Recent advances on fine-tuning engineering strategies of CeO2-based nanostructured catalysts exemplified by CO2 hydrogenation processesRecent advances on fine-tuning engineering strategies of CeO2-based nanostructured catalysts exemplified by CO2 hydrogenation processes Ανασκόπηση Review 2025-05-272023enCeria-based oxides have been extensively involved in a wide range of catalytic applications due to their intriguing properties, related mostly to their superior redox features in conjunction with peculiar metal-support interaction phenomena. Most importantly, the fine-tuning of key interrelated factors, such as the size, morphology and electronic state of the catalyst’s counterparts, can exert a profound influence on the intrinsic characteristics and interfacial reactivity with pronounced implications in catalysis. The present review, while also elaborating our recent efforts in the field, aims to provide key fundamental and practical aspects in relation to the rational design and functionalization strategies of ceria-based catalysts, exemplified by the CO2 hydrogenation processes, namely, CO2 methanation and reverse water–gas shift (rWGS) reactions. Firstly, a description of the most prominent catalytically relevant features of cerium oxide is provided, focusing on reducibility and metal-support interaction phenomena, followed by a brief overview of the current status of ceria-based catalysts for various energy and environmental applications. Then, the main implications of fine-tuning engineering via either appropriate synthesis routes or aliovalent doping on key activity descriptors are thoroughly discussed and exemplified by state-of-the-art ceria-based catalysts for CO2 hydrogenation. It is clearly revealed that highly active and cost-efficient ceria-based catalytic materials can be obtained on the grounds of the proposed functionalization strategy, with comparable or even superior reactivity to that of noble metal catalysts for both the studied reactions. In a nutshell, it can be postulated that the dedicated fabrication of CeO2-based systems with augmented redox capabilities and, thus, oxygen vacancies abundance can greatly enhance the activation of gas-phase CO2 towards CO or CH4. Besides, the morphology-engineering of CeO2-based catalysts can notably affect the CO2 hydrogenation performance, by means of an optimum metal-ceria interphase based on the exposed facets, whereas doping and promotion strategies can effectively shift the reaction pathway towards the selective production of either CO or CH4. The conclusions derived from the present work can provide design and fine-tuning principles for cost-efficient, highly active and earth-abundant metal oxide systems, not only for the CO2 hydrogenation process but for various other energy and environmental applications.This research has been co-financed by the European Union NextGenerationEU under the call RESEARCH-CREATE-INNOVATE 16971 Recovery and Resilience Facility (project code: TAEDK-06169).http://creativecommons.org/licenses/by/4.0/Catalysts132Varvoutis_et_al_Catalysts_13(2)_2023.pdfChania [Greece]Library of TUC2025-05-27application/pdf14.0 MBfree Varvoutis Georgios Lykaki Maria Λυκακη Μαρια Marnellos, Georges E Konsolakis Michail Κονσολακης Μιχαηλ MDPI CO2 hydrogenation CeO2-based catalysts Size/shape/electronic functionalization Rational design Metal-support interactions Reverse water–gas shift Methanation reactions