Deciphering the Origin of Higher Shell Coordination on Single Iron Catalysts for Resilient Modulating Persulfate Oxidation Into Singlet Oxygen Pathway

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Abstract Precise manipulation of coordination structure single‐atom sites and establishment schematic microenvironment‐oxidation pathway relations remain significant challenges in Fenton‐like chemistry. Herein, incorporating sulfur heteroatoms into the higher shell FeN 4 (Fe‐NSC) exhibited a volcano trend p ‐hydroxybenzoic acid oxidation, aligning with number positions dopant. Specifically, S moderate electronegativity larger atomic radii triggers long‐range electronic interactions, which provoke Fe 3d orbital splitting spin electron rearrangement, resulting crossover states d xy 2 yz 1 xz z 21 . As result, partial filling e g t orbitals σ/π antibonding between 2p optimized adsorption–desorption behaviors key oxygenated intermediates from peroxymonosulfate activation. Thus, optimal binding configuration weakens Fe─O bonding accelerates PMS dissociation to yield C‐S‐N Fe‐O*, subsequently couples form O nearly 100% selectivity. The Fe‐NSC‐functionalized membrane outstanding long‐term reusability continuous flow reactor further validated practical application perspective. This study provides insight at both levels for rational design spin‐polarized catalysts its functions fine‐tuning oxidation pathways environmental catalysis.

Language: Английский

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Scalable progress for advanced bifunctional electrocatalysts for practical zinc-air batteries

Journal of Energy Storage, Journal Year: 2025, Volume and Issue: 109, P. 115230 - 115230

Published: Jan. 2, 2025

Language: Английский

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Constructing Janus Structures and Rich Electron Pool in 2D TMTe Nanostructures To Achieve OER/ORR Electrocatalysts

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

Through first-principles structure search calculations, we have identified ten hitherto unknown two-dimensional (2D) Janus-wrinkled TMTe monolayers (TM = Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os, and Hf) by screening 3d, 4d, 5d transition metal atoms. These exhibit high stability metallic conductivity. Among the discovered materials, 2D PdTe (ηOER/ORR 0.46/0.22 V) PtTe 0.46/0.32 can demonstrate superior bifunctional catalytic performance for oxygen evolution reduction reactions (OER/ORR), with lower overpotential than state-of-the-art IrO2 OER Pt (111) ORR, respectively. The TM- Te-sides originating from unique Janus configurations play a crucial role in ORR activities, Furthermore, stacking monolayer structures, eight new (TMTe)2 bilayers conductivity be achieved, which possess an internal layer, forming rich electron pool. This effectively improves adsorption activity on some bilayers, including (PdTe)2, (PtTe)2, (RhTe)2, (IrTe)2, transferring more electrons to adsorbed O2 molecule, leading considerably (ηORR 0.16–0.44 V). Moreover, detailed analyses of mechanisms been conducted. intriguing findings offer insights designing low-cost high-performance electrocatalysts reactions, potential replace related noble catalysts used water splitting, fuel cells, metal-air batteries, etc.

Language: Английский

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Borrowing Hydrogen Mechanism in Amine Alkylation by Single Atom Nickel Catalysts

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11332 - 11342

Published: July 15, 2024

The alkylation of amines with alcohols by borrowing hydrogen (BH) is a versatile synthetic route to various relevant compounds, including drugs and agrochemicals. atom economy this reaction, water as the sole byproduct, entails complex mechanism in which alcohol activation can follow multiple competing pathways. interest single catalysts (SACs) combining advantages homogeneous heterogeneous systems motivated computational study on BH catalyzed nickel SACs. We found that oxidation, charge, spin states system, well geometry support, all have strong influence mechanism. pyrrolic support was most reactive dicationic state nearly degenerate singlet triplet configurations. free energy catalyst hydrogenation H2 strongly correlated its reactivity, thus being useful descriptor. Further, followed an unusual reaction pathway takes delivers H equivalents, metal playing spectator role. This provides insights for further development

Language: Английский

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Catalysis under electric-/magnetic-/electromagnetic-field coupling

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 19, 2024

This review outlines recent advances in field-regulated catalysis and reveals the key role of dipole manipulation by electric/magnetic/electromagnetic fields.

Language: Английский

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Ferromagnetic Fe-TiO2 spin catalysts for enhanced ammonia electrosynthesis

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 28, 2025

Abstract Magnetic field effects (MFE) of ferromagnetic spin electrocatalysts have attracted significant attention due to their potential enhance catalytic activity under an external magnetic field. However, no catalysts demonstrated MFE in the electrocatalytic reduction nitrate for ammonia (NO 3 RR), a pioneering approach towards NH production involving conversion from diamagnetic NO − paramagnetic NO. Here, we report Fe-TiO 2 investigate on RR. possesses high density atomically dispersed Fe sites and exhibits intermediate-spin state, resulting ordering through ferromagnetism. Assisted by field, achieves Faradaic efficiency (FE) up 97% yield 24.69 mg cat 1 at −0.5 V versus reversible hydrogen electrode. Compared conditions without FE is increased ~21.8% ~ 3.1 times, respectively. In-situ characterization theoretical calculations show that polarization enhances critical step hydrogenation NOH optimizing electron transfer pathways between NO, significantly boosting RR activity.

