One‐Pot Synthesis of Heterobimetallic Metal–Organic Frameworks (MOFs) for Multifunctional Catalysis

Iqbal, Bilal; Saleem, Murtaza; Arshad, Sidra; Rashid, Jamshaid; Hussain, Naveed; Zaheer, Muhammad

doi:10.1002/chem.201901939

Cited by 125 publications

(60 citation statements)

References 72 publications

(90 reference statements)

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“…The reason might be that thiourea was adsorbed into the SyA‐Co 2 Fe‐ST′s channel through by capillary action or cover the MOF surface via intermolecular interaction, leading to its decreased pore size and slightly increased specific surface area than that of SyA‐Co 2 Fe. Therefore, the rich supermicropores of SyA‐Co 2 Fe‐ST might expose more catalytic active sites, whereas mesopores should facilitate the charge and mass transport in the OER process as the previously reported other electrocatalysts with hierarchical porosity . X‐ray photoelectron spectrum (XPS) was also conducted to investigate the chemical state, bonding situation, and surface electronic structure of the SyA‐Co 2 Fe and SyA‐Co 2 Fe‐ST catalysts (Figure ).…”

Section: Methodsmentioning

confidence: 96%

See 1 more Smart Citation

Rational Design of a N,S Co‐Doped Supermicroporous CoFe–Organic Framework Platform for Water Oxidation

et al. 2020

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It remains ac hallenge to rational design of an ew metal-organic framework (MOF)a sh ighly efficient direct electrocatalysts for the oxygen evolution reaction(OER). Herein, we developed as imple and effective method to explore an ew pillaredlayered MOF with syringic acid as ap romising OER electrocatalyst. The isostructuralm ono-, heterobimetallic MOF and N,S codoped MOF by mixing thiourea were quicklys ynthesized in a high yield under solvothermal condition. Moreover,t he optimized N,S co-doped MOF exhibits the lowest overpotential of 254 mV at 10 mA cm À2 on ag lass carbon electrode andas mall Ta fel slope of 50 mV dec À1 ,e specially,t his catalysta lso possesses long-term electrochemical durability for at least 16 h. According to the characterization, the incorporationo fNa nd S atoms into this heterobimetallic CoFe-based MOF could modify its pore structure,t une the electronic structure, accordingly,i mprove the mass and electron transportation,a nd facilitate the formation of active species, as ac onsequence, the improveda ctivity of this new N,S co-doped MOF for OER should be mainly be ascribed to higher electrochemical activation toward the actives peciesv ia in situ surface modification during the OER process.Metal-organic frameworks (MOFs), especially,p illared-layered MOFs, are rising star materials in the field of materials science because of their ultrafinep orosity,r ich active metal-sites and tunable structures, which have attracted enormousi nterest and have aw idespread application in catalysis, energy conversion technologies, and environmentally friendly technologies. [1][2][3][4][5][6][7][8][9][10][11][12][13] In particular,M OFs have been employed as high active electrocatalysts to improvet he sluggish reactionk inetics of water oxidation[ i.e.,t he oxygen evolution reaction (OER)] as one of the determine steps and the key processes in water splitting and metal-air batteries. [5][6][7][8][9][10][11][12][13] However,m ost of direct MOFs as electrocatalysts have poor long-term electrochemical durability in reaction media (strong acid or strongb ase), limiting their practical application in the field of water splitting since the long-term stability and high activity are equally importantf or catalysts. [14][15][16][17][18][19] Besides, it is criticalt hat improving MOF conductivity to enhancet heir intrinsic catalytic activity because of their low electronic conductivity and poor mass permeability.O ne effective strategy is to fabricate their derivatives through high temperature pyrolysis or chemical conversions, [20][21][22][23][24][25][26][27][28][29][30][31][32][33] such as metal oxides or hydroxides, [24][25][26] carbonbased derivatives, [27][28][29][30] and composite materials. [31][32][33] Although these derivatives exhibit improved electrocatalytic performance compared with the pristine MOFs precursors, during the pyrolysis, the intrinsics tructure of MOFs has been destroyed, simultaneously,t hese expensive organic ligands have been decomposed, severely hampering their practically largesca...

