First-row transition metal-based materials derived from bimetallic metal–organic frameworks as highly efficient electrocatalysts for electrochemical water splitting

Sanati, Soheila; Morsali, Ali; Garcı́a, Hermenegildo

doi:10.1039/d1ee03614a

Cited by 211 publications

(108 citation statements)

References 291 publications

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“…The CPE element represents the surface porosity. An ideal electrocatalyst generally requires high surface area, porous structure, abundant active sites, and a synergic effect between the constituting components. − Any of these characteristics can have a significant influence on the electrocatalytic performance. A high surface area and an increased content of the electroactive metal centers in the structure can increment the number of accessible active sites on the electrocatalyst surface.…”

Section: Resultsmentioning

confidence: 99%

Pillared-MOF@NiV-LDH Composite as a Remarkable Electrocatalyst for Water Oxidation

et al. 2022

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Oxygen evolution reaction (OER) represents a highly important electrochemical transformation in energy storage and conversion technologies. Considering the low rate of this four-electron half-reaction, there is a demand for efficient, stable, and noble-metal-free electrocatalysts to improve the kinetic and economical parameters. In this work, a new pillared-MOF@NiV-LDH nanocomposite based on a Co II metal−organic framework (pillared-MOF) and heterometallic Ni/ V-layered double hydroxide (NiV-LDH) was assembled via a simple protocol, characterized, and explored as an electrocatalyst in OER. A remarkable electrocatalytic efficiency of pillared-MOF@NiV-LDH in 1 M KOH is evidenced by a low overpotential (238 mV at 10 mA cm −2 current density) and a small value of the Tafel slope (62 mV dec −1 ). These parameters are very close to those of the reference IrO 2 electrocatalyst and are superior to the majority of the LDH-and MOF-based systems previously applied for OER. Excellent stability of pillared-MOF@NiV-LDH was confirmed by the chronopotentiometry tests for 70 h and linear-sweep voltammetry after 7000 cycles. Features such as rich electroactive sites, porous structure, high surface area, and synergic effect between pillared-MOF and NiV-LDH are likely responsible for the remarkable electrocatalytic efficiency of this electrocatalyst in OER. Despite prior reports on the application of NiV-LDH in OER, the present study describes the first example where this type of LDH is blended with MOF to generate a nanocomposite material. The interface between the two components of the composite can improve the electronic structure and, in turn, the electrocatalytic behavior. The introduction of this composite paves the way toward the synthesis of other multicomponent materials with potential applications in different energy fields.

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Section: Resultsmentioning

confidence: 99%

Pillared-MOF@NiV-LDH Composite as a Remarkable Electrocatalyst for Water Oxidation

et al. 2022

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“…As a prominent class of crystalline compounds, metal–organic frameworks (MOFs) feature porous structures constructed from metal cations or clusters and organic linking ligands. − This class of materials has attracted a colossal attention in many fields, owing to their structural and chemical tunability, high surface area, controllable morphologies, multiple active sites, adjustable porous structures, and variable chemical functionalities. − Because MOFs can feature π bonding in their structures, the electron transfer between the organic ligands and metals can significantly enhance the NLO effect. − To further improve the NLO performance of these materials, the charge transfer can be tuned by the introduction of strong electron-acceptor/donor groups so that the energy gap can decline by reinforcing the resulting conjugated systems. − Among a variety of MOFs, NU-1000 ([Zr 6 (μ 3 -OH) 4 (μ 3 -O) 4 (OH) 4 (H 2 O) 4 (μ 8 -TBAPy) 2 ], Scheme ) has been regarded as an ideal NLO material because of a diversity of features, which include good stability, high size of pores for postsynthetic modifications, tunable electronic structure with π-conjugated organic linkers, large NLO coefficient, and narrow linear adsorption. − The application of MOFs in the NLO field is, however, accompanied by several limitations such as insufficient thermostability and optical transparency, which can potentially be overcome by blending MOFs with other materials to generate hybrid composites. , …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Postsynthetic Modification of NU-1000 for Designing a Polyoxometalate-Containing Nanocomposite with Enhanced Third-Order Nonlinear Optical Performance

