Recent Advances in Transition Metal-Catalysed Homogeneous Hydrogenation of Carbon Dioxide in Aqueous Media (original) (raw)
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Catalytic valorization of CO2 by hydrogenation: current status and future trends
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Terrestrial environmental and biological systems are being threatened by the tremendous amount of human carbon dioxide emissions. Therefore, is crucial to develop a sustainable energy system based on CO2 as chemical feedstock. In this review an introduction to the CO2 activation and transformation has been made, together with a more comprehensive study of the catalytical reduction of CO2 to methane, methanol and formic acid, which are currently contemplated as chemical feedstocks and/or promising energy carriers and alternative fuels.
Inorganics
The increase in anthropogenic CO2 concentrations and associated environmental issues have demanded the development of technologies for CO2 utilization. Among various potential solutions to decrease CO2 emissions and achieve carbon neutrality, the recycling of post-combustion CO2 into value-added chemicals and fuels is considered one of the most economically attractive processes. In this regard, due to its large global demand and versatile applications in the chemical and energy sectors, methanol serves as the most appealing target for the chemical utilization of CO2. However, direct hydrogenation of CO2 to MeOH has proved challenging due to selectivity issues and high energy input, mainly dependent on CO2-emitting fossil energy sources. To address these challenges, an alternative indirect CO2-to-MeOH methodology has been proposed, which involves the hydrogenation of CO2 via the intermediate formation of well-known CO2 derivatives, such as formates, carbonates, formamides, carbamates...
Promising Catalytic Systems for CO2 Hydrogenation into CH4: A Review of Recent Studies
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The increasing utilization of renewable sources for electricity production turns CO2 methanation into a key process in the future energy context, as this reaction allows storing the temporary renewable electricity surplus in the natural gas network (Power-to-Gas). This kind of chemical reaction requires the use of a catalyst and thus it has gained the attention of many researchers thriving to achieve active, selective and stable materials in a remarkable number of studies. The existing papers published in literature in the past few years about CO2 methanation tackled the catalysts composition and their related performances and mechanisms, which served as a basis for researchers to further extend their in-depth investigations in the reported systems. In summary, the focus was mainly in the enhancement of the synthesized materials that involved the active metal phase (i.e., boosting its dispersion), the different types of solid supports, and the frequent addition of a second metal oxi...
Heterogeneous Hydrogenation of CO2
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This chapter mainly focusses on the heterogeneous hydrogenation of carbon dioxide especially for the production of chemicals like higher alcohols and dimethyl carbonate. The discussion deals with the various catalysts studied and the optimization of conditions for the production of chemicals and the type of reactors employed.
Thermochemical CO 2 Hydrogenation to Single Carbon Products: Scientific and Technological Challenges
Catalytic conversion of CO 2 to chemicals and fuels is a "two birds, one stone" approach toward solving the climate change problem and energy demand−supply deficit in the modern world. Recent advances in mechanistic insights and design of suitable catalysts for direct thermocatalytic hydrogenation of CO 2 to C1 products are thoroughly discussed in this Review. The role of catalyst composition and process conditions in determining the selective pathways to various products like carbon monoxide, methanol, methane, and dimethyl ether has been overviewed in light of thermodynamic and kinetic considerations. After extensive elaboration of the main motivation of the reaction pathways, catalytic roles, and reaction thermodynamics, we summarize the most important macroscopic aspects of CO 2 hydrogenation technology development, which include reactor innovations, industrial status of the technology, life cycle assessment and technoeconomic analysis. Finally, a critical perspective on the future challenges and opportunities in both the core fronts and overall technology development is provided.
Carbon monoxide hydrogenation, preparation and characterization of model compounds
Journal of Molecular Catalysis, 1981
Polynuclear rhodium carbonyl complexes are present during the rhodium catalyzed conversion of carbon monoxide and hydrogen to alcohols. High pressure f.t.-i.r. analyses of reaction solutions containing [Rh17(CO)32-(S)2]3− suggest a catalyst manifold composed, almost exclusively, of that cluster. A related complex, [Rh17(CO)32−n(S)2(CHO)n](3 + n)−, has been prepared.The reactions of LiBH(C2H5)3 and LiBD(C2H5)3 with Os3(CO)12, Ru3-(CO)12, Ir4(CO)12, and Rh4(CO)12 have been studied by i.r., 1H and 2H n.m.r. and 13C n.m.r. With the exception of the rhodium containing system, results suggest the formation of formaldehyde and methanol in these reactions, as well as the existence of previously unreported polynuclear transition metal formyl complexes.Formyl complexes have been implicated as key intermediates in the manganese or cobalt catalyzed conversion of carbon monoxide and hydrogen to methanol. Mass spectral studies suggest that the reaction of acetic [13C] formic anhydride with sodium pentacarbonylmanganate, to give 13CO substituted pentacarbonylmanganese hydride, proceeds via formation of a short-lived neutral formyl complex, (CO)5Mn−13CHO.
Chemical reviews, 2017
The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions.