Hydrogen‐Bond‐Assisted Electrocatalytic Semi‐Oxidation of 5‐Hydroxymethylfurfural into 2,5‐Diformylfuran by Operando Dissociated N‐Oxyl Mediator DOI Open Access
Ying Yin, Ximeng Lv, Zhuoran Lv

et al.

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

Published: Oct. 8, 2024

Abstract The conversion of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF) is a promising approach for enhancing biomass utilization. Nevertheless, traditional methods using noble metal catalysts face challenges due high costs and poor selectivity towards DFF. Herein, we developed novel catalytic electrode integrating N ‐hydroxyphthalimide (NHPI) into metal‐organic framework on hydrophilic carbon cloth. This design significantly enhances the selective adsorption HMF stronger hydrogen‐bond interaction between electrode's surface C(sp 3 )−OH group in compared 2 )=O Additionally, electro‐driven dissociation NHPI‐linker generates stabilized ‐Oxyl radicals that promote semi‐oxidation under neutral conditions. As result, this achieves yield rate 138.2 mol cat −1 h with 96.7 % HMF‐to‐DFF conversion. work introduces strategy designing electrodes radicals, offers method electrocatalytic DFF synthesis, leveraging HMF.

Language: Английский

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

Yan Xin,

Jian Tian, Xianqiang Xiong

et al.

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

Citations

5
MOF-Based Electrocatalysts: An Overview from the Perspective of Structural Design DOI

Nana Sun,

Syed Shoaib Ahmad Shah, Zhongyuan Lin

et al.

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

Citations

5
Ion Exchange‐Mediated 3D Cross‐Linked ZIF‐L Superstructure for Flexible Electrochemical Energy Storage DOI

Hongye Ding,

Zheng Liu, Ju Xie

et al.

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

Citations

13
Recent strategies to improve the electroactivity of metal–organic frameworks for advanced electrocatalysis DOI Creative Commons

Runzhi Wei,

Xiao Li, Aziz B. Ibragimov

et al.

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

Citations

11
In-situ synthesis to promote surface reconstruction of metal–organic frameworks for high-performance water/seawater oxidation DOI

Guohao Na,

Hongshun Zheng,

Mingpeng Chen

et al.

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

Published: Aug. 28, 2024

Language: Английский

Citations

10
Electronic Structure Regulation by Fe Doped Ni‐Phosphides for Long‐term Overall Water Splitting at Large Current Density DOI

Yanju Long,

Pingping Jiang, Peisen Liao

et al.

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

Citations

9
Unraveling the Role of Functional Groups of Terephthalate in Enhancing the Electrochemical Oxygen Evolution Reaction of Nickel–Organic Framework Nanoarrays DOI
Chong Lin, Shun Wang, Xuetong Zhang

et al.

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

Published: Jan. 23, 2025

The platelike nickel-terephthalate-type metal-organic framework nanoarrays (Ni-BDC NAs) on carbon cloth are obtained by employing agaric-like Ni(OH)2 NAs as sacrificial templates. microenvironment of Ni-BDC is modulated various neighboring functional groups (-NH2, -NO2, and -Br) the carboxylate ligand, exerting minimal destructive effects structure morphology NAs. electrochemical oxygen evolution reaction (OER) Ni-BDC-NH2 NAs, Ni-BDC-NO2 Ni-BDC-Br exhibited a significant enhancement compared to that alone, evidenced both experimental theoretical assessments. presence exerts positive influence electronic coupling between Ni O atoms, thereby facilitating thermodynamically favorable formation *O intermediates sites accelerating kinetics OER. findings presented here provide valuable insights for design utilization carboxylic acid molecules with group effects, enhancing activity OER across diverse centers.

Language: Английский

Citations

1
Molecular Nanojunction Catalyst for Oxygen Evolution Reaction DOI Open Access
Kuo Wei, Zhiping Liu, Guangyuan Feng

et al.

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

Published: Jan. 26, 2025

Abstract Achieving close integration and strong electronic communication between molecular catalysts conductive substrates is crucial for developing the stability catalytic activity of nanomaterials. However, constructing heterostructure catalyst usually need complex demanding synthesis processes. Herein, a facile universal “molecular nanojunction” strategy developed to prepare with high by improving coplanarity nanojunction facilitating efficient electron transfer. The density function theory (DFT) calculations in situ characterization indicate that reduces excessive * OH adsorption accelerates deprotonation process, thereby promoting oxygen generation. shows better evolution reaction (OER) performance than most reported catalysts. What's more, are applied alkaline anion exchange membrane (AEM) electrolysis cells, exhibiting excellent performance.

Language: Английский

Citations

1
Ferrocene-MOFs: Optimizing OER Kinetics for Water Splitting DOI

Aling Zhou,

Jiasui Huang,

Lixia Wang

et al.

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

Published: Feb. 27, 2025

Optimizing the adsorption and desorption kinetics of oxygen evolution reaction (OER) is crucial for efficient overall water splitting. Herein, we report a series porous ferrocene-based metal–organic framework (MFc-MOF, M = Co, Ni, Fe, Mn) nanoflowers featuring close π–π stacking lattice structure as model catalysts, explore structure–activity relationship. Operando electrochemical impedance spectroscopy implies that synthesized CoFc-MOF@NF facilitates intermediate desorption. It exhibits an ultralow overpotential 189 mV at 10 mA cm–2 maintains stability 250 h. In splitting device, when serves anode, it yields significantly lower cell voltage than commercial RuO2 shows excellent 100 situ Raman reveals surface transforms into CoFeOOH, OER-active species, while preserving MOF framework. The inner MOF's ferrocene units act electron-transfer mediators. These findings highlight CoFc-MOF@NF's potential leading catalyst sustainable hydrogen production, combining high catalytic activity, rapid kinetics, robust stability. This work presents new approach to balance activity in MOF-based OER catalysts.

Language: Английский

Citations

1
Rationally-Constructed Porous Nanosheet Ni2P–Ni5P4 Heterostructures for Robust Oxygen Evolution Electrode DOI

Min Jie Wang,

Bingjie Zhou, Yangyang Feng

et al.

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

Citations

1