Ligand Functionalized Iron‐Based Metal‐Organic Frameworks for Efficient Electrocatalytic Oxygen Evolution

Qi, Qianglong; Tai, Jun; Hu, Jue; Zhang, Zihan; Dai, Linqing; Song, Hongchuan; Shao, Minhua; Zhang, Chengxu; Zhang, Libo

doi:10.1002/cctc.202101242

Cited by 18 publications

(18 citation statements)

References 70 publications

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“…One is to fabricate nanostructured MOFs with coordinatively unsaturated metal sites, such as ultrathin MOF nanosheets, [ 3 ] nanotubular arrays, [ 4 ] or defect‐rich MOFs. [ 5 ] Another strategy focuses on exploring ligands with different functional groups [ 6 ] and connectors, [ 7 ] or varying metal atoms from a single component such as Ni, [ 8 ] Co, [ 9 ] Cu, [ 10 ] to bi‐ and trimetal components. In addition, interfacial regulation, heterometals alternating sequence and layer‐by‐layer assembled strategies were also devoted to improving the electrocatalytic OER activity of MOF catalysts.…”

Section: Introductionmentioning

confidence: 99%

Rationally Reconstructed Metal–Organic Frameworks as Robust Oxygen Evolution Electrocatalysts

Zhang

Mei

et al. 2022

Advanced Materials

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Although the metal-organic framework (MOF) based materials have become one of the most important types of electrocatalysts for the sluggish oxygen evolution reaction (OER), a novel design strategy for the MOF structure is highly needed to overcome the current development bottleneck of the electrochemical performance. Reconstructing MOFs towards a designed framework structure provides breakthrough opportunities to achieve unprecedented OER electrocatalytic performance, but has rarely, if ever, been proposed and investigated yet due to the signi cant challenges during the synthesis. Here, we report the rst successful fabrication of a robust OER electrocatalyst by precision reconstruction of an MOF structure from MOF-74-Fe to MIL-53(Fe)-2OH with different coordination environments at the active sites.Theoretical calculations have revealed that the Fe sites in MIL-53(Fe)-2OH with uncoordinated phenolic hydroxyls are more electroactive than that in MOF-74-Fe. Bene ting from this desired electronic structure, the designed MIL-53(Fe)-2OH catalyst exhibits unprecedentedly high intrinsic OER activity, including a low overpotential of 215 mV at 10 mA cm−2, low Tafel slope of 45.4 mV dec−1 and high turnover frequency (TOF) of 1.44 s−1 at the overpotential of 300 mV, which is 81 times higher than the TOF of the commercial IrO2 catalyst (0.0177 s−1). The radically reduced eg-t2g crystal eld splitting in Fe-3d and thus the much suppressed electron hopping barriers through the synergistic effects of the O species from the coordinated carboxyl groups and the uncoordinated phenolic groups guarantee the e cient OER in MIL-53(Fe)-2OH. Consistent with the DFT calculations, the real-time kinetic simulation reveals that the conversion from O* to OOH* is the rate-determining step on the active sites of MIL-53(Fe)-2OH. This work establishes a MOF platform to systematically investigate the structure-property relationship for rationally designing and fabricating robust OER electrocatalysts in the future.

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Section: Introductionmentioning

confidence: 99%

Rationally Reconstructed Metal–Organic Frameworks as Robust Oxygen Evolution Electrocatalysts

Zhang

Mei

et al. 2022

Advanced Materials

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“…As shown in Figure g, the characteristic peak located at ∼8.90° for the Fe 3 -MOF-BDC sample slightly shifted to 8.45° for Fe 3 -MOF-BDC-NH 2 , 8.47° for Fe 3 -MOF-BDC-OH, 8.50° for Fe 3 -MOF-BDC-NO 2 , and 8.44° for Fe 3 -MOF-BDC-DH. The shift of the peaks is probably ascribed to the strain effect caused by the introduction of functional groups in BDC. − The FT-IR patterns in Figure S4c–e also prove the successful synthesis of all of the target MOF samples, where characteristic peaks of functional groups can easily be found. − …”

Section: Resultsmentioning

confidence: 76%

“…24,25 For Fe 2p in Figure S10d, two pairs of peaks can be observed, located at 714.13 and 727.22 eV of Fe 3+ and 710.83 and 723.95 eV of Fe 2+ , confirming the coexistence of Fe 2+ and Fe 3+ and the predominant form of Fe 2+ present as the Fe state in Fe 3 -MOF-BDC/BDC-NH 2 . 17,24 Importantly, the Fe 2p 3/2 peaks in Fe 3 -MOF-BDC-NH 2 have a slightly positive shift compared to Fe 3 -MOF-BDC, which further verifies the change of the electronic structure of Fe 3 -MOF-BDC after aminoterephthalic acid (BDC-NH 2 ) was utilized. 26,27 At the same time, the crystal color of Fe 3 -MOF-BDC-NH 2 became dark gray from grayish green for Fe 3 -MOF-BDC, which visually verifies the change of the electronic structure (Figure S11).…”

