Cobalt Metal–Organic Framework Based on Two Dinuclear Secondary Building Units for Electrocatalytic Oxygen Evolution

Gutiérrez‐Tarriño, Silvia; Olloqui‐Sariego, José Luis; Calvente, Juan José; Palomino, Miguel; Espallargas, Guillermo Mı́nguez; Jordá, José L.; Rey, Fernando; Oña‐Burgos, Pascual

doi:10.1021/acsami.9b13655

Cited by 42 publications

(28 citation statements)

References 60 publications

(107 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: Methodssupporting

confidence: 80%

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: Methodssupporting

confidence: 80%

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

et al. 2020

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“…383 Molecular species are either directly incorporated into the nano-voids of these porous materials or used as building blocks for the formation of novel frameworks. [384][385][386] These strategies are based on the assumption that the nanoscale confinement effect disables the intermolecular deactivation routes of molecular WOCs. Therefore, many of these systems offer the benefit of investigating molecular reaction pathways, while circumventing the issue of aggregationinduced destabilization.…”

Section: Combining the Advantages Of Molecular And Heterogeneous Wocsmentioning

confidence: 99%

Molecular and heterogeneous water oxidation catalysts: recent progress and joint perspectives

et al. 2021

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“…Inspired by different inorganic OER catalysts having multimetallic nodes, Gutiérrez-Tarriño et al prepared a MOF formulated as {[Co 2 (BTC)1,3(DMF) 2 ]-[Co 2 (BTC)1,3(DMF) 2 py]} (Co 2 -MOF) which constituted of two dissimilar binuclear secondary building units (SBUs); out of which, one of the SBUs was made up of two crystallographically independent cobalt centers. 78 Unfortunately, chemical stability studies revealed that the Co 2 -MOF was unstable in the presence of protic solvents like ethanol, water and their mixture, and was readily being hydrolysed to a different mononuclear cobalt-MOF. But it could be evaded by dispersing Co 2 -MOF in an alcoholic solution of Nafion.…”

Section: A Mofs With Polynuclear (Metal Cluster) Nodesmentioning

confidence: 99%

Evolution of metal organic frameworks as electrocatalysts for water oxidation

et al. 2020

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Cobalt Metal–Organic Framework Based on Two Dinuclear Secondary Building Units for Electrocatalytic Oxygen Evolution

Cited by 42 publications

References 60 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

Molecular and heterogeneous water oxidation catalysts: recent progress and joint perspectives

Evolution of metal organic frameworks as electrocatalysts for water oxidation

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