Abstract
The electrification of organic syntheses is a vividly growing research field and has attracted tremendous attention by the chemical industry. This review highlights aspects of electrosynthesis that are rarely addressed in other articles on the topic: the energy consumption and energy efficiency of technically relevant electro-organic syntheses.
Four examples on different scales are outlined.
Electro-organic synthesis has experienced a renaissance within the past years. This review addresses the energy efficiency or energy demand of electrochemically driven transformations as it is a key parameter taken into account by, for example, decision makers in industry. The influential factors are illustrated that determine the energy efficiency and discussed what it takes for an electrochemical process to be classified as “energy efficient.” Typical advantages of electrosynthetic approaches are summarized and characteristic aspects regarding the efficiency of electro-organic processes, such as electric energy consumption, are defined. Technically well-implemented examples are described to illustrate the possible benefits of electrochemical approaches. Further, promising research examples are highlighted and show that the conversion of fine chemicals is rather attractive than the electrochemical generation of synthetic fuels.
Similar content being viewed by others
References
Waldvogel S.R. and Janza B.: Renaissance of electrosynthetic methods for the construction of complex molecules. Angew. Chem. Int. Ed. 53, 7122–7123 (2014).
Wiebe A., Gieshoff T., Möhle S., Rodrigo E., Zirbes M., and Waldvogel S.R.: Electrifying organic synthesis. Angew. Chem. Int. Ed. 57, 5594–5619 (2018).
Anastas P.T. and Kirchhoff M.M.: Origins, current status, and future challenges of green chemistry. Acc. Chem. Res. 35, 686–694 (2002).
Frontana-Uribe B.A., Little R.D., Ibanez J.G., Palma A., and Vasquez-Medrano R.: Organic electrosynthesis: A promising green methodology in organic chemistry. Green Chem. 12, 2099–2119 (2010).
Pollok D. and Waldvogel S.R.: Electro-organic synthesis: A 21st Century Technique. Chem. Sci. (2020). In progress. doi:10.1039/D0SC01848A.
Moeller K.D.: Using physical organic chemistry to shape the course of electrochemical reactions. Chem. Rev. 118, 4817–4833 (2018).
Waldvogel S.R., Lips S., Selt M., Riehl B., and Kampf C.J.: Electrochemical arylation reaction. Chem. Rev. 118, 6706–6765 (2018).
Yan M., Kawamata Y., and Baran P.S.: Synthetic organic electrochemical methods since 2000: On the verge of a renaissance. Chem. Rev. 117, 13230–13319 (2017).
Puettner H.: Organic Electrochemistry, 4th ed., Chapter 31, Lund H. and Hammerich O.: (Crc Press Inc, Boca Raton, 2000), pp. 1259–1307.
Hamann C.H., Hamnett A., and Vielstich W.: Electrochemistry (Wiley-VCH, Weinheim, 2007), pp. 159–164.
Bard A.J., Stratmann M., Schaefer H.J., and Jörissen J.: Practical aspects of preparative scale electrolysis. Encyclopedia of Electrochemistry 8, 35 (2004).
Chen C., Khosrowabadi Kotyk J.F., and Sheehan S.W.: Progress toward commercial application of electrochemical carbon dioxide reduction. Chem 4, 2571–2586 (2018).
De Luna P., Hahn C., Higgins D., Jaffer S.A., Jaramillo T.F., and Sargent E.H.: What would it take for renewably powered electrosynthesis to displace petrochemical processes? Science 364, 1–9 (2019).
Nitopi S.A., Bertheussen E., Scott S.B., Liu X., Engstfeld A.K., Horch S., Seger B., Stephens I.E.L., Chan K., Hahn C., Nørskov J.K., Jaramilo T.F., and Chorkendorff I.: Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 119, 7610–7672 (2019).
Yang N., Waldvogel S.R., and Jiang X.: Electrochemistry of carbon dioxide on carbon electrodes. ACS Appl. Mater. Interfaces 8, 28357–28371 (2016).
Higgins D., Hahn C., Xiang C., Jaramillo T.F., and Weber A.Z.: Gas-diffusion electrodes for carbon dioxide reduction: A new paradigm. ACS Energy Lett. 4, 317–324 (2019).
