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View Article Online Paper Faraday Discussions widely known 12 Principles of Green Chemistry, introduced in 1998 by Anastas and Warner, which has now become an almost standard means of assessing green processes.9 However, it has to be admitted that the full statement of the principles is quite lengthy. So, more recently, a condensed version of these principles was introduced, based on the acronym PRODUCTIVELY, to provide a list that could conveniently (and legibly) be shown on a single PowerPoint slide.10 Here we provide an equivalent condensed list for CO2 CHEMISTRY in the hope that it will help to highlight the most pertinent issues and to structure future discussions of CDU. The list is shown in Fig. 1 as it was presented in the Intro- ductory Lecture and below we expand these principles and explain how they might be applied. Catalysis is crucial CO2 is notoriously unreactive in organic synthesis and in reductive processes. It can be considered a thermodynamic minimum with only highly energy rich compounds being able to react with it. Such reactions do not necessarily require a catalyst. For example, once heated, magnesium metal reacts with CO2 in a highly exothermic reaction11 (2Mg + CO2 / 2MgO + C) but the reaction yields elemental carbon which is not necessarily a useful starting point for making chemicals, especially given the nancial and energy costs of obtaining metallic magnesium. Thus, nearly all reactions for making chemicals from CO2 really need to use catalysts.12,13 Heterogeneous catalysts are able to promote important transformations of carbon dioxide such as the famous Sabatier reaction CO2 + 4H2 / CH4 + 2H2O.14 Homogeneous catalysts are very selective for many synthetically useful C–C and C–X bond formation processes.15,16 Electro- and photochemical transformations of CO2 also require suitable catalyst materials or molecular catalysts due to the large over-potential for CO2 reduction to its radical anion.17 Nature's ingenious catalytic processes for construction of its entire material basis from CO2 can serve as motivation to develop man-made catalysts for industrial implementation. Origin of the CO2? CO2 can be sequestered from many industrial processes and other sources.18 The need for catalysis may well place quite severe restrictions on the purity of the CO2. Trace impurities could easily poison catalysts or oxidize expensive ligands. Fortunately, the large disparity between global CO2 production and the possible consumption by the chemical industry means that operators of chemical processes can afford to be quite choosy about the source of their CO2. For example, some processes may require relatively dry CO2 and could benet from fears of pipeline corrosion in CCS that are leading to relatively stringent proposals for acceptable levels of H2O currently for any captured CO2 to be transported by pipeline.19 At the same time, using atmospheric CO2 will always carry a large energy cost because of the need to move very large masses of air to obtain a sufficient ux of CO2 through one's chemical process. It may well be hard to beat photosynthesis by plants/trees/algae as a means of deriving carbon compounds from the atmosphere, even though such photosynthesis oen requires very large amounts of fresh water, a commodity that may well be in short supply in the This journal is © The Royal Society of Chemistry 2015 Faraday Discuss., 2015, 183, 9–17 | 11 Open Access Article. Published on 03 November 2015. Downloaded on 30/08/2016 10:44:04. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.PDF Image | The Twelve Principles of CO2 CHEMISTRY
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