Isostructural Ni^II Metal–Organic Frameworks (MOFs) for Efficient Electrocatalysis of Oxygen Evolution Reaction and for Gas Sorption Properties

Abstract

Design ands ynthesis of stable, active and cost-effective electrocatalystf or water splitting applicationsi sa n emerging area of research, given thed epletion of fossil fuels. Herein, two isostructuralN i II redox-activem etal-organic frameworks (MOFs) containing flexible tripodal trispyridyl ligand (L)a nd linear dicarboxylates such as terephthalate (TA) and 2-aminoterphthalate (H 2 NTA) are studied fort heir catalytic activity in oxygen evaluation reaction( OER). The 2D-layered MOFs form 3D hydrogen bonded frameworks containing one-dimensional hydrophilic channels that are filled with water molecules. The electrochemical studies reveal that MOFs display an efficient catalytic activity towards oxygen evolutionr eactioni na lkaline conditions with an overpotential as low as 356 mV.F urther,t hese 2D-MOFs exhibit excellenta bility to adsorb water vapor (180-230 cc g À1 at 273 K) and CO 2 (33 cc g À1 at 273 K). The presence of hydrophilic functionality in the frameworks was found to significantly enhancet he electrocatalytic activity as well as H 2 Os orption.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

V═O Functionalized {Tm2}–Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO2 and Oxidation of Mustard Gas

“…Just as expected, all of the epoxide derivatives could be successfully transformed into the corresponding carbonates with high conversion rate of above 93%, as demonstrated in Table ; the corresponding 1 H NMR spectra of products are given in Figures S13–S16. With regard to the difference in catalytic efficienciesa, entries 1–4 exhibit a higher conversion rate in comparison to entry 5; a similar phenomenon has been found in other documented MOF-based catalysts. − From our speculation, the reasons include mainly (i) epoxide derivatives with a large molecular size will affect their accessibility into the nanochannels and (ii) large substituents on the epoxides with strong steric hindrance will influence the opportunity to contact with catalytically active sites. Moreover, in comparison to the previously reported monometallic Ln-organic framework, − cation-exchanged NUC-11 exhibited a faster catalytic efficiency.…”

Recent Progress of Two‐Dimensional Metal‐Organic Frameworks and Their Derivatives for Oxygen Evolution Electrocatalysis

“…2D Ni-based MOFs consisting of Ni units with different organic linkers have been investigated in the past few years, as summarized in Table 1. [45,62,65] Du et al [45] utilized a phthalocyanine (Pc) unit as a key organic fragment to construct a πconjugated 2D NiPc-MOF via a bottom-up method, exhibiting a layered morphology (thickness: 100-200 nm) as confirmed by AFM. The NiPc-MOF registered an OER η of 350 mV at 10 mA cm À 2 on a fluorine-doped tin oxide (FTO) substrate.…”

“…Although 2D MOF electrocatalysts are intensively studied in the past few years, the unsatisfactory stability and conductivity of 2D MOFs limit their further OER application. For example, Biradha and associates [65] synthesized a Ni MOF (NH 2 TA-MOF) composed of a flexible tripodal tris-pyridyl ligand and 2aminoterpthalate (H 2 NTA), displaying a η of 356 mV at 10 mA cm À 2 and a poor stability of 3.3 h. Alternatively, 2D MOF derivatives, either with or without metal component, obtained via pyrolysis in certain atmosphere and other post-treatment routes can potentially overcome these challenges. [48,87] Among these, MOF-derived metal-free carbon materials exhibit relatively poor OER catalytic performance, [88,89] which is likely due to water oxidation occurring at overpotentials, where oxidation of the carbon components can occur, compromising the structure.…”

“…2D Ni‐based MOFs consisting of Ni units with different organic linkers have been investigated in the past few years, as summarized in Table 1 [45,62,65] . Du et al [45] .…”

A Composite Bifunctional Oxygen Electrocatalyst for High‐Performance Rechargeable Zinc–Air Batteries

“…Tremendous efforts have been devoted to exploring bifunctional ORR/OER electrocatalysts including transition-metalcompounds, [24][25][26][27][28][29] metal-organic frameworks, [30][31][32][33][34][35][36][37] and heteroatomdoped nanocarbon. [38][39][40][41][42][43][44] Nevertheless, their bifunctionale lectrocatalytic performances remainu nsatisfactory with single active site.…”