Photo-thermal catalysis has recently emerged as an alternative route to drive chemical reactions using light as an energy source. Through the synergistic combination of photo- and thermo-chemical ...contributions of sunlight, photo-thermal catalysis has the potential to enhance reaction rates and to change selectivity patterns, even under moderate operation conditions. This review provides the fundamentals of localized surface plasmon resonance (LSPR) that explain the photo-thermal effect in plasmonic structures, describes the different mechanistic pathways underlying photo-thermal catalysis, suggests methodologies to disentangle the reaction mechanisms and proposes material design strategies to improve photo-thermal performance. Ultimately, the goal is to pave the way for the wide implementation of this promising technology in the production of synthetic fuels and chemicals.
Photo-thermal catalysis has recently emerged as an alternative route to drive chemical reactions using light as an energy source.
Utilization of CO2 as feedstock to produce fine chemicals and renewable fuels is a highly promising field, which presents unique challenges in its implementation at scale. Heterogeneous catalysis ...with its simple operation and industrial compatibility can be an effective means of achieving this challenging task. This review summarizes the current developments in heterogeneous thermal catalysis for the production of carbon monoxide, alcohols, and hydrocarbons from CO2. A detailed discussion is provided regarding structure–activity correlations between the catalyst surface and intermediate species which can aid in the rational design of future generation catalysts. Effects of active metal components, catalyst supports, and promoters are discussed in each section, which will guide researchers to synthesize new catalysts with improved selectivity and stability. Additionally, a brief overview regarding process design considerations has been provided. Future research directions are proposed with special emphasis on the application scope of new catalytic materials and possible approaches to increase catalyst performance.
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Ketenes in the limelight: The influential role of ketenes has never been adequately acknowledged in zeolite chemistry and catalysis; unlike other first generation highly reactive intermediates, such ...as carbocations, carbanions, radicals, and carbenes. In fact, the role that ketenes play during catalysis—whether beneficial or detrimental—is a contentious subject that requires further consideration.
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In the realm of solids, metal–organic frameworks (MOFs) offer unique possibilities for the rational engineering of tailored physical properties. These derive from the modular, molecular make‐up of ...MOFs, which allows for the selection and modification of the organic and inorganic building units that construct them. The adaptable properties make MOFs interesting materials for photocatalysis, an area of increasing significance. But the molecular and porous nature of MOFs leaves the field, in some areas, juxtapositioned between semiconductor physics and homogeneous photocatalysis. While descriptors from both fields are applied in tandem, the gap between theory and experiment has widened in some areas, and arguably needs fixing. Here we review where MOFs have been shown to be similar to conventional semiconductors in photocatalysis, and where they have been shown to be more like infinite molecules in solution. We do this from the perspective of band theory, which in the context of photocatalysis, covers both the molecular and nonmolecular principles of relevance.
Metal–organic frameworks (MOFs) offer unique possibilities for the rational engineering of tailored physical properties. Nevertheless, the molecular and porous nature of MOFs leaves the field juxtapositioned between semiconductor physics and homogeneous photocatalysis. This Review reflects on how MOFs can resemble conventional semiconductors and how they are more like infinite molecules in solution.
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Metal-organic frameworks (MOFs) represent a fascinating class of solid crystalline materials which can be self-assembled in a straightforward manner by the coordination of metal ions or clusters with ...organic ligands. Owing to their intrinsic porous characteristics, unique chemical versatility and abundant functionalities, MOFs have received substantial attention for diverse industrial applications, including membrane separation. Exciting research activities ranging from fabrication strategies to separation applications of MOF-based membranes have appeared. Inspired by the marvelous achievements of MOF-based membranes in gas separations, liquid separations are also being explored for the purpose of constructing continuous MOFs membranes or MOF-based mixed matrix membranes. Although these are in an emerging stage of vigorous development, most efforts are directed towards improving the liquid separation efficiency with well-designed MOF-based membranes. Therefore, as an increasing trend in membrane separation, the field of MOF-based membranes for liquid separation is highlighted in this review. The criteria for judicious selection of MOFs in fabricating MOF-based membranes are given. Special attention is paid to rational design strategies for MOF-based membranes, along with the latest application progress in the area of liquid separations, such as pervaporation, water treatment, and organic solvent nanofiltration. Moreover, some attractive dual-function applications of MOF-based membranes in the removal of micropollutants, degradation, and antibacterial activity are also reviewed. Finally, we define the remaining challenges and future opportunities in this field. This Tutorial Review provides an overview and outlook for MOF-based membranes for liquid separations. Further development of MOF-based membranes for liquid separation must consider the demands of strict separation standards and environmental safety for industrial application.
