Dual Doping of B and Fe Activated Lattice Oxygen Participation for Enhanced Oxygen Evolution Reaction Activity in Alkaline Freshwater and Seawater

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(37)

Published: May 6, 2024

Abstract The exploitation of highly activity oxygen evolution reaction (OER) electrocatalysts is critical for the application electrocatalytic water splitting. Triggering lattice mechanism (LOM) expected to provide a promising pathway overcome sluggish OER kinetics, however, effectively enhancing involvement remains challenging. In this study, fabrication B, Fe co‐doped CoP (B, Fe─CoP) nanofibers reported, which serve as efficient electrocatalyst through phosphorization and boronation treatment Fe‐doped Co 3 O 4 nanofibers. Experimental results combined with theoretical calculations reveal that simultaneous incorporation both B can more trigger participation in CoFe oxyhydroxides reconstructed from Fe─CoP compared incorporating only or Fe. Therefore, optimized exhibit superb low overpotentials 361 376 mV at 1000 mA cm −2 alkaline freshwater natural seawater, respectively. present work provides significant guidelines innovative design concepts development following LOM pathway.

Language: Английский

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Substantial Impact of Spin State Evolution in OER/ORR Catalyzed by Fe–N–C

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6816 - 6826

Published: April 18, 2024

The Fe-embedded N-doped graphene (Fe–N–C) is the most representative single atom catalyst (SAC) that has shown great potentiality in electrocatalysis, such as oxygen reduction reaction (ORR) and evolution (OER). However, active moiety of Fe–N–C still elusive due to contradictory experimental results. Moreover, early simulations mainly focus on thermodynamic potential adsorbates, while effect spin multiplicity receives little attention. To explore role we employ constant-potential density functional theory (DFT) systematically study structural high-spin (HS) intermediate-spin (IS) FeN4 site (marked by FeN4HS/IS) OER ORR processes. With consideration multiplicity, our simulation shows spontaneous oxidation from Fe(II)N4IS Fe(III)N4HS at U = 0.4 V versus SHE. Further indicates FeN4IS undergoes a sequential adsorption *OH *OOH along with increase, which leads state transition IS HS. According free energy analysis, FeN4HS*OOH confirmed be practical centers OER, FeN4HS*OH are assigned center low high overpotentials. predicted activity agrees situ X-ray absorption near-edge spectroscopy (XANES) 57Fe Mössbauer measurement Xiao et al. [Microporous Framework Induced Synthesis Single-Atom Dispersed Fe-NC Acidic Catalyst its In Situ Reduced Fe-N4 Active Site Identification Revealed X-Ray Absorption Spectroscopy. ACS Catal. 2018, 8, 2824–2832]. Based geometry orbital bond length Fe–N coordination number Fe found have significant impact d splitting thus induce turnover HS/IS stability OER/ORR intermediates. Our brings comprehensive insights into Fe–N–C, reveals significance electrocatalysis benefits further theoretical design SACs perspective effects.

Language: Английский

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A Guide to Electrocatalyst Stability Using Lab-Scale Alkaline Water Electrolyzers

ACS Energy Letters, Journal Year: 2024, Volume and Issue: 9(2), P. 547 - 555

Published: Jan. 23, 2024

ADVERTISEMENT RETURN TO ISSUEPREVViewpointNEXTA Guide to Electrocatalyst Stability Using Lab-Scale Alkaline Water ElectrolyzersRaul A. MarquezRaul MarquezDepartment of Chemistry, The University Texas at Austin, 78712, United StatesMore by Raul Marquezhttps://orcid.org/0000-0003-3885-5007, Michael EspinosaMichael EspinosaDepartment Espinosahttps://orcid.org/0000-0002-9457-574X, Emma KalokowskiEmma KalokowskiDepartment Kalokowskihttps://orcid.org/0009-0000-5264-8464, Yoon Jun SonYoon SonMcKetta Department Chemical Engineering, Sonhttps://orcid.org/0000-0003-1704-2314, Kenta KawashimaKenta KawashimaDepartment Kawashimahttps://orcid.org/0000-0001-7318-6115, Thuy Vy LeThuy LeDepartment Lehttps://orcid.org/0009-0004-1422-1450, Chikaodili E. ChukwunekeChikaodili ChukwunekeDepartment Chukwunekehttps://orcid.org/0000-0003-0478-8387, and C. Buddie Mullins*C. MullinsDepartment StatesMcKetta StatesTexas Materials Institute, StatesCenter for Electrochemistry, StatesH2@UT, States*[email protected]More Mullinshttps://orcid.org/0000-0003-1030-4801Cite this: ACS Energy Lett. 2024, 9, 2, 547–555Publication Date (Web):January 23, 2024Publication History Received20 December 2023Accepted17 January 2024Published online23 inissue 9 February 2024https://doi.org/10.1021/acsenergylett.3c02758Copyright © 2024 American Society. This publication is available under these Terms Use. Request reuse permissions free access through this site. Learn MoreArticle Views5756Altmetric-Citations1LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated reflect usage leading up last few days.Citations number other articles citing article, calculated Crossref daily. Find more information about citation counts.The Altmetric Attention Score a quantitative measure attention that research has received online. Clicking on donut icon will load page altmetric.com with additional details score social media presence given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail (5 MB) Get e-AlertscloseSupporting Info (3)»Supporting Information Supporting SUBJECTS:Catalysts,Electrocatalysts,Electrodes,Stability,Testing assessment e-Alerts