Rademaekers K., Smith M., Yearwood J., Saheb Y., Moerenhout J., Pollier K., Debrosses N., Badouard T., Peffen A., Pollitt H., Heald S., and Altman M.: Study on energy prices, costs and subsidies and their impact on industry and households. Trinomics 74 (2018).
Li X., Anderson P., Jhong H.M., Paster M., Stubbins J.F., and Kenis P.J.A.: Greenhouse gas emissions, energy efficiency, and cost of synthetic fuel production using electrochemical CO2 conversion and the Fischer-Tropsch process. Energy Fuels 30, 5980–5989 (2016).
Pletcher D.: The cathodic reduction of carbon dioxide–What can it realistically achieve? A mini review. Electrochem. Commun. 61, 97–101 (2015).
Küngas R.: Review–Electrochemical CO2 reduction for CO production: Comparison of low- and high-temperature electrolysis technologies. J. Electrochem. Soc. 167, 044508 (2020).
Al-Rowaili F.N., Jamal A., Ba Shammakh M.S., and Rana A.A.: Review on recent advances for electrochemical reduction of carbon dioxide to methanol using metal-organic framework (MOF) and non-MOF catalysts: Challenges and future prospects. ACS Sustain. Chem. Eng. 6, 15895–15914 (2018).
Dexin Yang Y., Qinggong Z., Chunjun C., Huizhen L., Zhimin L., Zhijuan Z., Xiaoyu Z., Shoujie L., and Buxing H.: Selective electroreduction of carbon dioxide to methanol on copper selenide nanocatalysts. Nat. Commun. 10, 1–9 (2019).
Tackett B.M., Gomez E., and Chen J.G.: Net reduction of CO2 via its thermocatalytic and electrocatalytic transformation reactions in standard and hybrid processes. Nat. Catal. 2, 381–386 (2019).
Möhle S., Zirbes M., Rodrigo E., Gieshoff T., Wiebe A., and Waldvogel S.R.: Modern electrochemical aspects for the synthesis of value-added organic products. Angew. Chem. Int. Ed. 57, 6018–6041 (2018).
Wendt H., Vogt H., Kreysa G., Kolb D.M., Engelmann G.E., Ziegler J.C., Goldacker H., Jüttner K., Gallla U., Schmieder H., and Steckhan E.: Ullmann's Encyclopedia of Industrial Chemistry (Wiley, Weinheim, 2000); p. 73–85.
Vernon D.: Mechanisms of the electrohydrodimerization of activated olefins. The mechanism in proton donor poor solvents, a revelation. Acta Chem. Scand. 35, 51–52 (1981).
Vyazankin I.L. and Knunyants N.S.: Hydrodimerization of acrylonitrile. Proc. Natl. Acad. Sci. USA 6, 253–256 (1958).
Vaze A.S., Sawant S.B., and Pangarkar V.G.: Electrochemical oxidation of p-t-butyltoluene to p-t-butylbenzaldehyde. J. Appl. Chem. 28, 623–626 (1998).
Hannebaum H., Voss H., and Weiper-Idelmann A.: patent EP 0638665 B1, 1996.
Wang L., Kong Y., Jiang J., Wei D., Li P., Yang S., and Ting Y.: Optimal wastewater treatment using a packed-bed electrode reactor (PBER): From laboratory experiments to industrial-scale approaches. Chem. Eng. J. 334, 707–713 (2018).
Wiebe A., Schollmeyer D., Dyballa K.M., Franke R., and Waldvogel S.R.: Selective synthesis of partially protected nonsymmetric biphenols by reagent- and metal-free anodic cross-coupling reaction. Angew. Chem. Int. Ed. 55, 11801–11805 (2016).
Schäfer H.J.: Recent Contributions of Kolbe Electrolysis to Organic Synthesis (Springer, 2005), Berlin, Heidelberg; pp. 91–151. ISBN 978-3-540-48139-3.
Kirste A., Schnakenburg G., Stecker F., Fischer A., and Waldvogel S.R.: Anodic phenol: Arene cross-coupling reaction on boron-doped. Angew. Chem. Int. Ed. 49, 971–975 (2010).