et al. 2022

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For the advancement of laser technologies and optical engineering, various types of new inorganic and organic materials are emerging. Metal−organic frameworks (MOFs) reveal a promising use in nonlinear optics, given the presence of organic linkers, metal cluster nodes, and possible delocalization of π-electron systems. These properties can be further enhanced by the inclusion of solely inorganic materials such as polyoxometalates as prospective low-cost electron-acceptor species. In this study, a novel hybrid nanocomposite, namely, SiW 12 @NU-1000 composed of SiW 12 (H 4 SiW 12 O 40 ) and Zrbased MOF (NU-1000), was assembled, completely characterized, and thoroughly investigated in terms of its nonlinear optical (NLO) performance. The third-order NLO behavior of the developed system was assessed by Z-scan measurements using a 532 nm laser. The effect of two-photon absorption and self-focusing was significant in both NU-1000 and SiW 12 @NU-1000. Experimental studies suggested a much superior NLO performance of SiW 12 @NU-1000 if compared to that of NU-1000, which can be assigned to the charge-energy transfer between SiW 12 and NU-1000. Negligible light scattering, good stability, and facile postsynthetic fabrication method can promote the applicability of the SiW 12 @NU-1000 nanocomposite for various optoelectronic purposes. This research may thus open new horizons to improve and enhance the NLO performance of MOF-based materials through π-electron delocalization and compositing metal−organic networks with inorganic molecules as electron acceptors, paving the way for the generation of novel types of hybrid materials for prospective NLO applications.

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“…Water oxidation at anode is considered as the bottleneck for electrochemical water splitting as it is kinetically sluggish involving high energy reaction intermediates. [1][2][3] Therefore, the overall efficiency of water electrolysis depends on the development of highly active and stable water oxidation catalysts. [4] In this respect, transition metal-based catalysts have been demonstrated with excellent water oxidation activity.…”

Section: Introductionmentioning

confidence: 99%

Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

et al. 2022

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Herein, we have demonstrated the control over the structure of precatalysts to tune the properties of the active catalysts and their water oxidation activity. The reaction of K 3 [Fe(CN) 6 ] and Na 2 [Fe(CN) 5 (NO)] with Co(OH) 2 @CC produced precatalysts PC-1 and PC-2, respectively, with distinct structural and electronic features. The replacement of the À CN group with strong π-acceptor À NO modulates the electronic and atomic structure of PC-2. As a result, a facile electrochemical transformation of PC-2 into active catalyst FeÀ Co-(OH) 2 -Co(O)OH (AC-2) has been attained only in 15 CV cycles while 600 CV cycles are required for the electrochemical activation of PC-1 into AC-1. The X-ray absorption studies reveal the contraction of the CoÀ O and FeÀ O bond in AC-2 because of the presence of a higher amount of Co 3 + and Fe 3 + than in AC-1. The high valent Co 3 + and Fe 3 + modulates the electronic properties of AC-2 and assists in the OÀ O bond formation, leading to the improved water oxidation activity.

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First-row transition metal-based materials derived from bimetallic metal–organic frameworks as highly efficient electrocatalysts for electrochemical water splitting

Abstract: Electrochemical water splitting is a mature technology for hydrogen generation. Numerous studies have focused on the development of highly efficiency electrocatalysts to produce hydrogen and oxygen from water electrolysis through...

Cited by 211 publications

References 291 publications

Pillared-MOF@NiV-LDH Composite as a Remarkable Electrocatalyst for Water Oxidation

Pillared-MOF@NiV-LDH Composite as a Remarkable Electrocatalyst for Water Oxidation

Postsynthetic Modification of NU-1000 for Designing a Polyoxometalate-Containing Nanocomposite with Enhanced Third-Order Nonlinear Optical Performance

Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

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