Importing Antibonding‐Orbital Occupancy through Pd−O−Gd Bridge Promotes Electrocatalytic Oxygen Reduction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(52)

Published: Nov. 9, 2023

The active-site density, intrinsic activity, and durability of Pd-based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series carbon-based rare-earth (RE) oxides (Gd2 O3 , Sm2 Eu2 CeO2 ) by using RE metal-organic frameworks tune the ORR performance Pd sites through Pd-REx Oy interface interaction. Taking Pd-Gd2 /C as representative, it is identified that strong coupling between Gd2 induces formation Pd-O-Gd bridge, which triggers charge redistribution . screened exhibits impressive with high onset potential (0.986 VRHE ), half-wave (0.877 excellent stability. Similar results also found Pd-Sm2 /C, Pd-Eu2 Pd-CeO2 catalysts. Theoretical analyses reveal promotes electron transfer antibonding-orbital occupancy Pd-*OH optimization *OH adsorption rate-determining step ORR. pH-dependent microkinetic modeling shows close theoretical optimal activity ORR, outperforming Pt under same conditions. By its ascendancy superior Zn-air battery an air cathode, implying practicability.

Language: Английский

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Fe-N co-doped carbon nanofibers with Fe3C decoration for water activation induced oxygen reduction reaction

National Science Review, Journal Year: 2024, Volume and Issue: 11(10)

Published: June 3, 2024

Proton activity at the electrified interface is central to kinetics of proton-coupled electron transfer (PCET) reactions in electrocatalytic oxygen reduction reaction (ORR). Here, we construct an efficient Fe

Language: Английский

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Engineering Co‐N‐Cr Cross‐Interfacial Electron Bridges to Break Activity‐Stability Trade‐Off for Superdurable Bifunctional Single Atom Oxygen Electrocatalysts

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 29, 2024

Abstract Atomically dispersed metal‐nitrogen‐carbon (M‐N‐C) catalysts have exhibited encouraging oxygen reduction reaction (ORR) activity. Nevertheless, the insufficient long‐term stability remains a widespread concern owing to inevitable 2‐electron byproducts, H 2 O . Here, we construct Co‐N‐Cr cross‐interfacial electron bridges (CIEBs) via interfacial electronic coupling between Cr 3 and Co‐N‐C, breaking activity‐stability trade‐off. The partially occupied 3d‐orbitals of CIEBs induce rearrangement CoN 4 sites, lowering Co‐OOH* antibonding orbital occupancy accelerating adsorption intermediates. Consequently, suppress two‐electron ORR process approach apex Sabatier volcano plot for four‐electron pathway simultaneously. As proof‐of‐concept, is synthesized by molten salt template method, exhibiting dominant 4‐electron selectively extremely low yield confirmed Damjanovic kinetic analysis. demonstrates impressive bifunctional catalytic activity (▵E=0.70 V) breakthrough durability including 100 % current retention after 10 h continuous operation cycling performance over 1500 Zn‐air battery. hybrid configuration understanding mechanism reported here could shed new light on design superdurable M‐N‐C catalysts.

Language: Английский

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Boosting ORR/OER bifunctional electrocatalysis by promoting electronic redistribution of Fe-N-C on CoFe-FeNC for ultra-long rechargeable Zn-air batteries

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 359, P. 124485 - 124485

Published: Aug. 8, 2024

Language: Английский

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Earthworm‐Inspired Co/Co₃O₄/CoF₂@NSC Nanofibrous Electrocatalyst with Confined Channels for Enhanced ORR/OER Performance

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(26)

Published: Feb. 20, 2024

Abstract The rational construction of highly active and durable oxygen‐reactive electrocatalysts for oxygen reduction/evolution reaction (ORR/OER) plays a critical role in rechargeable metal‐air batteries. It is pivotal to achieve optimal utilization electrocatalytically sites valid control the high specific internal surface area. Inspiration designing can come from nature, as it full precisely manipulated efficient structures. Herein, inspired by earthworms fertilizing soil, 3D carbon nanofibrous electrocatalyst with multiple interconnected nanoconfined channels, cobalt‐based heterojunction particles enriched N, S heteroatoms (Co/Co 3 O 4 /CoF 2 @NSC confined channels) rationally designed, showing superior bifunctional electrocatalytic activity alkaline electrolyte, even outperforming that benchmark Pt/C‐RuO catalyst. This work demonstrates new method porous structural regulation, which channels within nanofibers are controllably formed spontaneous migration nanoparticles under CO atmosphere. Theoretical analysis reveals constructing Co/Co greatly adjust electron distribution, effectively lower barrier inter‐mediate reduce OER/ORR overpotential. introduces novel nature‐inspired strategy well‐designed architectures.

