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doi: 10.1039/d0dt01741hpmid: 32756705
Rational design and synthesis of efficient metal–organic frameworks (MOFs) as electrode modifiers for energy-related electrocatalytic applications are crucial for the development of clean-energy technologies. The present review focuses on recent work on robust earth-abundant heterogeneous catalysts based on pristine MOFs for the hydrogen evolution reaction (HER) and overall water splitting. These catalysts have been extensively studied as alternatives for noble metal-based ones, demonstrating “hydrogen economy” development prospects. In addition, novel strategies to enhance the conductivity, chemical stability and efficiency of MOF-based electrocatalysts are discussed. The best electrocatalysts even surpass the achievements of the platinum group of metals and MOF-derived catalysts in catalytic performance. The electrolytic cells with MOF-modified electrodes demonstrated excellent catalytic activity and can deliver a high current density at a voltage lower than that using the precious metal-based Pt/C cathodes and IrO2 anodes. In this review article, current approaches to design such MOF and MOF-modified electrode materials are summarized and analyzed.
Oswal, Preeti; Arora, Aayushi; Singh, Siddhant; Nautiyal, Divyanshu; Kumar, Sushil; Rao, Gyandshwar Kumar; Kumar, Arun
doi: 10.1039/d0dt01201gpmid: 32804180
Organochalcogen compounds have been used as the building blocks for the development of a variety of catalysts that have been studied comprehensively during the last two decades for several chemical transformations. Transfer hydrogenation (reduction of carbonyl compounds to alcohols) and oxidation of alcohols (conversion of alcohols to their respective ketones and aldehydes) are also among such chemical transformations. Some compilations are available in the literature on the development of catalysts, based on organochalcogen ligands, and their applications in Heck reaction, Suzuki reaction, and other related aspects. Some review articles have also been published on different aspects of oxidation of alcohols and transfer hydrogenation. However, no such article is available in the literature on the syntheses and use of organochalcogen ligated catalysts for these two reactions. In this perspective, a survey of developments pertaining to the synthetic aspects of such organochalcogen (S/Se/Te) based catalysts for the two reactions has been made. In addition to covering the syntheses of chalcogen ligands, their metal complexes and nanoparticles (NPs), emphasis has also been placed on the efficient conversion of different substrates during catalytic reactions, diversity in catalytic potential and mechanistic aspects of catalysis. It also includes the analysis of comparison (in terms of efficiency) between this unique class of catalysts and efficient catalysts without a chalcogen donor. The future scope of this area has also been highlighted.
Chen, Alexander N.; Skrabalak, Sara E.
doi: 10.1039/d0dt01168apmid: 32426778
As a nanocrystal's structural characteristics relate strongly to its properties, designing increasingly precise syntheses is important for making nanocrystals that are most tailored for a particular application. Importing concepts traditionally associated with the chemistry of small molecules has historically expanded the array of tools available to exert fine control over a nanocrystal's shape and architecture, and consequently its function. Here, we focus on recent work on using concepts from molecular chemistry such as regioselectivity and chemoselectivity in seeded or template-engaged syntheses, and generally draw attention to the idea of having anisotropic, spatially controlled reactivity on a nanocrystal's surface by design.
Xiong, Jianbo; Fan, Yaling; Luo, Feng
doi: 10.1039/d0dt02088epmid: 32856028
Nuclear power is becoming one of the major clean energies for its high efficiency and low load on the environment. Uranium is a key strategic resource for nuclear power. Uranium reclamation from aqueous systems is of great significance, not only in the usage of nuclear power but also for the remediation of nuclear leakage pollution. Recently, metal–organic frameworks (MOFs) with high porosity, regular pore structure and modifiable functional groups, have been considered as one of the most effective uranium adsorption materials. Specifically, the post-grafted functional groups possess strong affinity to uranium. This frontier summarizes the recent progresses on grafting functional groups in MOFs for U(vi) sorption from aqueous solutions. The adsorption performance, interaction mechanisms and the grafted functional groups are assessed in this study. Finally, personal perspectives on challenges and opportunities are discussed with the hope of supporting and providing some assistance to the designation of MOF-based U(vi) sorption materials.
Ivanchikova, Irina D.; Evtushok, Vasilii Yu.; Zalomaeva, Olga V.; Kolokolov, Danil I.; Stepanov, Alexander G.; Kholdeeva, Oxana A.
doi: 10.1039/d0dt02658apmid: 32959843
The zeolite imidazolate framework ZIF-8 exhibits superior catalytic performance in the epoxidation of the electron-deficient CC bond in menadione using aqueous hydrogen peroxide as the oxidant. The catalysis has a truly heterogeneous nature and the framework structure remains intact. This is the first example of oxidation catalysis with ZIF-8.
Celil Yüzer, A.; Genc, Eminegül; Harputlu, Ersan; Yanalak, Gizem; Aslan, Emre; Ocakoglu, Kasim; Hatay Patir, Imren; Ince, Mine
doi: 10.1039/d0dt02565hpmid: 32902548
A series of SubPcs comprising a carboxylic acid anchoring group at the peripheral (SubPcs 1, 2) or axial position (SubPc 3) were synthesized and used as sensitizers for photocatalytic H2 production, for the first time. SubPc 3/TiO2 shows the best photocatalytic activity with a hydrogen evolution rate of 1396 μmol h−1, which is much higher than that of SubPcs 1 and 2 (771 and 658 μmol g−1, respectively). This work clearly shows that considering their optical and redox properties, SubPcs are promising candidates for light-driven water splitting systems.
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