Alexakis A. and Polet D.: Biphenol-based phosphoramidite ligands for the enantioselective copper-catalyzed conjugate addition of diethylzinc. J. Org. Chem. 69, 5660–5667 (2004).
Brunel J.M. and Ce P.: BINOL: A versatile chiral reagent. Chem. Rev. 105, 857–898 (2005).
Monti C., Gennari C., and Piarulli U.: Enantioselective conjugate addition of phenylboronic acid to enones catalysed by a chiral tropos/atropos rhodium complex at the coalescence temperature. Chem. Commun. 42, 5281–5283 (2005).
Franke R., Selent D., and Bo A.: Applied hydroformylation. Chem. Rev. 112, 5675–5732 (2012).
Mormul J., Mulzer M., Rosendahl T., Rominger F., Limbach M., and Hofmann P.: Synthesis of adipic aldehyde by n-selective hydroformylation of 4-pentenal. Organometallics 34, 4102–4108 (2015).
Yadav J.S., Reddy B.V.S., Uma Gayathri K., and Prasad A.R.: [Bmim]PF6/RuCl3⋅xH2O: A novel and recyclable catalytic system for the oxidative coupling of β-naphthols. New J. Chem. 27, 1684–1686 (2003).
Hwang D., Chen C., and Uang B.: Aerobic catalytic oxidative coupling of 2-naphthols and phenols by VO (acac)2. Chem. Commun. 13, 1207–1208 (1999).
Sharma V.B., Jain S.L., and Sain B.: Methyltrioxorhenium-catalyzed aerobic oxidative coupling of 2-naphthols to binaphthols. Tetrahedron Lett. 44, 2655–2656 (2003).
Malkowsky I.M., Fröhlich R., Griesbach U., Pütter H., and Waldvogel S.R.: Facile and reliable synthesis of tetraphenoxyborates and their properties. Eur. J. Inorg. Chem. 8, 1690–1697 (2006).
Malkowsky I.M., Rommel C.E., Wedeking K., Fröhlich R., Bergander K., Nieger M., Quaiser C., Griesbach U., Pütter H., and Waldvogel S.R.: Facile and highly diastereoselective formation of a novel pentacyclic scaffold by direct anodic oxidation of 2,4-dimethylphenol. Eur. J. Org. Chem. 2006, 241–245 (2006).
Barjau J., Königs P., Kataeva O., and Waldvogel S.R.: Reinvestigation of highly diastereoselective pentacyclic spirolactone formation by direct anodic oxidation of 2,4-dimethylphenol. Synlett 15, 2309–2312 (2008).
Barjau J., Schnakenburg G., and Waldvogel S.R.: Diversity-oriented synthesis of polycyclic scaffolds by modification of an anodic product derived from 2,4-dimethylphenol. Angew. Chem. Int. Ed. 50, 1415–1419 (2011).
Rommel C., Malkowsky I., Waldvogel S. R., Pütter H., and Griesbach U.: patent WO 2005/075709 A2, 2005.
Malkowsky I.M., Rommel C.E., Fröhlich R., Griesbach U., Püttner H., and Waldvogel S.R.: Novel template-directed anodic phenol-coupling reaction. Chemistry 12, 7482–7488 (2006).
Rommel C. E., Malkowsky I., Waldvogel S., Puetter H., and Griesbach U.: Anodic dimerization of substituted benzenes for the production of biarylalcohols, PCT Int. Appl. WO 2005075709 A2 20050818, 2005.
Malkowsky I.M., Griesbach U., Pütter H., and Waldvogel S.R.: Unexpected highly chemoselective anodic ortho-coupling reaction of 2,4-dimethylphenol on boron-doped diamond electrodes. Eur. J. Org. Chem. 20, 4569–4572 (2006).
Kirste A., Nieger M., Malkowsky I.M., Stecker F., Fischer A., and Waldvogel S.R.: Ortho-selective phenol-coupling reaction by anodic treatment on boron-doped diamond electrode using fluorinated alcohols. Chem. Eur. J. 15, 2273–2277 (2009).
