Nonmetallic High‐Entropy‐Engineered Nanocarbons for Advanced ORR Electrocatalysis

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

Abstract High‐entropy materials are poised to revolutionize science and industrial applications due their design flexibility, peculiar performance, broad applicability. In this study, we present a proof‐of‐concept high‐entropy engineered nanocarbon (HENC) co‐doped with five nonmetal elements (B, F, P, S, N), synthesized via in situ polymerization modification of ZIF‐8 followed by pyrolysis. The HENC exhibits outstanding performance as electrocatalyst for the oxygen reduction reaction (ORR), activity on par benchmark Pt/C electrocatalysts superior cyclic stability. Simulations all‐site calculations reveal that synergistic effects abundant heteroatoms increased system entropy facilitate formation *O 2 species, N, S acting key active elements, while co‐doping B F further enhances Notably, HENCs have been validated cathode catalysts zinc–air batteries, achieving an impressive peak power density 604 mW cm −2 demonstrating long‐term stability over 16‐day period, outpacing commercial catalyst (542 ). This work not only enriches concept high advances understanding but also opens new avenue development high‐performance low‐cost catalysts.

Language: Английский

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Highly active air electrode catalysts for Zn‐air batteries: Catalytic mechanism and active center from obfuscation to clearness

Carbon Neutralization, Journal Year: 2024, Volume and Issue: 3(4), P. 501 - 532

Published: June 4, 2024

Abstract Carbon‐based materials have been found to accelerate the sluggish kinetic reaction and are largely subject overall Zn‐air batteries (ZABs) property, while their full catalytic mechanism is still not excavated because of indistinct internal structure immature in‐situ technology. Up now, systematic methods utilized study design promising high‐performance carbon‐based catalysts. To resolve real active units mechanism, developing molecular catalyst a significant strategy. Herein, review will initiate briefly introduce working principle composition ZABs. An important statement correspondingly provided about typical mechanisms for air cathode material. It also presents tremendous endeavors on performance stability Furthermore, combined with theoretical calculation, self‐defined sites analyzed understand character, where subsequently summarized discussed through highlighting unambiguous controllable structure, in hope surfacing optimum catalyst. Building fundamental understanding catalysts, this expected provide guidance direction toward designing future mechanistic studies ORR electrocatalysts.

Language: Английский

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Self‐Assembled Covalent Triazine Frameworks Derived N, S Co‐Doped Carbon Nanoholes with Facilitating Ions Transportation Toward Remarkably Enhanced Oxygen Reduction Reaction and for Zinc–Air Batteries

Small, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 15, 2024

3D assembled carbon materials, featuring unique hierarchical porosity and interconnected channels, are essential for the advancement of emerging zinc-air batteries (ZABs). In this study, nitrogen (N) sulfur (S) co-doped nanoholes (N/S-CNHs) synthesized through a straightforward procedure involving self-assembly followed by carbonization. This process utilizes hybrid self-assembled covalent triazine framework sodium lignosulphonate (CTF@LS) as multifunctional precursor. The resulting N/S-CNHs exhibit distinctive microstructure composed interwoven nanoclusters, which facilitates efficient ion electron transport during electrocatalytic process. incorporation N S atoms intriguingly alters wetting properties catalyst microenvironment, thereby significantly facilitating transfer key intermediates their interaction with electrolyte. Consequently, optimized N/S-CNH-900 demonstrates remarkable activity ORR (E

Language: Английский

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Electronic and porous structure engineering of coordination polymer-derived carbon for enhanced bifunctional oxygen electrocatalysts

International Journal of Hydrogen Energy, Journal Year: 2025, Volume and Issue: 102, P. 1411 - 1420

Published: Jan. 17, 2025

Language: Английский

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Bimetallic self-supported AuCu alloy aerogel with abundant diffusion channels for regulating oxygen reduction reaction by electronic structure modulation for zinc-air battery application

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 159930 - 159930

Published: Jan. 1, 2025

Language: Английский

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Cu and P co-doped nitrogen-doped hierarchical carbon for enhanced oxygen reduction reaction in zinc-air battery

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

High-performance Fe-based nitrogen-doped carbon oxygen reduction catalysts have been widely reported, but the Fenton reaction faced by such has hindered their practical application in fuel cells. The development of inexpensive, effective, and durable non-Fe electrocatalysts is important for advancing cell technology. In this work, we introduced a molecular coordination chemistry method to synthesize Cu- P-co-doped hierarchical (Cu-P-N-C) (ORR) electrocatalyst pyrolyzing mixture phytate melamine. refined Cu-P-N-C material showcased three-dimensional, porous, interconnected nanosheet structure with an ultra-high specific surface area abundance active sites. catalyst displayed half-wave potential (E1/2) 0.86 VRHE, higher than that commercial Pt/C 0.1 M KOH. It was also found maintain impressive long-term stability, retaining 95.4% its initial activity after extensive testing. When integrated into zinc-air batteries (ZABs), observed deliver exceptional performance, achieving high peak power density 164.5 mW cm-2, promising capacity 807 mA h g-1, remarkable stability. These findings underscore as candidate next-generation ORR new energy devices.