Language: Английский

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Manipulating electron redistribution between iridium and Co₆Mo₆C bridging with a carbon layer leads to a significantly enhanced overall water splitting performance at industrial-level current density

Chemical Science, Journal Year: 2024, Volume and Issue: 15(30), P. 11890 - 11901

Published: Jan. 1, 2024

Ir nanoparticles on Co 6 Mo C nanofibers bridging with a carbon layer have been fabricated as efficient bifunctional electrocatalysts for water splitting, presenting ultrahigh electrocatalytic performance at ampere-level current density.

Language: Английский

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Inhibiting Dissolution of Active Sites in 80 °C Alkaline Water Electrolysis by Oxyanion Engineering

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 29, 2024

Abstract Commercial alkaline water electrolysers typically operate at 80 °C to minimize energy consumption. However, NiFe‐based catalysts, considered as one of the most promising candidates for anode, encounter bottleneck high solubility such temperatures. Herein, we discover that dissolution NiFe layered double hydroxides (NiFe‐LDH) during operation not only leads degradation anode itself, but also deactivates cathode splitting, resulting in decay overall electrocatalytic performance. Aiming suppress dissolution, employed oxyanions inhibitors electrolyte. The added phosphates electrolyte inhibit loss NiFe‐LDH active sites 400 mA cm −2 1/3 original amount, thus reducing rate performance by 25‐fold. Furthermore, usage borates, sulfates, and carbonates yields similar results, demonstrating reliability universality site inhibitor, its role elevated electrolysis.

Language: Английский

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Exploring Structural Evolution Behaviors of Ligand‐Defect‐Rich Ferrocene‐Based Metal‐Organic Frameworks for Electrochemical Oxygen Evolution via Operando X‐Ray Absorption Spectroscopy

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

Published: June 25, 2024

Abstract Metal‐organic frameworks (MOFs) have exhibited encouraging catalytic activity for the oxygen evolution reaction (OER), a crucial process water electrolysis to produce green hydrogen. Nonetheless, distinguishing source of and establishing structure‐composition‐property relationships MOFs during OER processes remain challenging. Here, first time, operando X‐ray absorption spectroscopy (XAS) is utilized monitor structural identify active components ferrocene‐based (Ni‐Fc) OER. Ligand‐defect‐rich Ni‐Fc synthesized via co‐deposition method. After electrochemical activation, exhibits superior electrocatalytic (228 mV at 10 mA cm −2 in 0.1 m KOH), which highly competitive compared with state‐of‐the‐art electrocatalysts. Operando XAS analysis ex‐situ characterizations reveal reconstruction into amorphous NiFe‐catalysts (a‐NiFe) activation process, further real phases (a‐NiFe‐C) under potential greater than 1.45 V (vs RHE). In phases, in‐situ formed deprotonated oxygen‐defected Ni oxyhydroxide analogues act as sites, while Fe hydroxide derived from ligands optimize electronic structure sites improving activity. Density functional theory (DFT) indicates reduced energy barrier a‐NiFe‐C pristine MOFs, supporting improved latter.

