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View Article Online Faraday Discussions Paper Therefore, the introduction of innovative process technology, particularly continuous processing could have a signicant impact on the economics of the process. The synthesis of formic acid from CO2 and H2 provides an illustrative example, where the thermodynamics of the reaction require additional stabili- zation of the product in the reaction stage that needs to be overcome during the downstream product separation.32,33 Sustainability is essential Long term sustainability is a major reason, if not the major reason, for developing CO2-based chemistry. Therefore, it has to be a criterion for judging the viability of any proposed process. However elegant the catalysis, one must always look at the whole life cycle; the energy and/or chemical resources needed to make the catalyst may well reveal that an otherwise attractive process is totally unsustainable. Furthermore, it is important to stress that sustainability involves more than demonstrating that a particular catalyst is based on abundant and easily obtained elements. Although the sustainability of a process can only be reasonably estab- lished by Life Cycle34 or similar assessments (DOI: 10.1039/c5fd00038f), which are quite lengthy procedures, it may oen be easier and quicker to recognize processes that are obviously unsustainable. Thermodynamics cannot be beaten As in other areas of chemistry, the thermodynamics of CO2-based processes depend on where one draws the system boundary. For example, the hydrogena- tion of CO2 mentioned above, CO2 + 4H2 / CH4 + 2H2O, is exothermic, provided that one does not consider the energy involved in generating the hydrogen. Thermodynamics assume that systems are in equilibrium. Therefore, although thermodynamics cannot be beaten, it may be possible to side-step thermody- namic barriers by deliberately avoiding equilibrium situations, for example in plasma processing (DOI: 10.1039/c5fd00053j and DOI: 10.1039/c5fd00045a). Furthermore, even an endothermic process using CO2 can be advantageous, if the alternative routes consume even more energy to arrive at the same product or function. This emphasises again that one must consider the whole system with clearly dened boundary conditions in making an evaluation, and most evalua- tions are only valid in comparison, rather than as absolute values. Renewable (& reasonable) energy input Since the aim of CO2 Chemistry is to avoid use of fossil carbon in the manufacture of chemicals, it is clearly not sensible to incorporate less CO2 into the chemicals than one creates by burning fossil carbon to generate the energy needed to make those chemicals. Otherwise, one might as well start with the fossil carbon as the feedstock. Therefore, renewable energy might seem to be the panacea for CO2- based chemistry. If renewable energy sources are coupled with CO2 as the carbon source, this could decouple the carbon emission from the energy sector and the feedstock.22,23 Of course, this does not eliminate the challenge of devising energy efficient processes. Also renewable energy will not be “for free”, either economi- cally or environmentally. Furthermore, if renewable energy does become available 14 | Faraday Discuss., 2015, 183, 9–17 This journal is © The Royal Society of Chemistry 2015 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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