Language: Английский

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Regulating the Isomerization Geometry and Energy State of Covalent Organic Frameworks for Enhanced Oxygen Reduction Activity

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

Published: Feb. 19, 2025

Abstract Embedding isomer entities onto crystalline frameworks with precisely defined spatial distributions represents a promising approach to enhancing the efficiency of oxygen reduction reaction (ORR) in fuel cells. However, accurately constructing covalent organic (COFs) regulate energy state effectively remains significant challenge. Herein, an innovative geometric isomerization strategy aimed at minimizing rotational barrier (ΔE), average local ionization (ALIE), and Gibbs free (ΔG) for ORR within COFs is proposed. Based on this strategy, isomeric Py‐COF‐αα 2,2‐substitution, Py‐COF‐ββ 3,3‐substitution, Py‐COF‐αβ 2,3‐substitution mainchain have been obtained. The electronic states intermediate adsorption capabilities are finely tuned through modification, yielding controllable chemical activity. Notably, lower ΔE between thiophenes achieves remarkable performance, evidenced by half‐wave potential 0.77 V vs reversible hydrogen electrode (RHE), surpassing most reported metal‐free electrocatalysts. Combined theoretical prediction situ Raman spectra, it revealed that increased dipole moment non‐uniform charge distribution caused endows pentacyclic‐carbon (thiophene β‐position) far from sulfur atoms efficient catalytic This work has opened up novel paradigm underscores pivotal role regulation facilitating catalysis.

Language: Английский

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Constructing Pentagonal Topological Defects in Carbon Aerogels for Flexible Zinc‐Air Batteries

Small, Journal Year: 2025, Volume and Issue: unknown

Published: March 16, 2025

Abstract In the context of energy conversion, design and synthesis high‐performance metal‐free carbon electrocatalysts for oxygen reduction reaction (ORR) is crucial. Herein, a one‐step nitrogen doping/extraction strategy proposed to fabricate 3D nitrogen‐doped aerogels (NCA‐Cl) with rich pentagonal topological defects. The NCA‐Cl electrocatalyst exhibits superb ORR activity, displaying half‐wave potential 0.89 V vs RHE 0.74 under alkaline (0.1 m KOH) acidic HClO 4 ) media, respectively, thanks balanced * OOH intermediate adsorption desorption induced by defects dopants. aqueous zinc‐air battery (ZAB) equipped cathode delivers peak power density 206.6 mW cm −2 , specific capacity 810.6 mAh g −1 durability 400 h, flexible ZAB also performed convincingly. This work provides an effective formation enhancement electrocatalytic activity carbon‐based catalysts.

Language: Английский

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Nitrogen, sulfur co-coordinated iron single-atom catalysts with the optimized electronic structure for highly efficient oxygen reduction in Zn-air battery and fuel cell

Journal of Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 671, P. 643 - 652

Published: May 27, 2024

Language: Английский

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Triple Templates Directed Synthesis of Nitrogen‐Doped Hierarchically Porous Carbons from Pyridine Rich Monomer as Efficient and Reversible SO₂ Adsorbents

Small, Journal Year: 2024, Volume and Issue: 20(46)

Published: Aug. 2, 2024

Abstract Herein, a variety of 2,6‐diaminopyridine (DAP) derived nitrogen‐doped hierarchically porous carbon (DAP‐NHPC‐T) prepared from carbonization‐induced structure transformation DAP‐Zn‐SiO 2 ‐P123 nanocomposites are reported, which facilely solvent‐free co‐assembly block copolymer templates P123 with pyridine‐rich monomer DAP, Zn(NO 3 ) and tetramethoxysilane. In the pyrolysis process, SiO promote formation mesoporous supermicroporous structures in DAP‐NHPC‐T, while high‐temperature volatilization Zn contributed to generation micropores. The DAP‐NHPC‐T possess large BET surface areas (≈956–1126 m g −1 ), hierarchical porosity micro‐supermicro‐mesoporous feature high nitrogen contents (≈10.44–5.99 at%) tunable density pyridine‐based sites (≈5.99–3.32 at%), exhibiting good accessibility reinforced interaction SO . Consequently, show capacity (14.7 mmol , 25 °C 1.0 bar) /CO /N IAST selectivities, extraordinary dynamic breakthrough separation efficiency cycling stability, far beyond any other reported metal‐free carbon. As verified by situ spectroscopy theoretical calculations, boost adsorption via unique charge transfer, mechanism reaction model have been finally clarified.

Language: Английский

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