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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Enhanced Photocatalytic Efficiency Through Oxygen Vacancy‐Driven Molecular Epitaxial Growth of Metal–Organic Frameworks on BiVO₄

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

Published: Jan. 19, 2025

Abstract Efficient charge separation at the semiconductor/cocatalyst interface is crucial for high‐performance photoelectrodes, as it directly influences availability of surface charges solar water oxidation. However, establishing strong molecular‐level connections between these interfaces to achieve superior interfacial quality presents significant challenges. This study introduces an innovative electrochemical etching method that generates a high concentration oxygen vacancy sites on BiVO 4 surfaces (Ov‐BiVO ), enabling interactions with oxygen‐rich ligands MIL‐101. reduces formation energy and promotes conformal growth . The Ov‐BiVO /MIL‐101 composite exhibits ideal interface, achieving impressive photocurrent density 5.91 mA cm −2 1.23 V RHE , along excellent stability. high‐performing photoanode enables unbiased tandem device /MIL‐101‐Si cell system, solar‐to‐hydrogen efficiency 4.33%. integration mitigates states enhances internal electric field, facilitating migration photogenerated holes into MIL‐101 overlayer. process activates highly efficient Fe catalytic sites, which effectively adsorb molecules, lowering barrier oxidation improving kinetics. Further studies confirm broad applicability vacancy‐induced molecular epitaxial in various MOFs, offering valuable insights defect engineering optimizing enhancing photocatalytic activity.

Language: Английский

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Ion Exchange‐Mediated 3D Cross‐Linked ZIF‐L Superstructure for Flexible Electrochemical Energy Storage

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 17, 2024

Metal-organic frameworks (MOFs) are considered as a promising candidate for advancing energy storage owing to their intrinsic multi-channel architecture, high theoretical capacity, and precise adjustability. However, the low conductivity poor structural stability lead unsatisfactory rate cycling performance, greatly hindering practical application. Herein, we propose sea urchin-like Co-ZIF-L superstructure using molecular template induce self-assembly followed by ion exchange method, which shows improved conductivity, successive channels, stability. The can gradually etch superstructure, leading reconstruction of with three-dimensional (3D) cross-linked ultrathin porous nanosheets. Moreover, control Co Ni ratios construct effective micro-electric field synergistically enhance rapid transfer electrons electrolyte ions, improving CoNi-ZIF-L.

Language: Английский

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Recent strategies to improve the electroactivity of metal–organic frameworks for advanced electrocatalysis

Deleted Journal, Journal Year: 2024, Volume and Issue: 1(2), P. 181 - 206

Published: Aug. 4, 2024

Abstract Metal–organic frameworks (MOFs) have emerged as promising materials in the realm of electrocatalysis due to their high surface area, tunable porosity, and versatile chemical functionality. However, practical application has been hampered by inherent limitations such low electrical conductivity a limited number active metal sites. Researchers addressed these challenges through various strategies, including enhancing incorporating conductive nanoparticles, modifying structure composition MOFs replacing nodes functionalizing linkers, preparing catalysts thermal processes decarburization conversion into oxides, phosphides (MPs), sulfides (MSs). This review provided comprehensive summary strategies that were employed enhance electroactivity for improved electrocatalytic performance recent years. It also explored future directions potential innovations design synthesis MOF‐based electrocatalysts, offering valuable insights advancing sustainable energy technologies.

Language: Английский

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Rationally-Constructed Porous Nanosheet Ni₂P–Ni₅P₄ Heterostructures for Robust Oxygen Evolution Electrode

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: March 14, 2025

The development of superior non-noble-metal-based oxygen evolution reaction (OER) electrocatalysts is essential for large-scale hydrogen production. In this study, an integrated porous nanosheet Ni2P-Ni5P4 heterostructures were designed as excellent OER electrocatalyst. synthesized demonstrated notable activity, achieving a small overpotential 260 mV to sustain typical 10 mA cm-2 current density, along with exceptional durability over 2000 CV cycles. distinctive structure enhances the exposure active sites and improves mass transport efficiency. Density functional theory (DFT) calculations revealed that d-band center Ni was shifted downward, reducing adsorption strength critical oxygen-containing intermediates (*O, *OH, *OOH) in heterostructures. This modification lowered barrier rate-determining step (RDS) involving transformation from *O *OOH, thereby boosting inherent activity. Additionally, partial electron localization combination RDS intermediate observed by functions (ELFs) Ni2P-Ni5P4, weakening overall interaction. Further crystal orbital Hamiltonian population confirmed reduced Ni-O net bonding energy 0.69 eV adsorbed compared Ni2P (1.49 eV) Ni5P4 (1.12 aligning DFT ELF findings. These results provide promising approach valuable guidance design cost-effective suitable storage applications, including metal-air cells water oxidation processes.