Language: Английский

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Electrochemical reduction for modulating spin state of nickel: A pathway to improved water and seawater oxidation

Applied Physics Letters, Journal Year: 2025, Volume and Issue: 126(4)

Published: Jan. 27, 2025

Understanding the electronic structure of catalysts is crucial for analyzing electrocatalyst behavior. Here, we present a straightforward method to modify configuration active sites in nickel-iron-niobium layered double hydroxides (NiFeNb-LDHs) via electrochemical reduction (ER), uncovering key factors that enhance oxygen evolution reaction (OER) activity. The results indicate ER-NiFeNb-LDHs display excellent OER performance and long-term stability over 60 h various electrolytes (271.99 mV@50 mA cm−2 1M KOH 280.56 +0.5M NaCl). Furthermore, cell voltage two-electrode electrolyzer ǁ Pt/C achieves current density 50 at an ultra-low 1.58 V, significantly outperforming commercial RuO2ǁPt/C. X-ray absorption spectroscopy, magnetic characterization, functional theory calculations reveal unsaturated coordination environment created by ER modifies state distribution between eg t2g orbitals, effectively lowering spin nickel enhancing its

Language: Английский

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Practical Applications of Grand-canonical Electronic Structure Calculations in Electrochemical Simulation

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 1470 - 1477

Published: Feb. 2, 2025

Modeling electrified interfaces has long been a great challenge in electrochemistry. In recent years, the grand-canonical treatment for electrons gradually developed, and its combination with density functional theory widely used to simulate electrochemical processes on an atomistic scale. this Perspective, we aim discuss several practical applications of powerful technique after short review necessary fundamentals. We will begin capacitor-based parametrization method calculated results. If considering electrodes under different applied potentials as materials, can be viewed kind "quadratic scaling relation", which might reduce overall computational costs by data postanalysis rather than algorithm development. Following example abnormal potential-independent energetic curve within bandgap area, turn topic semiconducting electrodes. Meanwhile, specific behaviors also indicate that besides reaction thermodynamics kinetics, detailed electronic structure system well described electrons. Several possibilities further are proposed correspondingly summarized at end paper. believe calculations greatly enrich our understanding fundamental mechanisms environments.

Language: Английский

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Theoretical Insights into the Selectivity of Single-Atom Fe–N–C Catalysts for Electrochemical NO_x Reduction

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

Single-atom Fe-N-C catalysts have attracted significant attention in the NOx reduction reaction (NOxRR). However, origin of their selectivity NOxRR remains unclear, impeding further advancements application. Herein, we investigate potential-driven competitive mechanism for NH3 and NH2OH production over single-atom pyridinic-FeN4 pyrrolic-FeN4 sites using constant-potential density functional theory calculations. The is linked to switching Fe 3d orbitals as they interact with intermediates. between determined by applied potentials. predominantly generates at higher potentials (-0.6 -1.2 V, vs SHE), while favored lower (0.6 -0.6 V). shows a similar potential-dependent product distribution, crossover potential -1.0 V. selectivity-determining intermediates (SDIs) are *NH2OH *NH2 + *OH. governed interacting SDIs, from dumbbell-shaped 3dz2 four-leaf clover-like 3dxz, 3dyz, 3dx2-y2, which plays crucial role controlling distribution based on These findings offer new insights into NOxRR.

Language: Английский

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Electronic Communication Between Single Atomic Nickel and Iron‐Nitrogen Species Promote the Bifunctional Oxygen Evolution and Reduction for Efficient Rechargeable Zinc‐Air Battery

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Abstract The reversible oxygen evolution/reduction reaction (OER/ORR) have been recognized as the key electrochemical process for next‐generation energy conversion and storage (ECS) devices, such fuel cells metal‐air batteries. However, intrinsic large overpotential barrier caused by oxygen‐containing intermediates (*OH, *O, *OOH) greatly hamper kinetics of OER/ORR. In this work, a dual‐functional OER/ORR electrocatalyst composed Ni single atomic sites FeN 0.0324 nanoclusters within unique core–shell structure @NiN 4 /C is constructed. Benefiting from efficient synergistic electronic effect , exhibits excellent electrocatalytic activities OER with an 258 mV at 10 mA cm −2 ORR half‐wave potential (E 1/2 ) 0.89 V. A liquid zinc‐air battery assembled achieves maximum peak power density 180.9 mW cycle endurance stability more than 150 h. Density functional theory (DFT) calculation indicates that d ‐band center near Fermi level NiN ‐FeN shifted upward in comparison pristine H, which effectively optimizes adsorption *O alleviates troublesome process. This study provides new platform construction electrocatalysts field devices.

Language: Английский

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