Harnessing renewable energy with CO 2 for the chemical value chain: challenges and opportunities for catalysis
2016; Royal Society; Volume: 374; Issue: 2061 Linguagem: Inglês
10.1098/rsta.2015.0315
ISSN1471-2962
AutoresJürgen Klankermayer, Walter Leitner,
Tópico(s)CO2 Reduction Techniques and Catalysts
ResumoYou have accessMoreSectionsView PDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareShare onFacebookTwitterLinked InRedditEmail Cite this article Klankermayer Jürgen and Leitner Walter 2016Harnessing renewable energy with CO2 for the chemical value chain: challenges and opportunities for catalysisPhil. Trans. R. Soc. A.3742015031520150315http://doi.org/10.1098/rsta.2015.0315SectionYou have accessReview articleHarnessing renewable energy with CO2 for the chemical value chain: challenges and opportunities for catalysis Jürgen Klankermayer Jürgen Klankermayer Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, Aachen 52074, Germany Google Scholar Find this author on PubMed Search for more papers by this author and Walter Leitner Walter Leitner Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, Aachen 52074, Germany Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany [email protected] Google Scholar Find this author on PubMed Search for more papers by this author Jürgen Klankermayer Jürgen Klankermayer Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, Aachen 52074, Germany Google Scholar Find this author on PubMed and Walter Leitner Walter Leitner Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, Aachen 52074, Germany Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany [email protected] Google Scholar Find this author on PubMed Published:28 February 2016https://doi.org/10.1098/rsta.2015.03151. Background and motivationToday's energy systems and material value chains rely on the fossil feedstocks oil, gas and coal as energy carriers and carbon resources. Their exploitation involves either direct incineration to generate power and heat, or stepwise and controlled functionalization to generate the products of the chemical value chain including polymers, fabrics, pharmaceuticals, cosmetics, dyes, etc. Both processes ultimately convert the reduced forms of carbon, which have stored energy from the Sun over millions of years, to CO2. It is becoming increasingly obvious that the rate of consumption of the finite resources and the concomitant carbon dioxide liberation in the range of 40 Gt of CO2 per year is putting the fossil age on a non-sustainable trajectory. Consequently, two questions can be asked: — Can CO2 be used as a carbon source for sustainable production of chemicals?— How can the transition to carbon neutral energy systems be managed?Figure 1 shows that these two challenges might be turned into an opportunity when linked through selective catalytic processes using CO2 as the central carbon source and H2 as the energy carrier. These two simple molecules seem to be related to each other like fire and ice. Hydrogen is a very energy-rich molecule, as every chemistry student has witnessed with the 'Knallgas reaction' in the undergraduate demonstration lecture. Once the bond in the H2 molecule is activated with a suitable catalyst, the two H-centres eagerly seek new partners and hydrogenation reactions are ubiquitous transformations in the refining and chemical industries. Carbon dioxide, known as 'dry ice' in the solid state, is the thermodynamic sink of carbon on Earth. It is also kinetically inert, i.e. quite reluctant to undergo chemical reactions with other partners to form carbon–carbon or carbon–hydrogen bonds. The present contribution will discuss recent examples that illustrate how the combination of these two seemingly opposite characteristics holds great potential to establish novel processes at the interface between the energy and chemical sector. Figure 1. Harnessing renewable energy into the chemical value chain by using CO2 as a carbon source. The figure shows the increasing energy content of CO2-derived molecules upon reduction. Each of the reduction levels provides an entry into broad molecular diversity if the reduction is coupled to bond breaking and bond formation processes, leading to incorporation of the C1 units into larger and more complex molecular structures as required for intermediates and final products of the chemical value chain. (Online version in colour.)Download figureOpen in new tabDownload PowerPointInspiration comes—as always—from Mother Nature. She uses the energy of the Sun to generate reduction equivalents in the form of electrons (e−) and protons (H+) for the reduction of CO2 to carbohydrates Cn(H2O)n (e.g. glucose=C6H12O6) as the basis of its material product chain. Mimicking this process by photo- or electro-catalytic reduction of CO2 as 'artificial photosynthesis' is an exciting and extremely promising long-term research area. In the meantime, there might also be an opportunity for a technological shortcut [1]. Reduction equivalents can be produced in the form of H2 by water electrolysis with established and scalable technologies using renewable primary energy sources such as wind, photovoltaics or