Exploring the Performance Improvement of the Oxygen Evolution Reaction in a Stable Bimetal–Organic Framework System

Wang, Xiaoli; Dong, Long‐Zhang; Qiao, Man; Tang, Yawei; Liu, Jiang; Li, Yafei; Li, Shun-Li; Su, Jiaxin; Lan, Ya‐Qian

doi:10.1002/ange.201803587

Cited by 69 publications

(22 citation statements)

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“…22,26 Recent studies further demonstrate the capabilities of heterometallic clusters as the nodes of multivariate MOFs for heterogeneous catalysis. [27][28][29][30] These findings suggest it highly promising to achieve both stability and reactivity of Co-MOF photocatalysts by introducing proper high-valent cations into Co(II) clusters as heterometallic nodes. Nevertheless, such Co-MOFs have been rarely reported so far, 31 mostly due to the challenging fabrications tending toward the mixtures of monometallic MOFs or incomplete substitutions in the metal nodes.…”

Section: Introductionmentioning

confidence: 97%

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Fang

Wen

et al. 2022

CCS Chem

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Assembling the reactive low-cost Co clusters and photo-responsive ligands in the form of metal-organic frameworks is a promising strategy to construct efficient water-oxidizing photocatalysts but now restricted by the poor water stability. Introducing high valent cations in the clusters to build heterometallic Co-MOFs might be a solution, yet the precise fabrication is still challenging. Herein, starting from the pre-synthesized trinuclear Co2Ti clusters, a novel bimetallic Co-MOF (named as PFC-20-Co2Ti) capable of single-crystal diffraction for precise structure information was achieved. The incorporation of the single-site Ti(IV) cation endows the MOF with increased charge density in metal nodes and optimized catalytic kinetics, resulting in greatly improved water stability and ultrahigh photocatalytic activities for O2 evolution. The single-site Ti incorporation in nodes was proved to be a universal methodology to acquire stable and active MOF catalysts based on wide-range transition metals such as Ni and Mn. This work echoes MOFs' capability of precisely structural design and pave a new way to construct target heterogeneous catalysts with superior performence.

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Section: Introductionmentioning

confidence: 97%

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Fang

Wen

et al. 2022

CCS Chem

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“…Benchmark OER catalysts.While an initial overview of MOF OER catalysts demonstrates competitive, if not superior activity to non-MOF OER catalysts, it should be immediately noted that the most active MOF catalysts are united not by any fundamental property of the MOF but by the metal foam substrate that they are deposited on 182,[332][333][334][335][338][339][340][341][342]346. The use of metal foams and other highsurface-area supports is problematic for performance benchmarking because the current density is a descriptor that assumes a flat catalyst.…”

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confidence: 99%

Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives

et al. 2020

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More than 95% (in volume) of all today's chemical products are manufactured through catalytic processes, making research into more efficient catalytic materials a thrilling and very dynamic research field. In this regard, Metal Organic Frameworks (MOFs) offer great opportunities for the rational design of new catalytic solids, as highlighted by the unprecedented number of publications appearing over the last decade. In this review, the recent advances in the application of MOFs in heterogeneous catalysis are discussed. MOFs with intrinsic thermo-catalytic activity, as hosts for the incorporation of metal nanoparticles, as precursors for the manufacture of composite catalysts and those active in photo and electrocatalytic processes are critically reviewed. The review is wrapped up with our personal view on future research directions.

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“…Analysis results indicated that the Mn and Fe distribute uniformly within the structure (Figure S3) and the stoichiometry of Fe/Mn is approximately in 2 : 1 (Tables S3, S4, and S10), consistent with the previous reports. [ 39 ] The phase purity of bulk samples and the repeatability of the synthesis method were verified by PXRD patterns (Figure S2).…”

Section: Resultsmentioning

confidence: 95%

“…[ 33 ] Previous studies have shown that Fe 3 ( μ 3 ‐O)‐cluster, which is easy to prepare and convenient to completely or partly replace Fe by a specific metal atom (M), could be viewed as one of the most popular secondary building units (SBUs) to construct chemical stable MOFs with heterometallic synergy. [ 38‐43 ] To this regard, we attempt to introduce Mn into Fe 3 ( μ 3 ‐O) SBU and finally get Fe 3– x Mn x ( μ 3 ‐O)‐cluster based MOFs with high chemical stability and catalytic activity in oxidative coupling of amines.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Fe₂Mn(μ₃‐O)(COO)₆ Cluster Based Stable MOF for Oxidative Coupling of Amines via Heterometallic Synergy

Wang

Meng

et al. 2021

Chin. J. Chem.

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Main observation and conclusion The direct catalytic oxidative coupling of amines is one of the attracting methods for the synthesis of a variety of pharmaceutical or industrial needed imines. Numerous earth‐abundant manganese based salts, oxides, and complexes have been applied in this reaction. However, these compounds suffered from difficult separation, large catalyst loading, complicated reactivation or indeterminate activity. Considering the facts that metal‐organic frameworks (MOFs) with crystalline structure, precise composition, and enormous surface area have superior performance in heterogeneous catalytic reactions, herein, we introduced Mn into [Fe3(μ3‐O)(CH3COO)6], one of the precursors for the preparation of stable MOFs, and got [Fe2Mn(μ3‐O)(CH3COO)6] cluster. After ligand replacement with biphenyl‐3,4’,5‐tricarboxylic acid (BPTC), heterometallic cluster‐based [Fe2Mn(μ3‐O)(BPTC)2(DMF)2(H2O)] (1) was obtained. As expected, 1 is stable and able to catalyze the homo‐ or cross‐coupling of amines effectively and selectively with 0.9 mol% catalyst loading at room temperature. Control experiments indicated that the catalytic activity of 1 mainly stems from Mn sites and that Fe synergistically contributes to the stability. Additionally, 1 is recyclable and can be reused easily for at least 8 runs without obvious decrease in catalytic ability. To our knowledge, 1 should be the first heterometallic cluster‐based MOF with defined structure suitable for the synthesis of diverse imines from oxidative coupling of amines under mild conditions, which may shed light on the easy preparation of effective heterogeneous catalysts for organic synthesis.

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Exploring the Performance Improvement of the Oxygen Evolution Reaction in a Stable Bimetal–Organic Framework System

Cited by 69 publications

References 50 publications

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives

Fe₂Mn(μ₃‐O)(COO)₆ Cluster Based Stable MOF for Oxidative Coupling of Amines via Heterometallic Synergy

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Exploring the Performance Improvement of the Oxygen Evolution Reaction in a Stable Bimetal–Organic Framework System

Cited by 69 publications

References 50 publications

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives

Fe2Mn(μ3‐O)(COO)6 Cluster Based Stable MOF for Oxidative Coupling of Amines via Heterometallic Synergy

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Fe₂Mn(μ₃‐O)(COO)₆ Cluster Based Stable MOF for Oxidative Coupling of Amines via Heterometallic Synergy