Sustained Water Oxidation by a Catalyst Cage‐Isolated in a Metal–Organic Framework

Nepal, Binod; Das, Siddhartha

doi:10.1002/anie.201301327

Cited by 122 publications

(88 citation statements)

References 33 publications

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“…However, there are non-trivial considerations associated with this strategy too. 92 Catalytic testing using the impregnated MOF in the presence of sacrificial oxidant K-oxone yielded a TOF of 0.02 (mol dioxygen per mol of caged manganese dimer)s À1 . A dual-compartment reactor, comprising independent electrolytic cells for water oxidation and ECPB reduction was recently described.…”

Section: Mof Supported Electrocatalytically Driven Water Splittingmentioning

confidence: 99%

Metal organic frameworks for photo-catalytic water splitting

Meyer

Ranocchiari

Bokhoven

2015

Energy Environ. Sci.

294

173

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Metal organic frameworks (MOFs) have recently debuted as participants and solid supports in catalytic water splitting. Their porosity and structural versatility offer a tantalising consolidation of the components needed for solar light harvesting and water splitting. Herein, we describe a selection of relevant contemporary investigations that employ electrocatalysis, chemically introduced redox partners, and photo-catalysts to generate dioxygen and dihydrogen from water. The role of semiconducting MOFs in these systems is addressed, in tandem with band gap control by linker functionalisation and doping. Considered holistically, MOFs offer an impressive physical, spatial and chemical versatility with which to support and sustain water splitting reactions. Major challenges toward practical implementation do remain, but opportunities for development are evidently numerous. Broader contextGrowing experimental and computational evidence suggests that metal organic frameworks (MOFs) can make a meaningful contribution to catalytically promoted water splitting. They offer an impressive physical, spatial, chemical and electronic mutability with which to support and sustain water splitting halfreactions. Their classical features -thermal stability, large surface area, high porosity and modularity -define them as versatile solid supports. Building on a vast library of existing frameworks, post-synthetic modification techniques allow further tailoring of intrinsic MOF properties and functionality. Compelling parallels are now being drawn between semiconductors and a select group of MOFs that are capable of sustaining a photo-generated charge separated state and using the resultant charge carriers to perform chemical transformations. In this perspective we describe a selection of contemporary electrocatalytic, chemically promoted, and photo-catalytic investigations that apply MOFs to water oxidation and reduction half reactions. We highlight successful strategies employed by the scientific community for engineering of catalytic sites, managing redox half-reactions, introducing light sensitisation and band gap tuning -all within the confines of a framework. Major challenges toward practical application certainly remain, but the adaptive nature of MOFs stands to make a poignant contribution to the discourse on photo-catalysed water splitting.Scheme 1 Proton reduction (1) and water oxidation (2) half reactions (NHE, 25 1C, pH 0). ; Tel: +41 (0)56 310 5843 † During the period between submission and revision of our manuscript a couple of examples of water reduction carried out by, or in the presence of MOFs, have appeared in the literature. We refer readers to the papers by: Du et al. concerning a nickel mercaptopyrimidine MOF with a TOF of 10.6 h À1 in the presence of triethylamine and fluorescein under blue light, 124 and Chen et al. describing a photosensitised MOF encapsulating a platinum dihydrogen evolving catalyst (Ru-Pt@UiO-67). 125

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Section: Mof Supported Electrocatalytically Driven Water Splittingmentioning

confidence: 99%

Metal organic frameworks for photo-catalytic water splitting

Meyer

Ranocchiari

Bokhoven

2015

Energy Environ. Sci.