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Section: Methodsmentioning

confidence: 96%

“…For SyA‐Co 2 Fe, two peaks at 710.88 and 724.53 eV can be assigned to Fe 2p 3/2 and Fe 2p 1/2 , respectively . The binding energy of 710.25, 724.4 and a small satellite peak at 717.6 eV implied the presence of Fe 2+ species . There are still two relatively weak peaks at 713.26 and 731.18 eV, which are assigned to Fe 3+ ion .…”

Section: Methodsmentioning

confidence: 99%

Rational Design of a N,S Co‐Doped Supermicroporous CoFe–Organic Framework Platform for Water Oxidation

et al. 2020

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“…For Fe-MIL-88B, the vibration of the central oxygen in the planar Fe3O cluster with D3h symmetry produced an adsorption peak at approximately 613 cm -1 . However, when one iron in the trinuclear metal cluster was replaced with another metal ion, the symmetry was reduced from D3h to C2v [49]. For this reason, the intensity of this band was obviously lower in the mixed-metal cluster samples, while the band corresponding to Fe2MO (M = Mn, Co, or Ni) at 695 cm -1 was prominent.…”

Section: Resultsmentioning

confidence: 97%

“…The adsorption peak of νas(-COO-) for pure terephthalic acid appeared at 1684 cm -1 , but in the spectrum of Fe2M-MIL-88B, no obvious peak was observed at this position. Instead, νas(-COO-) and νs(-COO-) adsorption bands corresponding to the coordination bonds between the ligands and the trinuclear oxo-centered metal clusters were present at 1583 and 1397 cm -1 , indicating the absence of free ligand in the as-prepared materials and the coordination of all the ligands to metal clusters [48,49]. Additionally, the peak at 751 cm -1 , which is attributed to the vibration of the C-H bonds of benzene rings, further demonstrated the presence of coordinated organic ligands [44,49].…”

Section: Resultsmentioning

confidence: 99%

Iron-based binary metal-organic framework nanorods as an efficient catalyst for the oxygen evolution reaction

Zhang

et al. 2021

Chinese Journal of Catalysis

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“…A series of spindle‐shaped bimetallic MOFs with a variable Fe/Co ratio, successfully synthesized via a one‐pot solvothermal approach by Bushra et.al in 2019 exhibit excellent activity for OER. In an alkaline medium, the best material (Fe/Co=1) with high porosity and synergetic effect between MOF and two metals results in overpotential (410 mV), Tafel slope (60 mV/dec),and long term stability for 6 hours, as shown in Figure 18 c, d [199] …”

Section: Materials For Oermentioning

confidence: 97%

Recent Advances in Electrocatalysis of Oxygen Evolution Reaction using Noble‐Metal, Transition‐Metal, and Carbon‐Based Materials

2020

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A considerable concern in exploring clean, efficient, and renewable energy resources to effectively replace fossil fuels and to combat the environmental problems and energy scarcities for a sustainable future has been observed. In this context, hydrogen is a clean, renewable, energetically efficient fuel with infinite potential for the future, which can generate a large amount of energy through the electrocatalytic splitting of earth‐abundant water resources. Noble metals, owing to their extraordinary efficiency and stability, are state‐of‐the‐art catalysts for the oxygen evolution reaction (OER) process. However, their scarcity and high cost hamper their commercialization. To replace these expensive noble‐metal‐based materials, researchers are extensively working on the development of cost effective, stable, conductive, and efficient non‐noble metal based materials such as transition metal oxides, borides, nitrides, sulfides, phosphides, selenides, perovskites oxides, and layered double hydroxides, where the incorporation of heteroatoms improves the electrocatalytic activity by modifying the electronic structure and enhances the conductivity and stability. In the case of transition‐metal based metal organic frameworks (MOFs) and MOF‐derived materials, the unique structure of MOFs with a high surface area and porosity, as well as rich redox chemistry of transition metals, leads to excellent response towards the OER process. Moreover, direct utilization of carbonaceous materials or making their composites with transition metals not only enhances the conductivity due to their conductive nature but also promotes stability by strongly binding with the electrocatalyst. Owing to the presence of functional groups on the surface or through different interactions, they provide multiple paths for facile electron and ion transport due to the sheet/network like structure, which help in the fine dispersion of electrocatalyst due to high surface area, prevent agglomeration, and in turn results in improved electrocatalytic activity. Besides these advances, a) there is still a need for a thorough understanding of reaction mechanism via in situ spectroscopic techniques to further optimize the composition and design of electrocatalyst to get desired results, b) the stability of the materials should be further enhanced to practically utilize synthesized material under harsh conditions without degradation, and c) the utilization of these optimized OER catalysts in a solar cell to consume solar energy (renewable energy source), remains a key requirement of the modern era.

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One‐Pot Synthesis of Heterobimetallic Metal–Organic Frameworks (MOFs) for Multifunctional Catalysis

Cited by 125 publications

References 72 publications

Rational Design of a N,S Co‐Doped Supermicroporous CoFe–Organic Framework Platform for Water Oxidation

Rational Design of a N,S Co‐Doped Supermicroporous CoFe–Organic Framework Platform for Water Oxidation

Iron-based binary metal-organic framework nanorods as an efficient catalyst for the oxygen evolution reaction

Recent Advances in Electrocatalysis of Oxygen Evolution Reaction using Noble‐Metal, Transition‐Metal, and Carbon‐Based Materials

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