water. Coupling the generated 'carbon-free' (better: low-carbon) hydrogen with CO2 via selective catalytic transformation opens up the possibility for energy storage systems, moving up and down the oxidation level of the C1 products [2,3]. At the same time, there are entries into the chemical value chain at each oxidation state of carbon, if additional bonds are formed in the catalytic process. Thus, the CO2/H2 couple can be used as a C1 synthon, allowing for sustainable processes across the chemical value chain [4]. Most significantly, this can open up novel synthetic pathways following the green chemistry principles even in conventional H2 sources [5]. Thus, the development of such a catalytic process does not require renewable energy sources as a necessary prerequisite to be implemented, but may in fact facilitate their introduction by providing additional economic outlets for the system-inherent overcapacities.2. Recent progress and illustrative examplesThe reduction sequence of CO2 by H2 addition and H2O elimination can follow two distinct mechanistic principles. Firstly, the reverse water gas shift reaction (rWGS) can convert carbon dioxide and hydrogen to carbon monoxide and water. As long as there is still H2 present, this generates in situ the mixture CO/H2 known as 'syngas', a versatile starting material for carbonylation and reductive carbonylation processes. Alternatively, the reduction occurs by stepwise transfer of hydrides and protons onto the CO2 unit, working its way through the formate, formaldehyde, methoxy and methyl stages. In either case, the formal reduction can lead to the C1 products shown in figure 1 or to structures of higher complexity if the intermediates can be engaged into additional bond-forming processes.Interestingly, there is currently no technical catalyst to guide this sequence to a direct hydrogenation of carbon dioxide to formaldehyde (CH2O) that corresponds to the oxidation stage of carbohydrates as produced from photosynthesis. There are, however, highly active and selective systems for the synthesis of products at the other three stages. Each level corresponds to an increase in energy content of the C1 molecules, and methane in particular is discussed as the molecular carrier of renewable energy in this context. The full reduction of CO2 with hydrogen can also be achieved through a modification of the Fischer–Tropsch technology to obtain liquid hydrocarbon mixtures. Whereas the methanization typically occurs via direct reduction (Sabatier reaction), the CO2-based Fischer–Tropsch routes to liquid hydrocarbons are typically installed as two-step processes with a separate syngas-generating rWGS unit. As part of the German 'Energiewende', a number of pilot- and demonstration-scale activities are operated to explore the potential of these so-called 'power-to-gas' and 'power-to-fuels' technologies to curb the inherent fluctuations in renewable energy production (http://www.fona.de/de/energiewende, accessed 1 November 2015). Paradoxically, the obvious attractiveness is at the same time the major challenge of these concepts: the products are fully compatible with the entry into the existing fossil-based infrastructure—and hence compete with the fossil resources in economic terms. As the fossil raw materials are sequentially upgraded throughout the chemical value chain, an entry at a higher valorization level is likely to provide a lower economic barrier for the concept of 'power-to-chemicals'.Methanol is frequently advocated as a potential key molecule at the interface of the energy and chemical value chain [6–8]. An example for a commercially operated methanol plant using carbon dioxide together with low-carbon hydrogen is the GRI plant in Iceland, which exploits the specific local supply of geothermal energy (http://www.carbonrecycling.is, accessed 1 November 2015). The typical heterogeneous Zn/Cu/Al2O3 catalysts used in today's syngas-based methanol production provide pathways for direct CO2 reduction, as analysed in great detail by a combination of experimental and computational methods [9]. Most recently, the first organometallic complex was described that allows the same multi-step transformation to occur at a homogeneously dissolved molecular unit (figure 2) [10]. A key feature of this catalyst was the combination of ruthenium as the central metal with the tridentate phosphine ligand triphos, which combines a very high thermal robustness with a precisely controlled coordination geometry. Although there are striking mechanistic similarities between the surface and the solution phase processes, they are operated in very different engineering solutions. Whereas tubular gas/solid reactors are the state of the art with the heterogeneous catalyst, a liquid/liquid biphasic system can be envisaged for the homogeneous case. This might open up new operating windows, in particular for smaller scale operations, that cannot capitalize on the economy of scale provided in today's syngas-based megamethanol plants. Figure 2. The first organometallic catalyst for the hydrogenation of CO2 to methanol [10]. (Online version in colour.)Download figureOpen in