Computational catalysis on the conversion of CO₂ to methane—an update

Abstract

The reliance on fossil fuels intensifies CO₂ emissions, worsening political and environmental challenges. CO₂ capture and conversion present a promising solution, influenced by industrialization and urbanization. In recent times, catalytic conversion of CO₂ into fuels and chemical precursors, particularly methane, are gaining traction for establishing a sustainable, carbon-neutral economy due to methane’s advantages in renewable energy applications. Though homogeneous and heterogeneous catalysts are available for the conversion of CO₂ to methane, the efficiency is found to be higher in heterogeneous catalysts. Therefore, this review focuses only on the heterogeneous catalysts. In this context, the efficient heterogeneous catalysts with optimum utility are yet to be obtained. Therefore, the quest for suitable catalyst for the catalytic conversion of CO₂ to CH₄ is still continuing and designing efficient catalysts requires assessing their synthetic feasibility, often achieved through computational methods like density functional theory simulations, providing insights into reaction mechanisms, rate-limiting steps, catalytic cycle, activation of C=O bonds and enhancing understanding while lowering costs. In this context, this review examines the conversion of CO₂ to CH₄ using seven distinct types of catalysts, including single and double atom catalysts, metal organic frameworks, metalloporphyrins, graphdiyne and graphitic carbon nitrite and alloys with some case studies. The main focus of this review is to offer a detailed and extensive examination of diverse catalyst design approaches and their utilization in CH₄ production, with a specific emphasis on computational aspects. It explores the array of design methodologies used to identify reaction pathways and investigates the critical role of computational tools in their refinement and enhancement. We believe this review will help budding researchers to explore the possibilities of designing catalysts for the CO₂ to CH₄ conversion from computational framework.

Graphical abstract

Keywords

computational catalysis / single atom catalyst / CO₂ reduction / metalloporphyrins / double-atom catalyst / graphitic carbon nitrite

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Competing interests

The authors declare that they have no competing interests.

Acknowledgements

The authors (YMK, AR & RVS) dedicate this review to their esteemed professor, Dr. J. Princy Merlin, Principal of Bishop Heber College, Tiruchirappalli, whose three decades of selfless service have inspired thousands of students. Prince Joby, of 2nd M. Sc. Chemistry, has done this work at DST-FIST Sponsored Professor Edward Barnes Computation and Instrumentation Facility (PEBCIF) of the Department of Chemistry, Madras Christian College. Dr. R. Vijay Solomon thanks the Department of Chemistry, MCC for the support and encouragement. Dr. Y. Manojkumar acknowledges the management of Bishop Heber College (Autonomous), Tiruchirappalli-620 017, Tamil Nadu, India, for the support (Ref. No. 18.04.2023 MRP/1005/2023 (BHC)). Dr. Antony Rajendrdan acknowledges the support provided by the National Key Research and Development Program of China (Grant No. 2022YFE0208400).

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