294

173

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“…[34,[44][45][46][47][48][49][50] In addition, Jiao and Frei used silica-supported manganese oxide [51,52] whereas manganese oxide molecular sieves were successfully employed by Suib et al [53] Nepal and Das discovered that the immobilization of an active manganese-terpyridine complex in the pores of a metal-organic framework (MOF) resulted in enhanced photostability and subsequently in activity for the photochemical water oxidation. [54] Electrochemical water oxidation using electrodeposited manganese oxides has been the main theme of interest in the group of Dau for a long time. [16,[55][56][57][58] Lately, electrochemical water splitting using layered and three dimensional crosslinked manganese oxides were studied by the same group; they correlated the catalytic activity with the responsible structural motifs.…”

Section: Introductionmentioning

confidence: 99%

Nanostructured Manganese Oxides as Highly Active Water Oxidation Catalysts: A Boost from Manganese Precursor Chemistry

et al. 2014

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We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1

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“…[8][9][10][11][12] The known heterogeneous WOCs are metal oxides, including spinel oxides, monomeric, dimeric,a nd tetrameric molecular complexes, polyoxometalates (POMs) and POM-supported metal complexes,v arious nano-materials, electrodeposited metals from aqueous solutionso fm etal salts, amorphous metal-oxide thin-films, and metal-organic framework (MOF)-containing compounds. [2,[13][14][15][16][17] Although this large body of molecular transition-metal catalysts and active metal-oxide materials has been developed for water oxidation, substantial challenges remain for the ultimate goal of an efficient, inexpensive, and robust electrocatalyst. Among transition-metal catalysts, cobalt catalysts would be more economic in comparison to other expensive transition-metal-based (e.g.,r uthenium, iridium,r hodium, gold, etc.)…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Water Oxidation Catalyzed by an In Situ Generated α‐Co(OH)₂ Film on Zeolite‐Y Surface

Bose

Debgupta

Ramsundar

et al. 2017

Chemistry A European J

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The design and synthesis of an efficient and robust water-oxidation catalyst with inexpensive materials remains an important challenge in the context of artificial photosynthesis. Herein, as imple but unique technique is reported to in situ generate at hin-film of a-Co(OH) 2 on the surface of zeolite-Y [hereafter referred to as Y-a-Co(OH) 2 ] that acts as an efficient and stable catalyst for electrochemical water oxidation in alkaline medium. Catalyst Y-a-Co(OH) 2 is so stable that it retains its catalytic activity even after 2000 cyclic voltammetric cycles of water oxidation. Expectedly,t he chemical compositiono fa-Co(OH) 2 on the surface of zeolite-Y remainss ame as that of parentY -a-Co(OH) 2 after 2000 electrocatalytic cycles. AT afel slope as low as 59 mV decade À1 in 0.1 m KOH (pH 13) suggestsf aster oxygen evolution kinetics (overpotential = 329 mV;t urnover frequency = 0.35 mol O 2 (mol Co)À1 s À1 at 1mAcm À2 )t han the existing aCo(OH) 2 -based electrocatalysts operating in alkaline medium.

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Sustained Water Oxidation by a Catalyst Cage‐Isolated in a Metal–Organic Framework

Cited by 122 publications

References 33 publications

Metal organic frameworks for photo-catalytic water splitting

Metal organic frameworks for photo-catalytic water splitting

Nanostructured Manganese Oxides as Highly Active Water Oxidation Catalysts: A Boost from Manganese Precursor Chemistry

Electrochemical Water Oxidation Catalyzed by an In Situ Generated α‐Co(OH)₂ Film on Zeolite‐Y Surface

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Sustained Water Oxidation by a Catalyst Cage‐Isolated in a Metal–Organic Framework

Cited by 122 publications

References 33 publications

Metal organic frameworks for photo-catalytic water splitting

Metal organic frameworks for photo-catalytic water splitting

Nanostructured Manganese Oxides as Highly Active Water Oxidation Catalysts: A Boost from Manganese Precursor Chemistry

Electrochemical Water Oxidation Catalyzed by an In Situ Generated α‐Co(OH)2 Film on Zeolite‐Y Surface

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Electrochemical Water Oxidation Catalyzed by an In Situ Generated α‐Co(OH)₂ Film on Zeolite‐Y Surface