Language: Английский

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Electronic Structure Regulation by Fe Doped Ni‐Phosphides for Long‐term Overall Water Splitting at Large Current Density

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

Published: Aug. 13, 2024

Abstract Acquiring a highly efficient electrocatalyst capable of sustaining prolonged operation under high current density is paramount importance for the process electrocatalytic water splitting. Herein, Fe‐doped phosphide (Fe‐Ni 5 P 4 ) derived from NiFc metal−organic framework (NiFc‐MOF) (Fc: 1,1′‐ferrocene dicarboxylate) shows catalytic activity overall splitting (OWS). Fe‐Ni ||Fe‐Ni exhibits low voltage 1.72 V OWS at 0.5 A cm −2 and permits stable 2700 h in 1.0 m KOH. Remarkably, can sustain robust an extra‐large 1 1170 even alkaline seawater. Theoretical calculations confirm that Fe doping simultaneously reduces reaction barriers coupling desorption (O * →OOH , OOH →O 2 oxygen evolution (OER) regulates adsorption strength intermediates (H O H hydrogen (HER), enabling to possess excellent dual functional activity. This study offers valuable reference advancement durable electrocatalysts through regulation coordination frameworks, with significant implications industrial applications energy conversion technologies.

Language: Английский

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In-situ synthesis to promote surface reconstruction of metal–organic frameworks for high-performance water/seawater oxidation

Journal of Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 678, P. 795 - 805

Published: Aug. 28, 2024

Language: Английский

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Tuning the Reconstruction of Metal–Organic Frameworks during the Oxygen Evolution Reaction

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 15916 - 15926

Published: Oct. 11, 2024

Recently, there has been growing interest in the conversion of metal–organic frameworks (MOFs) into metal-hydroxide catalysts for alkaline oxygen evolution reactions (OERs). While studies have shown that initial OER performance MOF-derived intermediates surpasses traditional catalysts, ongoing debates persist regarding these catalysts' durability and electrochemical stability. Moreover, inevitable reorganization (aging) from disordered to ordered phases, particularly those primarily composed nickel oxyhydroxides, remains a topic discussion. To address issues, we propose straightforward approach mitigating MOF reconstruction modulating aging harsh environments by introducing additional organic carboxylate linkers electrolytes. Specifically, focus on two examples: Ni-BPDC-MOFs NiFe-BPDC-MOFs, formula [M2(OH)2BPDC] (M: Ni Fe; BPDC = 4,4′-biphenyldicarboxylate). Experimental results indicate electrolytes containing exhibit enhanced activity prolonged lifespan. Complemented situ Raman spectroscopy, our findings suggest manipulating coordination equilibrium linker involved Ni-MOF formation (linker assembly) leaching) leads more oxyhydroxide phases as active catalyst material, which shows performance.

Language: Английский

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Strategic Defect Engineering Enabled Efficient Oxygen Evolution Reaction in Reconstructed Metal‐Organic Frameworks

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

Published: Oct. 22, 2024

Abstract Metal‐organic frameworks (MOFs) have emerged as promising pre‐catalysts for oxygen evolution reaction (OER) due to their marvelous structural reconstruction process in strongly alkaline media. However, targeting design MOF structures achieve excellent OER performance of reconstructed products is a challenge. Here, strategic defect engineering used promote the products. Briefly, modified linkers with monocarboxylic acids (ferrocene carboxylic acid, FcCA) are incorporated into (NiBDC‐FcCA), leading its stepwise Fe‐doped Ni(OH) 2 and NiOOH during process, vacancy doping metal Fe persisting throughout multi‐step reconstruction. Benefiting from synergistic interaction vacancies doping, NiBDC‐FcCA delivers extremely enhanced current density at 1.6 V versus reversible hydrogen electrode by ≈9 times compared that NiBDC. Moreover, optimized NiBDC‐FcCA/Fe foam exhibits catalytic activity stability low overpotential 250 mV 200 mA cm −2 negligible decay after 1200 h 1 A . Density function theory calculations reveal weakens intermediate Ni sites, favoring formation OOH* accelerate process.

Language: Английский

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HCP-to-FCC Phase Transformation of Ruthenium Nanocrystals Selectively Activate Hydrogen Peroxide for Boosting Peroxidase-like Activity

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Due to the simultaneous activation of hydrogen peroxide (H2O2) and oxygen, Ru nanocrystals exhibit inherent peroxidase- oxidase-like activities, thereby limiting their extensive application in biosensing. Phase engineering holds great promise for enhancing catalytic activity selectivity but remains a challenge. Here, highly active with metastable face-centered cubic (fcc) structure were successfully synthesized via facile wet-chemical method followed by an etching step, enabling selective H2O2 demonstrating promising peroxidase-like activity. Compared thermodynamically favored hexagonal close-packed nanocrystals, resultant fcc shows over 5-fold enhancement maximum reaction velocity catalysis, while its performance exhibits minor decline, indicating transition from multienzyme specificity. Theoretical calculations reveal that phase transformation not only results upward shift d-band center enhance adsorption also regulates O–O bonding strength achieve activation. As proof concept, colorimetric sensor based on was constructed, achieving accurate sensitive detection organophosphorus pesticides. This work offers prospects highlights significance

Language: Английский

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