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Mechanisms of Solid–Gas Reactions: Reduction of Air Pollutants on Carbons

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Abstract

Ozone is a strong oxidizer and sulfur dioxide is a precursor to acid rain, both are air pollutants that can damage the respiratory tissues of animals and plants making them hazardous to the environment. They are isoelectronic valence O = X = O (X = S, O) molecules and their mechanism of reduction on carbons is similar. The solid–gas kinetics were studied in a flow system with a tubular reactor under differential and steady state conditions. Initial rates and product distribution were used to determine the stoichiometry of the reaction. The reduction of XO2 on carbons proceeds through a common primary mechanism with oxidized and reduced intermediates. The reactivity of the intermediates that were inserted on carbons (graphite, activated carbon, graphene oxide) modified by SO2 is selective with respect to aminolysis and thiolysis. A theoretical study of the chemisorption of SO2 on dehydrogenated pyrene as graphite active site model showed that at 900 °C the chemisorption occurs mainly on the diradical zigzag edge. Computational quantum chemistry calculations were carried out for the reduction of SO2 on graphite to produce elemental sulfur and CO2 using tetradehydrogenated-benzo[α]anthracene (TBA) as model. The mechanisms of the decarboxylation and sulfur transport steps were postulated. Ozonation of graphite showed that the 1,2,3-trioxolane decomposes to an oxyrene, eliminating O2. Both reactions, the SO2 and O3 with graphite, have the same experimental free energy of activation for the decarboxylation reaction. The results show that for SO2 the desulfurization has a much lower energetic demand than the decarboxylation route raising the important possibility of using the reaction of reduction of SO2 on carbons to reduce the acid rain, producing elemental sulfur as the main product, without increasing the greenhouse effect due to the formation of CO2.

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Acknowledgements

We thank the Brazilian Government Agency Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), and both the Spanish Ministerio de Educación, Cultura y Deporte, DGU, Project PHB2009-0057-PC, and the regional government Xunta de Galicia (Project Grupo Potencial Crecemento (GPC) ED431B 2017/59) for financial support.

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Authors and Affiliations

  1. Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, Brazil

    Eduardo Humeres & Nito Angelo Debacher

  2. Departamento de Engenharia Química e de Alimentos, Universidade Federal de Santa Catarina, Florianópolis, SC, Brazil

    Regina de F. P. M. Moreira

  3. Departamento de Química, Facultade de Ciencias & CICA, Grupo Reactividade Química e Fotorreactividade (React!), Universidade da Coruña, 15071 A, Coruña, Spain

    J. Arturo Santaballa & Moisés Canle

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  1. Eduardo Humeres
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  2. Nito Angelo Debacher
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  3. Regina de F. P. M. Moreira
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  4. J. Arturo Santaballa
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  5. Moisés Canle
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Correspondence to Eduardo Humeres or J. Arturo Santaballa.

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The first draft of the manuscript was written by Eduardo Humeres who performed the literature search and all authors commented on previous versions of the manuscript and data analysis. All authors critically revised the work and approved the final manuscript.

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Humeres, E., Debacher, N.A., Moreira, R.F.P.M. et al. Mechanisms of Solid–Gas Reactions: Reduction of Air Pollutants on Carbons. Top Catal 63, 817–832 (2020). https://doi.org/10.1007/s11244-020-01318-8

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