Recent progress in metal–organic frameworks (MOFs) for electrocatalysis

Industrial Chemistry and Materials, Journal Year: 2023, Volume and Issue: 1(1), P. 9 - 38

Published: Jan. 1, 2023

Recent progress of metal–organic framework (MOF) based catalysts in the electrocatalytic hydrogen evolution reaction, oxidation oxygen reduction reaction and nitrogen is summarized.

Language: Английский

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Manipulation on active electronic states of metastable phase β-NiMoO4 for large current density hydrogen evolution

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Oct. 13, 2021

Non-noble transition metal oxides are abundant in nature. However, they widely regarded as catalytically inert for hydrogen evolution reaction (HER) due to their scarce active electronic states near the Fermi-level. How largely improve HER activity of these kinds materials remains a great challenge. Herein, proof-of-concept, we design non-solvent strategy achieve phosphate substitution and subsequent crystal phase stabilization metastable β-NiMoO4. Phosphate is proved be imperative activation β-NiMoO4, which can efficiently generate promote intrinsic activity. As result, substituted β-NiMoO4 exhibits optimal adsorption free energy (-0.046 eV) ultralow overpotential -23 mV at 10 mA cm-2 1 M KOH HER. Especially, it maintains long-term stability 200 h large current density 1000 with an only -210 mV. This work provides route activating by stabilizing states.

Language: Английский

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Copper-Based Metal–Organic Framework Overcomes Cancer Chemoresistance through Systemically Disrupting Dynamically Balanced Cellular Redox Homeostasis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(11), P. 4799 - 4809

Published: Feb. 22, 2022

Chemodrug resistance is a major reason accounting for tumor recurrence. Given the mechanistic complexity of chemodrug resistance, molecular inhibitors and targeting drugs often fail to eliminate drug-resistant cancer cells, sometimes even promote chemoresistance by activating alternative pathways. Here, exploiting biochemical fragility high-level but dynamically balanced cellular redox homeostasis in we design nanosized copper/catechol-based metal-organic framework (CuHPT) that effectively disturbs this tilting balance toward oxidative stress. Within CuHPT starts disassembly triggered persistent consumption glutathione (GSH). simultaneously releases two structural elements: catechol ligands reductive copper ions (Cu+). Both them cooperatively function amplify production intracellular radical species (ROS) via auto-oxidation Fenton-like reactions through exhausting GSH. By drastically heightening stress, exhibits selective potent cytotoxicity multiple cells. Importantly, inhibits vivo growth doubles survival time tumor-bearing mice. Thus, along with CuHPT's good biocompatibility, our biochemical, cell biological, preclinical animal model data provide compelling evidence supporting notion copper-based MOF predesigned smart therapeutic against cancers precisely deconstructing their homeostasis.

Language: Английский

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Synergetic Cobalt‐Copper‐Based Bimetal–Organic Framework Nanoboxes toward Efficient Electrochemical Oxygen Evolution

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(50), P. 26397 - 26402

Published: Oct. 20, 2021

The development of efficient oxygen electrocatalysts and understanding their underlying catalytic mechanism are significant importance for the high-performance energy conversion storage technologies. Herein, we report novel CoCu-based bimetallic metal-organic framework nanoboxes (CoCu-MOF NBs) as promising catalysts toward electrochemical evolution reaction (OER), fabricated via a successive cation ligand exchange strategy. With highly exposed bimetal centers well-designed architecture, CoCu-MOF NBs show excellent OER activity stability, with small overpotential 271 mV at 10 mA cm-2 high turnover frequency value 0.326 s-1 an 300 mV. In combination quasi in situ X-ray absorption fine structure spectroscopy density-functional theory calculations, post-formed oxyhydroxide analogue during is believed to account NBs, where electronic synergy between Co neighbouring Cu atoms promotes O-O bond coupling fast kinetics.

