Incorporation of iron hydrogenase active sites into a highly stable metal–organic framework for photocatalytic hydrogen generation

Sasan, Koroush; Lin, Qipu; Mao, Chengyu; Feng, Pingyun

doi:10.1039/c4cc03946g

Cited by 176 publications

(129 citation statements)

References 40 publications

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“…Besides other UiO-66/UiO-66-NH 2 [55,[145][146][147][148][149][150] and MIL-101/ MIL-101-NH 2 [151,152] associated work, the photocatalytic performances of MOF-supported catalysts, including UiO-type MOFs, [153][154][155] MOF-5, [56] MIL-125-NH 2 , [156,157] MIL-53-NH 2 , [158] Zr-porphyrin-based MOF (ZrPF), [159] and NU-1000 [160] are also summarized in Table 3. Besides other UiO-66/UiO-66-NH 2 [55,[145][146][147][148][149][150] and MIL-101/ MIL-101-NH 2 [151,152] associated work, the photocatalytic performances of MOF-supported catalysts, including UiO-type MOFs, [153][154][155] MOF-5, [56] MIL-125-NH 2 , [156,157] MIL-53-NH 2 , [158] Zr-porphyrin-based MOF (ZrPF), [159] and NU-1000 [160] are also summarized in Table 3.…”

Section: Mofs As Supportsmentioning

confidence: 99%

Metal–Organic Framework Based Catalysts for Hydrogen Evolution

Zhu

Zou

2018

Advanced Energy Materials

385

199

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society is still heavily relying on chemical fuels. Therefore, the essential and realistic approaches to environmental and energy issues remain to be the exploration of clean and sustainable energy sources, in order to meet the ever-increasing energy demand. Thanks to its high energy density and environmental friendliness, hydrogen fuel comes into play as a muchanticipated new energy carrier, which is under intensive studies in the academic field. [4] Furthermore, we are already in the new era witnessing the transformation of hydrogen-powered technologies from science fictions to realities. UK is already in the process of replacing their traditional diesel-powered double decker buses with the hydrogen-powered version, which aims to phase out the former by 2018. [5] China announced its world's first hydrogen-powered tram, which was put into business service in the latter half of 2017. [6] Mercedes-Benz had even started its development of personal hydrogen-powered car, and Toyota had commercialized its hydrogen fuel-cell car branded "Mirai." [7,8] However, one critical issue remains to be the conflict between the hydrogen production efficiency and the demand for the mass distribution of hydrogen-powered technologies.Current industrial hydrogen production methods include coal gasification (followed by water-gas shift reaction), steam reforming, cryogenic distillation, and water splitting. [9] Coal gasification and steam reforming utilize the reaction between conventional fossil fuels and water to produce syngas (primarily CO and H 2 ) or CO 2 and H 2 mixture. However, both reactions require high temperatures (can be over 1000 °C) and pressures, which is an energy intensive process and has strict requirements on infrastructures. [10] The reaction products also need to be further separated to obtain relatively high-concentration of hydrogen. Cryogenic distillation takes the advantage of difference in gas boiling points, which can be applied to separate hydrogen from other gas components in the former two hydrogen production methods. However, cryogenic distillation is also an energy intensive process for low-temperature gas liquification. In comparison, hydrogen evolution reaction (HER) through water splitting is much-favored because of the following three prominent advantages: 1) Water splitting can be carried out at room temperature and ambient pressure, which is less restricted by infrastructure requirements. 2) Oxygen and hydrogen can be produced separately or selectively, which eliminate the need for gas separation. 3) Both the hydrogen source Highly efficient hydrogen evolution reactions (HERs) will determine the mass distributions of hydrogen-powered clean technologies in the future. Metal-organic frameworks (MOFs) are emerging as a class of crystalline porous materials. Along with their derivatives, MOFs have recently been under intense study for their applications in various hydrogen production techniques. MOF-based materials possess unique advantages, such as high specific surface area, crystalline porous str...

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Section: Mofs As Supportsmentioning

confidence: 99%

Metal–Organic Framework Based Catalysts for Hydrogen Evolution

Zhu

Zou

2018

Advanced Energy Materials

385

199

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“…Despite catalytically limiting conditions, namely; recombination of excited states pertaining to [Ru(bpy) 2 (bpy) À ] + and oxidised ascorbate, as well as impeded diffusion of the sensitiser; the activity of the MOF was still roughly three times better than that of the homogeneous adduct. 102 The [FeFe]@ZrPF MOF was assembled by room temperature diffusion of the mimic into the MOF over 48 hours, after which time the distinctive fluorescence emission of the porphyrin moieties was quenched. Accordingly, the authors theorise disproportionation of singly reduced active sites (X 1À ), which go on to form catalytically active doubly reduced species (X 2À ).…”

Section: Mof Supported Water Reductionmentioning

confidence: 99%

Metal organic frameworks for photo-catalytic water splitting

Meyer

Ranocchiari

Bokhoven

2015

Energy Environ. Sci.

292

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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“…However, the reaction stopped after a very short reaction time (< 2hours) due to catalyst deactivation. [47][48] Finally, it is interesting to note that while molecular cobaloximes are good catalysts as well, they also suffer, within comparable photochemical conditions, from low stability, with full inactivation after a few hours. [49][50] We also found that the cobaloxime precursor of PCoP was active using the ACN/TEOA system and Ru(bpy) 3 Cl 2 as the photosensitizer under the conditions used with PCoP (SI).As the amount of Co was comparable to that provided by the PCoP catalyst, the data show that the free cobaloxime was slightly less efficient.…”

Section: Acs Applied Materials and Interfacesmentioning

confidence: 99%

Porous–Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis

Haikal

Wang

Hassan

et al. 2016

ACS Appl. Mater. Interfaces

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Abstract.A number of permanently porous polymers containing Ru(bpy) n photosensitizer or a cobaloxime complex, as a protonreduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multi-topic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity towards hydrogen-evolution reaction (HER) with remarkable recyclability. We further demonstrated, in two cases, the ability to affect the excited state lifetime of the covalently-immobilized Ru(bpy) 3 complex attained through deliberate utilization of the organic linkers of variable dimensions. Overall, this approach facilitates construction of tunable porous solids, with hybrid composition and pronounced chemical and physical stability, based on the well-known Ru(bpy) n or the cobaloxime complexes.

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Incorporation of iron hydrogenase active sites into a highly stable metal–organic framework for photocatalytic hydrogen generation

Cited by 176 publications

References 40 publications

Metal–Organic Framework Based Catalysts for Hydrogen Evolution

Metal–Organic Framework Based Catalysts for Hydrogen Evolution

Metal organic frameworks for photo-catalytic water splitting

Porous–Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis

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