new tabDownload PowerPointWith the first organometallic catalyst available for the hydrogenation of CO2 to the methanol level, the potential of generating CH3 groups from CO2 and H2 was recognized for the synthesis of more complex molecules. As a first example, the methylation of amines has been demonstrated on the basis of the Ru-triphos system [11]. Since then, the reaction principle has been demonstrated into a synthetic strategy with a broad substrate scope including primary and secondary amines [11,12]. Most recently, even the selective formation of trimethylamine directly from ammonia, carbon dioxide and hydrogen has been demonstrated with this catalytic system [13]. Imines can also be used as substrates, either in isolated form or formed in situ from a primary amine and a carbonyl compound [14]. The latter transformation allows for the assembly of tertiary amines with three different substituents at nitrogen in a single, highly selective multi-component coupling. The synthesis of N-methyl groups utilizing CO2 and hydrogen under the formation of water as the only by-product is a much cleaner and less wasteful alternative than established methods employing stoichiometric and often toxicologically problematic methylating agents that also have a tendency for quarternization of the nitrogen centre.The most obvious functional group to be assembled from CO2 and H2 appears to be the carboxylic acid function R–C(O)OH. There are numerous organometallic catalytic systems for the synthesis of formic acid and its ester and amide derivatives [4]. Such catalytic processes have also been suggested for energy applications as hydrogen carriers or for formic acid fuel cells [15]. The formation of HC(O)OH from CO2 and H2 is thermodynamically uphill unless carried out in suitable reaction media, most of which rely on the joint action of a suitable solvent and a base to overcome the unfavourable entropic contribution [16]. Whereas this allows for systems that can be 'loaded and unloaded' in a fully recyclable manner, it results at the same time in a strongly reduced H2 storage capacity due to the necessary dilution. The alternative to isolate free formic acid from the reaction mixture is inherently a challenging and energy-consuming task as the reaction medium was designed to provide its stabilization in the first place. This 'thermodynamic dilemma' applies equally to concepts for hydrogen storage as well as for the production of formic acid as the chemical product.Significant progress has been made to address this challenge recently. BASF has developed a process that relies on a judicious choice of the amine to provide a phase separation of the HCOOH/amine product from the catalyst solution, followed by thermal cleavage of the amine adduct to liberate free HCOOH [17]. Other efforts focus on reaction media that do not require the presence of a base, thus reducing the number of components in the reaction/separation process. Whereas DMSO/amine solutions were introduced as favourable reaction media a long time ago [16], it was shown only recently that suitable catalysts allow for high formic acid concentrations also in DMSO alone [18]. The efficiency of a separation process for the DMSO/HCOOH/catalyst mixture has yet to be evaluated. Another option is the immobilization of the molecular catalyst in a continuous-flow reactor, where the immobilization matrix consists of a suitable combination of non-volatile solvent and base. Ionic liquids containing either covalently attached amine functionalities or coupled with polymeric bases have been shown to enable such processing concepts (figure 3). The formic acid formed in the reactive phase is stripped out from the reactor if CO2 is applied as the mobile phase under supercritical conditions [19]. This allows for a fully integrated one-step process requiring only a single operating unit. In all cases, however, the separation efficiency is still hampered by thermodynamics constraints of the overall cycle, and future research and development work is required to identify the most energy efficient overall reaction/separation sequence. Figure 3. Integrated process for the continuous-flow synthesis and isolation of formic acid (HCOOH) from H2 and CO2, using an ionic liquid-based immobilized catalytic system and supercritical carbon dioxide (scCO2) as the mobile phase [19]. (Online version in colour.)Download figureOpen in new tabDownload PowerPointThe synthesis of higher carboxylic acids through a formal 'hydrocarboxylation' reaction of olefins with CO2 and hydrogen was described also recently, providing high yields of saturated carboxylic acids from a variety of olefins (figure 4) [20]. For linear olefins, mixtures of regioisomers were obtained resembling the product composition of hydroformylation processes under similar conditions. Isotopic labelling experiments indicated that the reaction proceeds via two combined catalytic cycles: the rWGS and the hydroxy-carbonylation. The rhodium–phosphine catalytic system thus must fulfil a dual role: it adjusts the equilibrium between CO2/H2 and CO/H2O, and assembles the latter two components across the C=C double