Ayata S., Stefanova A., Ernst S., and Baltruschat H.: The electro-oxidation of water and alcohols at BDD in hexafluoroisopropanol. J. Electroanal. Chem. 701, 1–6 (2013).
Lips S., Wiebe A., Elsler B., Schollmeyer D., Dyballa K.M., Franke R., and Waldvogel S.R.: Synthesis of meta-terphenyl-2,2′′-diols by anodic C−C cross-coupling reactions. Angew. Chem. Int. Ed. 55, 10872–10876 (2016).
Cheng J. and Deming T.J.: Synthesis of polypeptides by ring-opening polymerization of α-amino acid N-carboxyanhydrides. Pept. Mater. 310, 1–26 (2011).
Lips S. and Waldvogel S.R.: Use of boron-doped diamond electrodes in electro-organic synthesis. ChemElectroChem 6, 1649–1660 (2019).
Selt M., Mentizi S., Schollmeyer D., Franke R., and Waldvogel S.R.: Selective and scalable dehydrogenative electrochemical synthesis of 3,3’,5,5’-tetramethyl-2,2’-biphenol. Synlett 30, 2062–2067 (2019).
Selt M., Franke R., and Waldvogel S.R.: Supporting-electrolyte-free and scalable flow process for the electrochemical synthesis of 3,3′,5,5′-tetramethyl-2,2′-biphenol. Org. Process Res. Dev. (2020). In progress. doi:10.1021/acs.oprd.0c00170.
Kirste A., Elsler B., Schnakenburg G., and Waldvogel S.R.: Efficient anodic and direct phenol-arene C,C cross-coupling: The benign role of water or methanol. J. Am. Chem. Soc. 134, 3571–3576 (2012).
Röckl J.L., Schollmeyer D., Franke R., and Waldvogel S.R.: Dehydrogenative anodic C−C coupling of phenols bearing electron-withdrawing groups. Angew. Chem. Int. Ed. 59, 315–319 (2020).
Kuilin L., Yanchen F., Ying Z., Yi Y., Jinrong W., Ying Z., and Qianfan Z.: Elastic Ag-anchored N-doped graphene/carbon foam for the selective electrochemical reduction of carbon dioxide to ethanol. J. Mater. Chem. A 6, 5025–5031 (2018).
Hoang T.T.H., Verma S., Ma S., Fister T.T., Timoshenko J., Frenkel A.I., Kenis P.J., and Gewirth A.A.: Nanoporous copper-silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO2 to ethylene and ethanol. J. Am. Chem. Soc. 140, 5791–5797 (2018).
Li F., Thevenon A., Rosas-Hernández A., Wang Z., Li Y., Gabardo C.M., Ozden A., Dinh C.T., Li J., Wang Y., Edwards J.P., Xu Y., McCallum C., Tao L., Liang Z.-Q., Luo M., Wang X., Li H., O'Brien C.P., Tan C.-S., Nam D.-H., Quintero-Bermudez R., Zhuang T.-T., Li Y.C., Han Z., Britt R.D., Sinton D., Agapie T., Peters J.C., and Sargent E.H.: Molecular tuning of CO2-to-ethylene conversion. Nature 577, 509–513 (2020).
García de Arquer F.P., Dinh C.-T.-, Ozden A., Wicks J., McCallum C., Kirmani A.R., Nam D.-H., Gabardo C., Seifitokaldani A., Wang X., Li Y.C., Li F., Edwards J., Richter L.J., Thorpe S.J., Sinton D., and Sargent E.H.: CO2 electrolysis to multicarbon products at activities greater than 1 A cm−2. Science 367, 661–666 (2020).
Acknowledgments
We are grateful for graphical support by Martin Klein. Support by the State Rhineland-Palatinate in frame of SusInnoScience is highly acknowledged.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Seidler, J., Strugatchi, J., Gärtner, T. et al. Does electrifying organic synthesis pay off? The energy efficiency of electro-organic conversions. MRS Energy & Sustainability 7, 42 (2020). https://doi.org/10.1557/mre.2020.42
Received:
Accepted:
Published:
DOI: https://doi.org/10.1557/mre.2020.42