Tuning the morphology and electron structure of metal-organic framework-74 as bifunctional electrocatalyst for OER and HER using bimetallic collaboration strategy

Cheng, Chen; Suo, Na; Han, Xinqi; He, Xingquan; Zhang, Dou; Lin, Zihan

doi:10.1016/j.jallcom.2021.158795

Cited by 45 publications

(27 citation statements)

References 42 publications

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“…The enhanced electrocatalytic OER activity of Mn-MOF/NF can be attributed to the strong intermolecular bimetallic synergistic interaction between Mn 2+ and Ni 2+ . 67 Moreover, the uniform and closely packed layered growth of the Mn-MOF upon the NF surface provides the promising exposure and maximum utilization of the electroactive metal ion sites, and substrate NF having good electrical conductivity facilitates necessary electron transport for the redox reaction. The hydrophilic nature of NF and its porous microholes and zigzag flow channels also enhance the mass transfer of the electrolyte by preventing overgrowth of the bubbles during the course of oxygen evolution.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The Mn-MOF/NF electrode has exhibited a similar kind of LSV curve even after 1000 cycles with an almost identical overpotential to the initial one, suggesting its superior stability and durability (Figure d). The enhanced electrocatalytic OER activity of Mn-MOF/NF can be attributed to the strong intermolecular bimetallic synergistic interaction between Mn 2+ and Ni 2+ . Moreover, the uniform and closely packed layered growth of the Mn-MOF upon the NF surface provides the promising exposure and maximum utilization of the electroactive metal ion sites, and substrate NF having good electrical conductivity facilitates necessary electron transport for the redox reaction.…”

Section: Resultsmentioning

confidence: 99%

“…This suggests that Mn-MOF/NF possesses a faster kinetics toward the OER than many recently reported NF-based electrodes (Section S7 and Table S3). The electron transfer from Mn 2+ to Ni 2+ in Mn-MOF/NF , evident from the positive shift in the binding energy of 0.86 eV for Mn 2p 3/2 for Mn-MOF/NF in high-resolution XPS analysis, leads to the decreased population of d-orbital electrons near Mn 2+ , favoring the adsorption of the oxygenated intermediates OH* and OOH* and O* on the surface of the Mn-MOF/NF electrode and enabling the OER kinetics to be faster . The OER kinetics would most likely proceed through the formation of a metal oxide hydroxide (MOOH) intermediate, followed by the subsequent decomposition of MOOH to form O 2 gas molecules .…”

Section: Resultsmentioning

confidence: 99%

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In Situ Grown Mn(II) MOF upon Nickel Foam Acts as a Robust Self-Supporting Bifunctional Electrode for Overall Water Splitting: A Bimetallic Synergistic Collaboration Strategy

Goswami

Ghosh

Pradhan

et al. 2022

ACS Appl. Mater. Interfaces

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The design of highly efficient, cost-effective non-noble metal-based electrocatalysts with superior stability for overall water splitting (OWS) reactions is of great importance as well as of immense challenge for the upcoming sustainable and green energy conversion technologies. Herein, a convenient and simple in situ solvothermal method has been adopted to fabricate a self-supported, binder-free 3D electrode (Mn-MOF/NF) by the direct growth of a newly synthesized carboxylate-based pristine Mn(II)-metal–organic framework (Mn-MOF) upon the conducting substrate nickel foam (NF). The binder-free Mn-MOF/NF electrode exhibits excellent performances toward OWS with ultralow overpotentials of 280 mV@20 mA cm–2 for the oxygen evolution reaction (OER) and 125 mV@10 mA cm–2 for the hydrogen evolution reaction (HER) with remarkable durability. Mn-MOF/NF can also attain a current density of 10 mA cm–2 with a low cell voltage of 1.68 V in a 0.1 M KOH solution in a two-electrode system for OWS. The direct growth of nonconducting electroactive Mn-MOF materials upon conducting substrate NF provides an excellent mass transport of the electrolyte with a relatively low contact resistance due to the strong catalyst–substrate contact and enhances the efficient electron transport for OWS. The redox chemical etching of the self-sacrificial substrate NF during solvothermal synthesis introduces redox-active Ni2+ in Mn-MOF/NF. Thus, the excellent OWS electrocatalytic activity can mainly be attributed to the bimetallic synergistic collaboration of the two redox active metal centers (Mn2+ and Ni2+) along with the excellent support surface of NF, which provides a high specific surface area and maximum utilization of the electroactive metal ion sites by preventing the self-aggregation of the active sites. The Mn-MOF/NF electrode also exhibits superb stability and durability for a prolonged time throughout the multiple cycles of full water splitting reactions. Therefore, this work elucidates a convenient and smart approach for constructing MOF-based bifunctional electrocatalysts for OWS.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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In Situ Grown Mn(II) MOF upon Nickel Foam Acts as a Robust Self-Supporting Bifunctional Electrode for Overall Water Splitting: A Bimetallic Synergistic Collaboration Strategy

