Shape effects of ceria nanoparticles on the water-gas shift performance of cuox /ceo2 catalysts

T1EDK-00094 UIDB/EQU/50020/2020 UIDB/00511/2020 CEECINST/00102/2018 UIDB/50006/2020 UIDP/50006/2020 DL 57/2017The copper–ceria (CuOx /CeO2 ) system has been extensively investigated in several catalytic processes, given its distinctive properties and considerable low cost compared to noble metal-based catalysts. The fine-tuning of key parameters, e.g., the particle size and shape of individual counterparts, can significantly affect the physicochemical properties and subsequently the catalytic performance of the binary oxide. To this end, the present work focuses on the morphology effects of ceria nanoparticles, i.e., nanopolyhedra (P), nanocubes (C), and nanorods (R), on the water–gas shift (WGS) performance of CuOx /CeO2 catalysts. Various characterization techniques were employed to unveil the effect of shape on the structural, redox and surface properties. According to the acquired results, the support morphology affects to a different extent the reducibility and mobility of oxygen species, following the trend: R > P > C. This consequently influences copper–ceria interactions and the stabilization of partially reduced copper species (Cu+ ) through the Cu2+ /Cu+ and Ce4+ /Ce3+ redox cycles. Regarding the WGS performance, bare ceria supports exhibit no activity, while the addition of copper to the different ceria nanostructures alters significantly this behaviour. The CuOx /CeO2 sample of rod-like morphology demonstrates the best catalytic activity and stability, approaching the thermodynamic equilibrium conversion at 350◦ C. The greater abundance in loosely bound oxygen species, oxygen vacancies and highly dispersed Cu+ species can be mainly accounted for its superior catalytic performance.publishersversionpublishe

Effect of fuel thermal pretreament on the electrochemical performance of a direct lignite coal fuel cell

Proceedings of the 20th International Conference on Solid State Ionics SSI-20The impact of fuel heat pretreatment on the performance of a direct carbon fuel cell (DCFC) is investigated by utilizing lignite (LG) coal as feedstock in a solid oxide fuel cell of the type: lignite | Co–CeO2/YSZ/Ag | air. Four LG samples are employed as feedstock: (i) pristine lignite (LG), and differently heat treated LG samples under inert (He) atmosphere at (ii) 200 °C overnight (LG200), (iii) 500 °C for 1 h (LG500) and (iv) 800 °C for 1 h (LG800). The impact of several process parameters, related to cell temperature (700–800 °C), carrier gas type (He or CO2), and molten carbonate infusion into the feedstock on the DCFC performance is additionally explored. The proximate and ultimate analysis of the original and pretreated lignite samples show that upon increasing the heat treatment temperature the carbon content is monotonically increased, whereas the volatile matter, moisture, sulfur and oxygen contents are decreased. In addition, although volatiles are eliminated upon increasing the treatment temperature and as a consequence more ordered carbonaceous structure remained, the heat treatment increases the reactivity of lignite with CO2 due mainly to the increased carbon content. These modifications are reflected on the achieved DCFC performance, which is clearly improved upon increasing the treatment temperature. An inferior cell performance is demonstrated by utilizing inert He instead of reactive CO2 atmosphere, as purging gas in the anode compartment, while carbonate infusion always results in ca. 70–100% increase in power output (15.1 mW cm− 2 at 800 °C). The obtained findings are discussed based also on AC impedance spectroscopy measurements, which revealed the impact of LG physicochemical characteristics and DCFC operating parameters on both ohmic and electrode resistances.The authors would like to acknowledge financial support from the European project “Efficient Conversion of Coal to Electricity — Direct Coal Fuel Cells”, which is funded by the Research Fund for Carbon & Steel (RFCR CT-2011-00004).Peer reviewe

Direct utilization of lignite coal in a Co–CeO2/YSZ/Ag solid oxide fuel cell

The feasibility of employing lignite coal as a fuel in a Direct Carbon Fuel Cell (DCFC) of the type: lignite|Co–CeO2/YSZ/Ag|air is investigated. The impact of several parameters, related to anodic electrode composition (20, 40 and 60 wt.% Co/CeO2), cell temperature (700–800 °C), carrier gas composition (CO2/He mixtures), and total feed flow rate (10–70 cm3/min), was systematically examined. The effect of molten carbonates on DCFC performance was also investigated by employing a eutectic mixture of lithium and potassium carbonates as carbon additives. In the absence of carbonates, the optimum performance (∼10 mW cm−2 at 800 °C), was achieved by employing 20 wt.% Co/CeO2 as anodic electrode and pure CO2 as purging gas. An inferior behavior was demonstrated by utilizing He instead of CO2 atmosphere in anode compartment and by increasing purging gas flow rate. Carbonates infusion into lignite feedstock resulted in a further increase of maximum power density up to 32%. The obtained findings are discussed based also on AC impedance spectroscopy measurements, which revealed the impact of DCFC operating parameters on both ohmic and electrode resistances.The authors would like to acknowledge financial support from the European project “Efficient Conversion of Coal to Electricity – Direct Coal Fuel Cells”, which is funded by the Research Fund for Carbon & Steel (RFCR-CT-2011-00004). In addition the authors are grateful to Prof. V. Stathopoulos and Mr. P. Pandis for conducting the Direct Current Four Point (DC4P) measurements.Peer reviewe

Surface Chemistry and Catalysis

Nowadays, heterogeneous catalysis plays a prominent role.[...

