Electrocatalytic Processes for the Valorization of CO2

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catalysts Article Electrocatalytic Processes for the Valorization of CO2: Synthesis of Cyanobenzoic Acid Using Eco-Friendly Strategies Silvia Mena , Iluminada Gallardo and Gonzalo Guirado * Departament de Química, Universitat Autònoma de Barcelona, Campus UAB, 08193 Bellaterra, Barcelona, Spain; silvia.mena@uab.cat (S.M.); iluminada.gallardo@uab.cat (I.G.) * Correspondence: gonzalo.guirado@uab.cat; Tel.: +34-93-581-4882 Received: 4 March 2019; Accepted: 15 April 2019; Published: 2 May 2019 􏰁􏰂􏰃 􏰅􏰆􏰇 􏰈􏰉􏰊􏰋􏰌􏰂􏰍 Abstract: Carbon dioxide (CO2) is a known greenhouse gas, and is the most important contributor to global warming. Therefore, one of the main challenges is to either eliminate or reuse it through the synthesis of value-added products, such as carboxylated derivatives. One of the most promising approaches for activating, capturing, and valorizing CO2 is the use of electrochemical techniques. In the current manuscript, we described an electrocarboxylation route for synthesizing 4-cyanobenzoic acid by valorizing CO2 through the synergistic use of electrochemical techniques (“green technology”) and ionic liquids (ILs) (“green solvents”)—two of the major entries in the general green chemistry tool kit. Moreover, the use of silver cathodes and ILs enabled the electrochemical potential applied to be reduced by more than 0.4 V. The “green” synthesis of those derivatives would provide a suitable environmentally friendly process for the design of plasticizers based on phthalate derivatives. Keywords: ionic liquids; carbon dioxide; electrochemistry; green chemistry; cyanobenzoic acid 1. Introduction Fossil fuels in the form of coal, oil, and natural gas account for 80% of the world’s energy use and have caused increases in the Greenhouse Gas (GHG) concentrations of the atmosphere. These have led to global warming, climate change, and ozone layer depletion, with destructive impacts on human society and the economy. In the last four decades, despite global attempts to mitigate emissions, the world saw more than 100% growth in annual CO2 emissions, which surpassed 32 billion tons in 2011. These global CO2 emissions will continue to increase and are projected to reach 36 billion tons in 2020, and double that by 2050 if appropriate climate change mitigation measures are not put in place [1–3]. In this sense, different research strategies are currently being developed for the activating, capturing, and valorizing of CO2. Hence, CO2 uses are generally classified into different categories, such as direct use and/or conversion to chemicals and energy [4–11]. Carboxylic acids and esters are important classes of chemicals that are widely found in pharmaceuticals, polymers, agrochemicals, natural products, and biological systems, and they have been widely applied as versatile building blocks in organic synthesis [12–14]. For instance, the utilization of CO2 as a C1 synthon for incorporation with lithium phenolate, or Grignard reagents for the synthesis of carboxylic acids have been well known for more than a century. On the other hand, metal-catalyzed direct insertion of CO2 into different compounds is another valuable method for the preparation of carboxylic acids with high selectivity. This approach is widely used to obtain carboxylic analogues from carbon–halide, carbon–boron, carbon–oxygen, aromatic and alkyl reagents, etc. [15–22]. Moreover, the development of new methods that take advantage of the abundant and inexpensive CO2 without catalysts (carbon monoxide, phenols, and others), for the transformation of aryl halides into their corresponding aryl carboxylic acid provides an attractive option for their assembly [23,24]. Catalysts 2019, 9, 413; doi:10.3390/catal9050413 www.mdpi.com/journal/catalysts

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