution state, the chemical environment around high‐density single metal atoms will change greatly (such as charge density, [ 56,135 ] electron spin state, [ 40,225 ] chemical bond parameter, [ 11,37 ] adsorption free energy, [ 149,165 ] etc. ), and whether ultrahigh‐density SACs are still stable under dynamic catalysis environment is worthy of in‐depth study.…”

Section: Scientific and Technological Challenges Of Afcsmentioning

confidence: 99%

Emerging Ultrahigh‐Density Single‐Atom Catalysts for Versatile Heterogeneous Catalysis Applications: Redefinition, Recent Progress, and Challenges

Liao

et al. 2022

Small Structures

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In recent years, single‐atom catalysts (SACs) with high metal loading have emerged in different heterogeneous catalysis fields and shown extraordinary catalytic properties. When there are enough coordination atoms (or functional groups) on the supports, it is possible to achieve a limit monolayer atom loading on the surface of supports with ultrahigh atom density (5–15 atoms nm−2) and extremely close site distance (0.2–0.5 nm), by using appropriate synthesis methods and procedures. These high‐density metal atoms usually have no or less metal bonds, which are mostly isolated by support atoms to form 3D foam‐like atomic constructions. Herein, a new notion of metal atomic foam catalysts (AFCs) is propsed to redefine these ultrahigh‐density SACs accommodated by specific supports. This new paradigm of 3D atomic construction for SACs has potential significance for both theoretical research and industrial applications. The latest major advancements in the controllable synthesis of AFCs on various supports (e.g., polymer, carbon, and metallic compound) via different methods (bottom‐up or top‐down approaches) are summarized. The latent catalytic principles and typical application cases of AFCs are emphasized in a wide range of heterogeneous catalysis fields (e.g., thermocatalysis, photocatalysis, electrocatalysis, etc.). The challenges and prospects of this newly 3D ultrahigh‐density AFCs materials in practical industrial application are pointed out as well.

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Coordination Number Dependent Catalytic Activity of Single‐Atom Cobalt Catalysts for Fenton‐Like Reaction

Liang

Wang

Zhao

et al. 2022

Adv Funct Materials

102

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Single‐atom catalysts (SACs) are widely investigated in Fenton‐like reactions for environmental remediation, wherein their catalytic performance can be further improved by coordination structure modulation, but the relevant report is rare. Herein, a series of atomically dispersed cobalt catalysts with diverse coordination numbers (denoted as CoNx, x represents nitrogen coordination number) are synthesized and their peroxymonosulfate (PMS) conversion performance is explored. The catalytic specific activity of CoNx is found to be dependent on coordination number of single atomic Co sites, where the lowest‐coordinated CoN2 catalyst exhibits the highest specific activity in PMS activation, followed by under‐coordinated CoN3 and normal CoN4. Experimental and theoretical results reveal that reducing coordination number can increase the electron density of single Co atom in CoNx, which governs the Fenton‐like performance of CoNx catalysts. Specifically, the entire Co–pyridinic NC motif serves as active centers for PMS conversion, where the single Co atom, and pyridinic N‐bonded C atoms along with nitrogen vacancy neighboring the unsaturated Co–pyridinic N2 moiety account for PMS reduction and oxidation toward radical and singlet oxygen (1O2) generation, respectively. These findings provide a useful avenue to coordination number regulation of SACs for environmental applications.

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Spin-State-Dependent Peroxymonosulfate Activation of Single-Atom M–N Moieties via a Radical-Free Pathway

Cited by 215 publications

References 45 publications

Mineral Modulated Single Atom Catalyst for Effective Water Treatment

Mineral Modulated Single Atom Catalyst for Effective Water Treatment

Emerging Ultrahigh‐Density Single‐Atom Catalysts for Versatile Heterogeneous Catalysis Applications: Redefinition, Recent Progress, and Challenges

Coordination Number Dependent Catalytic Activity of Single‐Atom Cobalt Catalysts for Fenton‐Like Reaction

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