This Tutorial Review highlights the achievements in the rational design and the latest applications of MOF-based membranes in liquid separation.
More than 95% (in volume) of all of today’s chemical products are manufactured through catalytic processes, making research into more efficient catalytic materials a thrilling and very dynamic ...research field. In this regard, metal–organic frameworks (MOFs) offer great opportunities for the rational design of new catalytic solids, as highlighted by the unprecedented number of publications appearing over the past decade. In this review, the recent advances in the application of MOFs in heterogeneous catalysis are discussed. MOFs with intrinsic thermocatalytic activity, as hosts for the incorporation of metal nanoparticles, as precursors for the manufacture of composite catalysts and those active in photo- and electrocatalytic processes are critically reviewed. The review is wrapped up with our personal view on future research directions.
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“Hard work today leads to success tomorrow” can be said for research on membranes of porous crystalline materials, which are ideal for size‐ and shape‐selective separations with low energetic effort. ...The realization of the first metal‐organic framework membranes may open up a plethora of applications, including functional coatings. The picture shows the separation of H2 and CO2 by a membrane on an alumina support.
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8.
Mixed‐Matrix Membranes Dechnik, Janina; Gascon, Jorge; Doonan, Christian J. ...
Angewandte Chemie,
August 1, 2017, Volume:
56, Issue:
32
Journal Article
Peer reviewed
Open access
Research into extended porous materials such as metal‐organic frameworks (MOFs) and porous organic frameworks (POFs), as well as the analogous metal‐organic polyhedra (MOPs) and porous organic cages ...(POCs), has blossomed over the last decade. Given their chemical and structural variability and notable porosity, MOFs have been proposed as adsorbents for industrial gas separations and also as promising filler components for high‐performance mixed‐matrix membranes (MMMs). Research in this area has focused on enhancing the chemical compatibility of the MOF and polymer phases by judiciously functionalizing the organic linkers of the MOF, modifying the MOF surface chemistry, and, more recently, exploring how particle size, morphology, and distribution enhance separation performance. Other filler materials, including POFs, MOPs, and POCs, are also being explored as additives for MMMs and have shown remarkable anti‐aging performance and excellent chemical compatibility with commercially available polymers. This Review briefly outlines the state‐of‐the‐art in MOF‐MMM fabrication, and the more recent use of POFs and molecular additives.
Challenging separations: The need for greater energy efficiency and the maximum use of limited resources has focused attention on improved separation technologies. For gas separations, mixed‐matrix membranes can provide enhanced separation performance and lead to more energy‐efficient, sustainable, and cost‐effective commercial applications.
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The field of metal-organic framework based mixed matrix membranes (M(4)s) is critically reviewed, with special emphasis on their application in CO2 capture during energy generation. After introducing ...the most relevant parameters affecting membrane performance, we define targets in terms of selectivity and productivity based on existing literature on process design for pre- and post-combustion CO2 capture. Subsequently, the state of the art in M(4)s is reviewed against these targets. Because final application of these membranes will only be possible if thin separation layers can be produced, the latest advances in the manufacture of M(4) hollow fibers are discussed. Finally, the recent efforts in understanding the separation performance of these complex composite materials and future research directions are outlined.
We report the synthesis of a highly active, selective, and stable catalyst for the hydrogenation of CO2 to short chain olefins in one single step by using a metal organic framework as catalyst ...precursor. By studying the promotion of the resulting Fe(41 wt %)-carbon composites with different elements (Cu, Mo, Li, Na, K, Mg, Ca, Zn, Ni, Co, Mn, Fe, Pt, and Rh), we have found that only K is able to enhance olefin selectivity. Further catalyst optimization in terms of promoter loading results in catalysts displaying unprecedented C2–C4 olefin space time yields of 33.6 mmol·gcat–1·h–1 at X CO2 = 40%, 320 °C, 30 bar, H2/CO2 = 3, and 24 000 mL·g–1·h–1. Extensive characterization demonstrates that K promotion affects catalytic performance by (i) promoting a good balance between the different Fe active phases playing a role in CO2 hydrogenation, namely, iron oxide and iron carbides and by (ii) increasing CO2 and CO uptake while decreasing H2 affinity, interactions responsible for boosting olefin selectivity.
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