Language: Английский

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Unraveling the Tandem Effect of Nitrogen Configuration Promoting Oxygen Reduction Reaction in Alkaline Seawater

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(24)

Published: April 10, 2024

Abstract Developing seawater‐based high‐performance oxygen reduction reaction (ORR) electrocatalysts is meaningful to renewable energy storage and conversion, the Fe‐based derivatives encapsulated by nitrogen (N) doped carbon are typical representative. Nevertheless, unrevealing mechanism of N configuration ORR activity chlorine resistance still a great challenge. In this work, feasible strategy developed prepare controllable pyridinic/pyrrolic‐N carbon‐coated (Fe x N‐NC). Drawing support from H 3 PO 4 blocking based in situ Fourier transform infrared spectroscopy (FTIR) test density‐functional theory (DFT) calculation, tandem effect pyridinic‐N pyrrolic‐N on proved. Additionally, low hydrogen peroxide (H 2 O ) yield 4e − pathway Fe N‐NC demonstrate that doping effectively reduces adsorption Cl , which consistent with DFT. The half‐wave potential (E 1/2 for reaches 0.874 V alkaline seawater, ZABs assembled as air cathode deliver remarkable power density (162 mW cm −2 ), along excellent long‐term durability (>400 h).

Language: Английский

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Short-range electronic engineering by coupling Fe phthalocyanines with MOF-derived N,S-doped carbon nanorods for oxygen reduction

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Language: Английский

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Structural Regulation Strategies of Atomic Cobalt Catalysts for Oxygen Electrocatalysis

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

Published: March 3, 2025

Abstract Oxygen electrocatalysis is a core reaction in renewable energy devices, greatly promoting the transformation and upgrading of structure. Nonetheless, performance conversion devices hindered by large overpotential slow kinetics oxygen electrocatalytic reactions. Recently, single‐atom catalysts (SACs) have emerged as promising contenders field because their exceptional metal atom utilization, distinctive coordination environment, adjustable electronic properties. This review presents latest advancements design Co‐based SACs for electrocatalysis. First, OER ORR mechanisms are introduced. Subsequently, strategies regulating structure summarized three aspects, including centers, support carriers. A particular emphasis given to relationship between properties catalysts. Afterward, applications explored. Ultimately, challenges prospects prospected.

Language: Английский

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Pauling‐Type Adsorption of O₂ Induced by Heteroatom Doped ZnIn₂S₄ for Boosted Solar‐Driven H₂O₂ Production

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Dec. 12, 2023

Abstract Breaking the trade‐off between activity and selectivity has perennially been a formidable endeavor in field of hydrogen peroxide (H 2 O ) photosynthesis, especially side‐on configuration oxygen (O on catalyst surface will cause cleavage O−O bonds, which drastically hinders H production performance. Herein, we present an atomically heteroatom P doped ZnIn S 4 with tunable adsorption to accelerate ORR kinetics essential for solar‐driven production. Indeed, spectroscopy characterizations (such as EXAFS situ FTIR) DFT calculations reveal that at substitutional interstitial sites, not only optimizes coordination environment Zn active but also facilitates electron transfer sites improves charge density, avoiding breakage bonds reducing energy barriers As result, is regulated from (Yeager‐type) end‐on (Pauling‐type), resulting accelerated 874.94 2107.66 μmol g −1 h . This finding offers new avenue toward strategic tailoring by rational design photocatalyst.

Language: Английский

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Bi₁‐CuCo₂O₄ Hollow Carbon Nanofibers Boosts NH₃ Production from Electrocatalytic Nitrate Reduction

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 6, 2024

Abstract Ammonia, as a high‐energy‐density carrier for hydrogen storage, is in great demand worldwide. Electrocatalytic nitrate reduction reaction (NO 3 RR) provides green NH production process. However, the complex pathways NO RR to and difficulty controlling intermediate products limit Herein, by incorporating atomic‐level bismuth (Bi) into CuCo 2 O 4 hollow carbon nanofibers, catalytic activity of electrocatalyst enhanced. The maximum Faradaic efficiency Bi 1 ‐CuCo 95.53%, with an yield 448.74 µmol h −1 cm −2 at −0.8 V versus RHE. Density Functional Theory calculations show that presence lowers barrier hydrogenation step from *NO H, while promoting mass transfer on release *NH reactivation surface‐active sites. Differential charge density also after doping, supplied catalyst − increases 0.62 0.72 e ‐ , thus reasoned enhanced activity. established nitrate‐Zn battery shows energy 2.81 mW implying potential application.

Language: Английский

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