Section: Resultsmentioning

confidence: 82%

“…For the C 1s spectra (Figure S10b), the three peaks located at around 288.0, 285.8, and 284.8 eV correspond to OC–O, C–O/C–N, and C–C, respectively . In Figure S10c, the high-resolution XPS spectrum of O 1s could be fitted into three peaks at around 533, 531.4, and 529.8 eV associated with the CO, C–O, and Fe–O bond electronic configurations, respectively. , For Fe 2p in Figure S10d, two pairs of peaks can be observed, located at 714.13 and 727.22 eV of Fe 3+ and 710.83 and 723.95 eV of Fe 2+ , confirming the coexistence of Fe 2+ and Fe 3+ and the predominant form of Fe 2+ present as the Fe state in Fe 3 -MOF-BDC/BDC-NH 2 . , Importantly, the Fe 2p 3/2 peaks in Fe 3 -MOF-BDC-NH 2 have a slightly positive shift compared to Fe 3 -MOF-BDC, which further verifies the change of the electronic structure of Fe 3 -MOF-BDC after aminoterephthalic acid (BDC-NH 2 ) was utilized. , At the same time, the crystal color of Fe 3 -MOF-BDC-NH 2 became dark gray from grayish green for Fe 3 -MOF-BDC, which visually verifies the change of the electronic structure (Figure S11). Thus, the introduction of an amino linker can cause defect strain and change the bond length of Fe–O/Fe–N and the electronic environment of the active center, thereby optimizing the binding energy of reaction intermediates and affecting the OER catalytic activity. ,, …”

Section: Resultsmentioning

confidence: 95%

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Molecular Regulation Based on Functional Trimetallic Metal–Organic Frameworks for Efficient Oxygen Evolution Reaction

et al. 2022

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Metal–organic frameworks (MOFs) as classic crystalline porous materials have attracted great interest in the catalytic field. However, how to realize molecular regulation of the MOF structure to achieve a remarkable oxygen evolution reaction (OER) electrocatalyst is still a challenge. Herein, we designed several series of special MOF materials to explore the relationship between the structure and properties as well as the related reactive mechanism. First, various metal centers, including Fe, Co, Ni, Zn, and Mg, were utilized to construct the first series of trimetallic MOF materials, namely, M3-MOF-BDC, where BDC = 1,4-benzenedicarboxylic acid, also known as terephthalic acid. Among of them, Fe3-MOF-BDC shows the best OER performance and only needs an overpotential of 312 mV at 10 mA cm–2. Then, functional BDC-X ligands (X = NH2, OH, NO2, DH) with various characteristic groups were selected to construct a new series, namely, Fe3-MOF-BDC-X, to further improve its OER electrocatalytic performance. As expected, Fe3-MOF-BDC-NH2 exhibited a greatly enhanced OER performance with ultralow Tafel slopes of 45 mV dec–1 and overpotentials of 280 mV at 10 mA cm–2 when the BDC-NH2 ligand was adopted, even superior to commercial IrO2 (323 mV) and most of the reported pristine MOFs as OER electrodes. Much higher structural stability was proven. The detailed structure–property relationship and mechanism are discussed. In a word, this work provides a very important theoretical basis for the design and exploration of new MOF electrocatalysts.

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“…[23] The presence of free functionalized organic sites have significant influence on the electrocatalysis and, based on this, Zhang and co-workers have developed two MOFs (FeÀ MOFÀ NHCHO and FeÀ MOFÀ NO 2 ) having free functional organic sites (À NHCHO and À NO 2 ) which show better electrocatalytic water oxidation than the parent MOF. [24] Again, the presence of unsaturated metal centre (UMC) has a tremendous effect on the electrocatalysis of MOFs. [25,26] UMCs allow the substrate to directly interact with the catalytically active centres and facilitate the catalysis.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Water Oxidation by Hydrolytically Stable Metal‐Organic Frameworks at Both Neutral and Alkaline Medium: Inverse Relation of Dimensionality with Catalytic Activity

et al. 2023

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Catalyst development for water splitting to afford hydrogen as a green source of energy is one of the major areas of research in the pursuit of sustainable energy technology solution. Herein, the electrocatalytic water oxidation behaviour of two different Co‐pdc (H2pdc=pyridine‐2,5‐dicarboxylic acid) based metal‐organic frameworks (MOFs) of different dimensionalities (2D and 1D) is reported. 2D‐MOF {[Co(pdc)(H2O)2] ⋅ H2O}n acts as the mother which transforms into daughter 1D‐MOF {[Co(pdc)(H2O)2] ⋅ 7H2O}n via consecutive dehydration and rehydration. Within 2D‐MOF, the Co2+ shows six coordinated octahedral geometry with two coordinated water molecules and for the 1D‐MOF, Co2+ shows five coordinated square pyramidal geometry having two coordinated water molecules and one open metal site. Both the MOFs show excellent stability over a pH range of 3 to 11 even after 24 hours and show OER activity from neutral to alkaline medium. The MOFs retain their crystalline structure even after OER at neutral pH but eventually gets decomposed; but they are converted into their (oxy)hydroxides at pH 14. Interestingly, 1D MOF shows superior activity in both neutral and alkaline medium over the 2D framework for OER due to presence of open metal sites, better electrical conductivity and larger electrochemically active surface area.

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Ligand Functionalized Iron‐Based Metal‐Organic Frameworks for Efficient Electrocatalytic Oxygen Evolution

Cited by 18 publications

References 70 publications

Rationally Reconstructed Metal–Organic Frameworks as Robust Oxygen Evolution Electrocatalysts

Rationally Reconstructed Metal–Organic Frameworks as Robust Oxygen Evolution Electrocatalysts

Molecular Regulation Based on Functional Trimetallic Metal–Organic Frameworks for Efficient Oxygen Evolution Reaction

Electrocatalytic Water Oxidation by Hydrolytically Stable Metal‐Organic Frameworks at Both Neutral and Alkaline Medium: Inverse Relation of Dimensionality with Catalytic Activity

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