Missing-linker metal-organic frameworks for oxygen evolution reaction

Xue, Ziqian; Liu, Kang; Liu, Qinglin; Li, Yinle; Li, Manrong; Su, Cheng‐Yong; Ogiwara, Naoki; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Liu, Min

doi:10.1038/s41467-019-13051-2

Cited by 462 publications

(346 citation statements)

References 57 publications

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“…X-ray absorption near-edge spectra (XANES) of Fe K-edge (Fig. 2c ) show obvious positive shift in FeAB–O compared with in FePc/AB, indicating the change of electronic structure of Fe 35 . Moreover, a pre-edge peak around 7114 eV can be indexed to the square-planar and centrosymmetric Fe–N 4 structure of FePc 36 – 38 .…”

Section: Resultsmentioning

confidence: 99%

Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction

et al. 2020

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Iron phthalocyanine (FePc) is a promising non-precious catalyst for the oxygen reduction reaction (ORR). Unfortunately, FePc with plane-symmetric FeN 4 site usually exhibits an unsatisfactory ORR activity due to its poor O 2 adsorption and activation. Here, we report an axial Fe-O coordination induced electronic localization strategy to improve its O 2 adsorption, activation and thus the ORR performance. Theoretical calculations indicate that the Fe-O coordination evokes the electronic localization among the axial direction of O-FeN 4 sites to enhance O 2 adsorption and activation. To realize this speculation, FePc is coordinated with an oxidized carbon. Synchrotron X-ray absorption and Mössbauer spectra validate Fe-O coordination between FePc and carbon. The obtained catalyst exhibits fast kinetics for O 2 adsorption and activation with an ultralow Tafel slope of 27.5 mV dec −1 and a remarkable half-wave potential of 0.90 V. This work offers a new strategy to regulate catalytic sites for better performance.

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Section: Resultsmentioning

confidence: 99%

Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction

et al. 2020

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“…Significantly by virtue of the versatile organic linkers and atomically dispersed metal structural building units, the microstructure and the electronic structure of MOFs could be well regulated via various strategies [27][28][29][30][31]. In particular, the introduction of functional groups or heteroatoms in the MOFs can not only affect the electron density around the atomically dispersed metal centers but also change the nucleophilicity, redox potential and stability of the catalysts, making them own great potential in electrocatalysis, photocatalysis and biocatalysis [32][33][34][35][36]. Recently, the enzyme-like property of MOFs has attracted the extensive interest of the research community.…”

Section: Introductionmentioning

confidence: 99%

Tuning Atomically Dispersed Fe Sites in Metal–Organic Frameworks Boosts Peroxidase-Like Activity for Sensitive Biosensing

Kang

Jiao

et al. 2020

Nano-Micro Lett.

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Although nanozymes have been widely developed, accurate design of highly active sites at the atomic level to mimic the electronic and geometrical structure of enzymes and the exploration of underlying mechanisms still face significant challenges. Herein, two functional groups with opposite electron modulation abilities (nitro and amino) were introduced into the metal–organic frameworks (MIL-101(Fe)) to tune the atomically dispersed metal sites and thus regulate the enzyme-like activity. Notably, the functionalization of nitro can enhance the peroxidase (POD)-like activity of MIL-101(Fe), while the amino is poles apart. Theoretical calculations demonstrate that the introduction of nitro can not only regulate the geometry of adsorbed intermediates but also improve the electronic structure of metal active sites. Benefiting from both geometric and electronic effects, the nitro-functionalized MIL-101(Fe) with a low reaction energy barrier for the HO* formation exhibits a superior POD-like activity. As a concept of the application, a nitro-functionalized MIL-101(Fe)-based biosensor was elaborately applied for the sensitive detection of acetylcholinesterase activity in the range of 0.2–50 mU mL−1 with a limit of detection of 0.14 mU mL−1. Moreover, the detection of organophosphorus pesticides was also achieved. This work not only opens up new prospects for the rational design of highly active nanozymes at the atomic scale but also enhances the performance of nanozyme-based biosensors.

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“…There are also reports focusing on the combination of heterogeneous components and 2D Co-based MOFs to optimize the electronic structure. [81][82][83] Such hybridization can also prevent MOF nanosheet agglomeration. For instance, Huang's group [81] incorporated 2D cobalt 1,4-benzenedicarboxylate (CoBDC) with Ti 3 C 2 T x nanosheets via an inter-diffusion reactionassisted process.…”

Section: Co-based Mof Hybridsmentioning

confidence: 99%

Recent Progress of Two‐Dimensional Metal‐Organic Frameworks and Their Derivatives for Oxygen Evolution Electrocatalysis

et al. 2020

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The development of high‐performance transition metal−based electrocatalysts for the oxygen evolution reaction (OER) is paramount for electrochemical secondary metal‐air batteries and water splitting. Two‐dimensional (2D) metal‐organic framework (MOF) nanosheets have recently emerged as a novel class of efficient electrocatalysts for OER, due to a high specific surface area, ultrasmall thickness and abundance of active sites. Here, we summarize recent progress in the preparation and characterization of 2D transition metal−based MOFs (e. g. Ni, Co and Cu), as well as their composites and derivatives, including metals/alloys, metal oxides/chalcogenides and metal phosphides/hydroxides, as OER electrocatalysts reported over the past several years. Design principles and preparation routes are presented. The performance of the electrocatalysts is directly compared in terms of overpotential (η) (thermodynamics) and electrocatalytic current density (kinetics), as well as operational stability (economics). Many of these materials exhibit superior catalytic activity compared to the noble metal−based catalysts such as RuO2 (η<300 mV at 10 mA cm−2), and considerable stability with negligible decay with operation over several hours to days. Challenges and perspectives of applying 2D MOFs and their derivatives for OER electrocatalysis are also discussed.

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Missing-linker metal-organic frameworks for oxygen evolution reaction

Cited by 462 publications

References 57 publications

Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction

Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction

Tuning Atomically Dispersed Fe Sites in Metal–Organic Frameworks Boosts Peroxidase-Like Activity for Sensitive Biosensing

Recent Progress of Two‐Dimensional Metal‐Organic Frameworks and Their Derivatives for Oxygen Evolution Electrocatalysis

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