bond to yield the saturated carboxylic acid. Meanwhile, the same principle was applied to the synthesis of carboxylic acid esters from olefins, CO2 and alcohols, whereby the alcohol serves as the hydrogen source for the reduction of CO2 in this case [21]. Figure 4. Synthesis of carboxylic acids by formal 'hydrocarboxylation' of olefins [20].Download figureOpen in new tabDownload PowerPointThe most elegant way to generate carboxylic acids from CO2 would be the direct catalytic carboxylation of C−H bonds. The transformation formally replaces the H−H bond to be activated in the synthesis of formic acid with a C−H bond in an aromatic or aliphatic substrate. As pointed out many years ago [16], this results in an analogous combination of thermodynamic and kinetic challenges (figure 5). As for today, however, molecular transformations required to arrive, for example, at a catalytic Kolbe–Schmitt reaction or an acetic acid process based on methane and CO2 remain elusive. The first promising examples using substrates of sufficient C−H acidity [22,23] or comprising directing groups [24] to enable the C−H bond activation step have been reported. Computational studies indicate, however, that the critical step in potential catalytic cycles results from the cleavage of the carboxylate intermediate under regeneration of an active species that is reactive enough to facilitate again the C−H activation [25]. As this step is both kinetically as well as thermodynamically uphill, there is again an obvious need for energy input that might be provided by renewable sources in the form of either electricity or heat. Given the enormous progress that organometallic catalysis has made to combine CO2 and H2, it seems only a matter of time until the carboxylation challenge will also be met, opening yet another opportunity for the harvest of renewable energy into the chemical value chain. Figure 5. Still a 'dream reaction'. Synthesis of carboxylic acids via direct carboxylation of C−H bonds compared with the well-established hydrogenation of CO2 to formic acid [16]. Thermodynamic data are for formic acid and acetic acid under standard conditions. (Online version in colour.)Download figureOpen in new tabDownload PowerPoint3. Conclusion and outlookArguably, catalysis is still far away from mastering the combination of CO2 and renewable energy as elegantly and efficiently as Nature does. The synthetic transformations described in this perspective represent, however, only a small fraction of the numerous promising steps in this direction arising from intensive research efforts around the world [4]. At the same time, the use of CO2 and hydrogen in organic synthesis can contribute to more sustainable chemical production processes even without the input of renewable energy [5]. Exploring their potential does therefore not depend on changes of the energy system as a necessary prerequisite, but rather opens up possibilities to harness renewable energy into the chemical value chain as an additional driver and motivation for this inevitable transition. Catalysis is the key science and technology to address this grand challenge and turn it into an exciting opportunity.Authors' contributionsBoth authors contributed equally to the concept and writing of this article.Competing interestsWe declare we have no competing interests.FundingWe gratefully acknowledge financial support for the research in the area of catalytic CO2 conversion from the Cluster of Excellence 'Tailor-Made Fuels from Biomass' and from the Project House 'Power-to-Fuels' funded by the Excellence Initiative of the German Federal State Governments to promote science and research at German universities, as well as from the research network 'Sustainable Chemical Synthesis (SusChemSys)' that is co-financed by the European Regional Development Fund (ERDF) and the State of North Rhine-Westphalia, Germany, under the operational programme 'Regional Competitiveness and Employment' 2007–2013.AcknowledgementsWe thank the colleagues, postdocs and PhD students who made the work both fruitful and enjoyable through their skilful experiments and stimulating intellectual contributions over the years. 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Thenert K, Beydoun K, Wiesenthal J, Leitner W and Klankermayer J (2016) Ruthenium-Catalyzed Synthesis of Dialkoxymethane Ethers Utilizing Carbon Dioxide and Molecular Hydrogen, Angewandte Chemie, 10.1002/ange.201606427, 128:40, (12454-12457), Online publication date: 26-Sep-2016. This Issue28 February 2016Volume 374Issue 2061Discussion meeting issue 'Catalysis making the world a better place' organised and edited by Graham J. Hutchings, C. Richard A. Catlow, C. Hardacre and Matthew G. Davidson Article InformationDOI:https://doi.org/10.1098/rsta.2015.0315Published by:Royal SocietyPrint ISSN:1364-503XOnline ISSN:1471-2962History: Manuscript accepted19/11/2015Published online28/02/2016Published in print28/02/2016 License:© 2016 The Author(s)Published by the Royal Society. All rights reserved. Citations and impact Keywordscatalysisrenewable energy Subjectsgreen chemistry
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