Goswami

Ghosh

Pradhan

et al. 2022

ACS Appl. Mater. Interfaces

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“…67 This result indicates that spontaneous oxidation of Ni 2+ valence into Ni 3+ to form nickel (oxy)hydroxide during the OER process results in the enhancement of OER performance. 61 However, the XRD pattern could still be indexed to the Ni(Pz), as compared in Figure S10c, indicating that only a surface layer of Ni(Pz) changed into nickel (oxy)hydroxide during OER and the major phase of Ni(Pz) is well maintained. 67 Thus, the abovementioned characterizations could confirm the activity and morphology stability of interconnected sheets of Ni(Pz)-E-PVP during OER catalysis.…”

Section: Electrochemical/catalytic Propertiesmentioning

confidence: 99%

Promoting the Oxygen Evolution Reaction via Morphological Manipulation of a Lamellar Nanorod-Assembled Ni(II)-Pyrazolate Superstructure

Farid

Mao

Ren

et al. 2022

ACS Appl. Mater. Interfaces

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Nanoscale pyrazolate-based coordination polymers (CPs) are becoming increasingly popular as electrocatalysts owing to their customizable compositions and structures. However, using them for oxygen evolution reaction (OER) is highly challenging due to their unsatisfactory catalytic efficiency and relatively low stability. Herein, a simple one-step solvothermal process was employed for the fabrication of polycrystalline nickel-pyrazolate [Ni(Pz)] with an unusual lamellar nanorod-assembled microsphere morphology for the first time using ethanol as a green organic solvent via controlling other physical parameters. Meanwhile, the Ni(Pz) structure and morphology are investigated to derive its formation process following the different monomeric feed ratios relying on the metal/ligand interactions of CP. Shaping the Ni(Pz) electrocatalyst in well-oriented lamellar nanorod-assembled microspheres brings the advantage of porosity and high specific surface area, which expedites mass/charge transport and contact with the electrolyte as well as creates less tortuous pathways for charge distribution, thus improving the charge homogeneity. These high-class structural features and polycrystalline nature of Ni(Pz)-E-PVP facilitate amazing catalytic OER activity with a low overpotential of 290 mV at 10 mA cm–2 and a Tafel slope of only 94 mV dec–1 beyond the yardstick material (i.e., RuO2) in alkaline solution. A suite of measurements, entailing X-ray photoelectron spectroscopy and density functional theory calculations, suggest that the rich Ni–N4 moieties in Ni(Pz)-E-PVP are central species providing adsorption sites for OER intermediates. This facile protocol is prophesied to commence the imminent development of noble metal-free, effective, and low-priced electrocatalysts for OER.

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“…5,6 Although noble metal-based materials such as Pt/ C and RuO 2 /IrO 2 for the hydrogen evolution reaction (HER) and OER at cathodic and anodic electrodes, respectively, have been considered to be the most advanced electrocatalysts, the high cost and shortage of raw materials greatly impede their large-scale application. [7][8][9][10] Hence, the rational design and fabrication of bifunctional electrocatalysts with low cost and high efficiency for overall water splitting are still significant and challenging.…”

Section: Introductionmentioning

confidence: 99%

Enhanced electrocatalytic activity of FeNi alloy quantum dot-decorated cobalt carbonate hydroxide nanosword arrays for effective overall water splitting

Zhao

Lei

et al. 2022

Nanoscale

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Tuning the morphology and electron structure of metal-organic framework-74 as bifunctional electrocatalyst for OER and HER using bimetallic collaboration strategy

Cited by 45 publications

References 42 publications

In Situ Grown Mn(II) MOF upon Nickel Foam Acts as a Robust Self-Supporting Bifunctional Electrode for Overall Water Splitting: A Bimetallic Synergistic Collaboration Strategy

In Situ Grown Mn(II) MOF upon Nickel Foam Acts as a Robust Self-Supporting Bifunctional Electrode for Overall Water Splitting: A Bimetallic Synergistic Collaboration Strategy

Promoting the Oxygen Evolution Reaction via Morphological Manipulation of a Lamellar Nanorod-Assembled Ni(II)-Pyrazolate Superstructure

Enhanced electrocatalytic activity of FeNi alloy quantum dot-decorated cobalt carbonate hydroxide nanosword arrays for effective overall water splitting

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