Language: Английский

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MOF-Based Electrocatalysts: An Overview from the Perspective of Structural Design

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 18, 2025

The electrocatalytic technique, as an efficient energy storage and conversion technology, has attracted significant attention to address exhaustion environmental pollution. Usually, the activity selectivity of reactions are largely dominated by dynamic process occurring on electrocatalysts. Therefore, high-performance electrocatalysts, which can dominate pathway barrier reactions, great significance for advancement technique. Metal-organic frameworks (MOFs), emerging crystalline porous materials, present structural component advantages including well-defined structure, high surface area, large porosity, diverse components, easy tailorability, demonstrating fantastic potential precise fabrication In this Review, strategies in electrocatalysts based MOF-related materials specifically introduced from aspects catalytic site design microenvironment modulation around sites. Furthermore, representative progress achieved various applications employing MOF-based is systematically summarized, with special emphasis MOFs performance optimization. Finally, remaining challenges future perspectives further highlighted.

Language: Английский

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Boosting OER Performance of NiFe‐MOFs via Heterostructure Engineering: Promoted Phase Transformation and Self‐optimized Dynamic Interface Electron Structure

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

Published: Jan. 28, 2025

Abstract How to manipulate heterostructure engineering achieve high‐efficiency oxygen evolution reaction (OER) remains a significant challenge. Herein, promising OER electrocatalyst with IrNi nanoalloys (≈3.29 ± 0.12 nm) anchored on NiFe‐MOFs (IrNi@NiFe‐MOFs), exhibiting promoted phase transformation and self‐optimized dynamic interface electronic structure, via one‐step hydrothermal method is designed developed. Specifically, IrNi@NiFe‐MOFs displays excellent performance low overpotential of 228 mV at 10 mA cm −2 , small Tafel slope 37.6 dec −1 robust stability 100 . Experimental theoretical calculations identify the actual active sites as IrNi@NiFeOOH further reveal that structure electron by engineering, boost its catalytic performance. Moreover, strong interactions unique resulting in better charge redistribution adaptive bonding (Ir─O─Ni/Fe bonds). This therefore plays critical role promoting transfer, facilitating intermediates, reducing energy barrier potential‐determining step, thereby boosting These findings provide new insights into development MOF‐based electrocatalysts engineering.

Language: Английский

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MXene-Assisted NiFe sulfides for high-performance anion exchange membrane seawater electrolysis

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

Published: Feb. 3, 2025

Anion exchange membrane seawater electrolysis is vital for future large-scale green hydrogen production, however enduring a huge challenge that lacks high-stable oxygen evolution reaction electrocatalysts. Herein, we report robust OER electrocatalyst AEMSE by integrating MXene (Ti3C2) with NiFe sulfides ((Ni,Fe)S2@Ti3C2). The strong interaction between (Ni,Fe)S2 and Ti3C2 induces electron distribution to trigger lattice mechanism, improving the intrinsic activity, particularly prohibits dissolution of Fe species during process via Ti-O-Fe bonding effectively, achieving notable stability. Furthermore, good retention sulfates abundant groups provide effective Cl- resistance. Accordingly, (Ni,Fe)S2@Ti3C2 achieves high activity (1.598 V@2 A cm-2) long-term durability (1000 h) in system. industrial current density (0.5 (500 achieved anode Raney Ni cathode efficiency 70% energy consumption 48.4 kWh kg-1 H2. development production crucial addressing shortages. Here, authors enhances stability, 1000 hours electrolysis.

Language: Английский

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Optimizing the Coordination Energy of Co‐N_x Sites by Co Nanoparticles Integrated with Fe‐NCNTs for Boosting PEMFC and Zn‐Air Battery Performance

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

Published: Jan. 12, 2025

Abstract Enhancing the catalytic performance and durability of M‐N─C catalyst is crucial for efficient operation proton exchange membrane fuel cells (PEMFCs) Zn‐Air batteries (ZABs). Herein, an approach developed in situ fabrication a MOFs‐derived porous carbon material, co‐loaded with Co nanoparticles (NPs) Co‐N x sites integrated onto Fe‐doped nanotubes (CNTs), named NP/SA ‐NC/Fe‐NCNTs. Incorporating polymer‐wrapped CNTs improves MOFs dispersion annealing at high temperature, which amplifies three‐phase boundary (TPB) by generating much more mesopores exposing additional active within catalysts layer. Furthermore, density functional theory (DFT) calculations indicate that presence NPs promotes conversion oxygen‐containing intermediates sites. The optimized display half‐wave potential 0.9 V (vs RHE) oxygen reduction reaction (ORR) low overpotential 327 mV 10 mA cm −2 evolution (OER) alkaline media, significantly outperforms counterpart single structure, as well noble‐metal‐based catalysts. Specifically, PEMFCs ZABs derived from ‐NC/Fe‐NCNTs exhibit power densities 702 192 mW , respectively. This work offers novel insights into synthesis composited bifunctional materials application.

Language: Английский

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