Language: Английский

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Ir Nanoparticles Anchored on Metal‐Organic Frameworks for Efficient Overall Water Splitting under pH‐Universal Conditions

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(17)

Published: March 2, 2023

The construction of high-activity and low-cost electrocatalysts is critical for efficient hydrogen production by water electrolysis. Herein, we developed an advanced electrocatalyst anchoring well-dispersed Ir nanoparticles on nickel metal-organic framework (MOF) Ni-NDC (NDC: 2,6-naphthalenedicarboxylic) nanosheets. Benefiting from the strong synergy between MOF through interfacial Ni-O-Ir bonds, synthesized Ir@Ni-NDC showed exceptional electrocatalytic performance evolution reaction (HER), oxygen (OER) overall splitting in a wide pH range, superior to commercial benchmarks most reported electrocatalysts. Theoretical calculations revealed that charge redistribution bridge induced optimization H2 O, OH* H* adsorption, thus leading accelerated electrochemical kinetics HER OER. This work provides new clue exploit bifunctional pH-universal splitting.

Language: Английский

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Metal-organic-framework-based materials as platforms for energy applications

Chem, Journal Year: 2023, Volume and Issue: 10(1), P. 86 - 133

Published: Oct. 10, 2023

Language: Английский

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In situ activation of Br-confined Ni-based metal-organic framework hollow prisms toward efficient electrochemical oxygen evolution

Science Advances, Journal Year: 2021, Volume and Issue: 7(46)

Published: Nov. 10, 2021

Structutral evolution of Br-Ni-MOF hollow prism catalysts during OER is promptly identified by operando XAFS spectroscopy.

Language: Английский

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Machine learning assisted high-throughput screening of transition metal single atom based superb hydrogen evolution electrocatalysts

Journal of Materials Chemistry A, Journal Year: 2022, Volume and Issue: 10(12), P. 6679 - 6689

Published: Jan. 1, 2022

Carbon-based transition metal (TM) single-atom catalysts (SACs) have shown great potential toward electrochemical water splitting and H 2 production.

Language: Английский

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Deciphering the Space Charge Effect of the p–n Junction between Copper Sulfides and Molybdenum Selenides for Efficient Water Electrolysis in a Wide pH Range

ACS Nano, Journal Year: 2022, Volume and Issue: 16(9), P. 15425 - 15439

Published: Aug. 29, 2022

Space charge transfer is crucial for an efficient electrocatalytic process, especially narrow-band-gap metal sulfides/selenides. Herein, we designed and synthesized a core-shell structure which ultrathin MoSe2 nanosheet coated CuS hollow nanoboxes (CuS@MoSe2) to form open p-n junction structure. The space effect in the region will greatly improve electron mass conduction, also have abundant active interfaces. It was used as bifunctional electrocatalyst water oxidation at wide pH range. exhibits low overpotential of 49 mV HER 236 OER current density 10 mA·cm-2 acidic pH, 72 219 alkaline 62 230 under neutral conditions. experimental results functional theory calculations testify that CuS@MoSe2 has strong with synergistic effect. built-in field can boost transport during process stabilize charged center junction. This be beneficial performance. work provides understanding semiconductor heterojunction applications regulating electronic sites.

Language: Английский

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Linker-Compensated Metal–Organic Framework with Electron Delocalized Metal Sites for Bifunctional Oxygen Electrocatalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(11), P. 4783 - 4791

Published: Feb. 22, 2022

Metal-organic frameworks with tailorable coordination chemistry are propitious for regulating catalytic performance and deciphering genuine mechanisms. Herein, a linker compensation strategy is proposed to alter the intermediate adsorption free energy on Co-Fe zeolitic imidazolate framework (CFZ). This grants zinc-air battery superior high current density capability small discharge-charge voltage gap of 0.88 V at 35 mA cm-2 an hourly fading rate less than 0.01% over 500 h. Systematic characterization theoretical modeling reveal that elevation closely correlated CFZ unsaturated metal nodes by S-bridging heterogeneous linkers, which exhibit electron-withdrawing characteristic drives delocalization d-orbital electrons. These rearrangements electronic structures establish favorable adsorption/desorption pathway key intermediates (OH*) stable environment in bifunctional oxygen electrocatalysis.

Language: Английский

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