Facet-Dependent Reactivity of Ceria Nanoparticles Exemplified by CeO2-Based Transition Metal Catalysts: A Critical Review

The rational design and fabrication of highly-active and cost-efficient catalytic materials constitutes the main research pillar in catalysis field. In this context, the fine-tuning of size and shape at the nanometer scale can exert an intense impact not only on the inherent reactivity of catalyst’s counterparts but also on their interfacial interactions; it can also opening up new horizons for the development of highly active and robust materials. The present critical review, focusing mainly on our recent advances on the topic, aims to highlight the pivotal role of shape engineering in catalysis, exemplified by noble metal-free, CeO2-based transition metal catalysts (TMs/CeO2). The underlying mechanism of facet-dependent reactivity is initially discussed. The main implications of ceria nanoparticles’ shape engineering (rods, cubes, and polyhedra) in catalysis are next discussed, on the ground of some of the most pertinent heterogeneous reactions, such as CO2 hydrogenation, CO oxidation, and N2O decomposition. It is clearly revealed that shape functionalization can remarkably affect the intrinsic features and in turn the reactivity of ceria nanoparticles. More importantly, by combining ceria nanoparticles (CeO2 NPs) of specific architecture with various transition metals (e.g., Cu, Fe, Co, and Ni) remarkably active multifunctional composites can be obtained due mainly to the synergistic metalceria interactions. From the practical point of view, novel catalyst formulations with similar or even superior reactivity to that of noble metals can be obtained by co-adjusting the shape and composition of mixed oxides, such as Cu/ceria nanorods for CO oxidation and Ni/ceria nanorods for CO2 hydrogenation. The conclusions derived could provide the design principles of earth-abundant metal oxide catalysts for various real-life environmental and energy applications

Surface and redox properties of cobalt-ceria binary oxides: on the effect of Co content and pretreatment conditions

tCeria-based transition metal catalysts have recently received considerable attention both in heteroge-neous catalysis and electro-catalysis fields, due to their unique physicochemical characteristics. Theircatalytic performance is greatly affected by the surface local chemistry and oxygen vacancies. The presentstudy aims at investigating the impact of Co/Ce ratio and pretreatment conditions on the surface andredox properties of cobalt-ceria binary oxides. Co-ceria mixed oxides with different Co content (0, 20,30, 60, 100 wt.%) were prepared by impregnation method and characterized by means of N2adsorption at−196◦C, X-ray diffraction (XRD), H2temperature-programmed reduction (H2-TPR) and X-ray photoelec-tron spectroscopy (XPS). The results shown the improved reducibility of Co/CeO2mixed oxides comparedto single oxides, due to a synergistic interaction between cobalt and cerium. Oxidation pretreatmentresults in a preferential localization of cerium species on the outer surface. In contrast, a uniform distri-bution of cobalt and cerium species over the entire catalyst surface is obtained by the reduction process,which facilitates the formation of oxygen vacancies though Co3+/Co2+and Ce3+/Ce4+redox cycles. Funda-mental insights toward tuning the surface chemistry of cobalt-ceria binary oxides are provided, pavingthe way for real-life industrial applications

H

The present study aims to examine and evaluate the concept of H2S decomposition to H2 production in (H2)-conducting electrochemical reactors. In such a complex process, one of the major issues raised is the optimal selection of materials for the electrochemical cell. Specifically, the anode electrode should exhibit high catalytic activity and electronic conductivity, in order to make the process efficient. In this context, and before the electrochemical tests, a number of transition metal catalysts supported on CeO2 were prepared using the wet impregnation method and tested for their performance regarding the activity/stability of the H2S decomposition reaction, in the absence and presence of H2O. The experimental results are accompanied by the corresponding thermodynamic calculations, at various reaction conditions. The physico-chemical characteristics of the employed catalysts were determined using the BET, XRD, SEM and elemental analysis methods. The experimental results showed that the catalysts 20% wt. Co/CeO2 and 30% wt. Co/CeO2 exhibit high H2S conversions, in the absence and presence of H2O respectively, comparable to conversions indicated by thermodynamics and with remarkable stability, which is attributed to the in-situ sulfation of catalysts’ active components during their exposure at the feedstock mixture

H2S in Black Sea: Turning an environmental threat to an opportunity for clean H2 production via an Electrochemical Membrane Reactor. Research progress in H2S-PROTON Project

The present study aims to examine and evaluate the concept of H2S decomposition to H2 production in (H2)-conducting electrochemical reactors. In such a complex process, one of the major issues raised is the optimal selection of materials for the electrochemical cell. Specifically, the anode electrode should exhibit high catalytic activity and electronic conductivity, in order to make the process efficient. In this context, and before the electrochemical tests, a number of transition metal catalysts supported on CeO2 were prepared using the wet impregnation method and tested for their performance regarding the activity/stability of the H2S decomposition reaction, in the absence and presence of H2O. The experimental results are accompanied by the corresponding thermodynamic calculations, at various reaction conditions. The physico-chemical characteristics of the employed catalysts were determined using the BET, XRD, SEM and elemental analysis methods. The experimental results showed that the catalysts 20% wt. Co/CeO2 and 30% wt. Co/CeO2 exhibit high H2S conversions, in the absence and presence of H2O respectively, comparable to conversions indicated by thermodynamics and with remarkable stability, which is attributed to the in-situ sulfation of catalysts’ active components during their exposure at the feedstock mixture

Recent Advances on Fine-Tuning Engineering Strategies of CeO₂-Based Nanostructured Catalysts Exemplified by CO₂ Hydrogenation Processes

Ceria-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