Sustainable conversion of carbon dioxide to formic acid with Rh-decorated phosphorous-doped fullerenes: a theoretical st
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ORIGINAL RESEARCH
Sustainable conversion of carbon dioxide to formic acid with Rh-decorated phosphorous-doped fullerenes: a theoretical study Maryam Anafcheh 1
&
Mansour Zahedi 2
Received: 19 March 2020 / Accepted: 18 August 2020 # Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract We performed density functional calculations to study conversion of carbon dioxide to formic acid through designed catalyst of Rh-decorated phosphorous-doped fullerenes. Two paths of reaction are considered for this conversion. In the first pathway, CO2 is transferred to formate intermediate using the catalyst, and then, through a sequence of oxidative addition and reductive elimination reactions, formic acid is released; density functional theory results showed that in this path the oxidative addition is an easy and quite exothermic process. It is also shown that the rate-determining step in the hydrogenation of CO2 catalyzed by Rh-decorated phosphorous-doped fullerene complexes is the release of formic acid from formate intermediate. In the other pathway after the formation of rhodium formate intermediate and then addition of H2, the formic acid complex is released directly through metathesis process; our results showed a moderate energy barrier for the metathesis process, in which the oxidation state of the Rh center does not change. This barrier is found to be much smaller than the barrier of the reductive process in the first pathway. Keywords Sustainable conversion . CO2 conversion . Metathesis process . Oxidative addition . Reductive elimination
Introduction As a reliable, cheap, and efficient source of energy, fossil fuels, e.g., coal, natural gas, and oil, provide roughly 80% of the world’s energy demand to meet basic human needs [1]. The combustion of fossil fuels apparently leads to the increase of the carbon dioxide (CO2) concentration from a preindustrial level of about 280 ppm to more than 415 ppm in 2019, anticipated that could reach a level of 470 ppm in 2050 [2–4]. A study by the International Energy Agency has
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s11224-020-01621-w) contains supplementary material, which is available to authorized users. * Maryam Anafcheh [email protected] 1
Department of Chemistry, Faculty of Physics and Chemistry, Alzahra University, Vanak, Tehran 19835-389, Iran
2
Department of Chemistry, Faculty of Sciences, Shahid Beheshti University, Evin, Tehran 19839-63113, Iran
anticipated that we need to reduce an amount of about 19% of the CO2 emission until 2050 [5, 6]. Reducing the concentration of heat-trapping carbon dioxide that is already in the air to combat global warming is a topic of growing interest [7–9]. There are various approaches to carbon dioxide removal, among which capture and conversion of CO2 is suggested as a highly cost-effective way [10–14]. Selective and efficient conversion of CO2 to a reusable form of carbon and sustainable production of fuel/ chemical feedstock is crucial [15–17]. Ca
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