Nickel-based cerium zirconate inorganic complex structures for CO2 valorisation via dry reforming of methane.

The increasing anthropogenic emissions of greenhouse gases (GHG) is encouraging extensive research in CO2 utilisation. Dry reforming of methane (DRM) depicts a viable strategy to convert both CO2 and CH4 into syngas, a worthwhile chemical intermediate. Among the different active phases for DRM, the use of nickel as catalyst is economically favourable, but typically deactivates due to sintering and carbon deposition. The stabilisation of Ni at different loadings in cerium zirconate inorganic complex structures is investigated in this work as strategy to develop robust Ni-based DRM catalysts. XRD and TPR-H2 analyses confirmed the existence of different phases according to the Ni loading in these materials. Besides, superficial Ni is observed as well as the existence of a CeNiO3 perovskite structure. The catalytic activity was tested, proving that 10 wt.% Ni loading is the optimum which maximises conversion. This catalyst was also tested in long-term stability experiments at 600 and 800°C in order to study the potential deactivation issues at two different temperatures. At 600°C, carbon formation is the main cause of catalytic deactivation, whereas a robust stability is shown at 800°C, observing no sintering of the active phase evidencing the success of this strategy rendering a new family of economically appealing CO2 and biogas mixtures upgrading catalysts.

Boosting Low-Temperature CO2 Hydrogenation over Ni-based Catalysts by Tuning Strong Metal-Support Interactions.

Rational design of low-cost and efficient transition-metal catalysts for low-temperature CO2 activation is significant and poses great challenges. Herein, a strategy via regulating the local electron density of active sites is developed to boost CO2 methanation that normally requires >350 °C for commercial Ni catalysts. An optimal Ni/ZrO2 catalyst affords an excellent low-temperature performance hitherto, with a CO2 conversion of 84.0 %, CH4 selectivity of 98.6 % even at 230 °C and GHSV of 12,000 mL g-1 h-1 for 106 h, reflecting one of the best CO2 methanation performance to date on Ni-based catalysts. Combined a series of in situ spectroscopic characterization studies reveal that re-constructing monoclinic-ZrO2 supported Ni species with abundant oxygen vacancies can facilitate CO2 activation, owing to the enhanced local electron density of Ni induced by the strong metal-support interactions. These findings might be of great aid for construction of robust catalysts with an enhanced performance for CO2 emission abatement and beyond.

Flexible NiRu Systems for CO2 Methanation: From Efficient Catalysts to Advanced Dual-Function Materials.

CO2 emissions in the atmosphere have been increasing rapidly in recent years, causing global warming. CO2 methanation reaction is deemed to be a way to combat these emissions by converting CO2 into synthetic natural gas, i.e., CH4. NiRu/CeAl and NiRu/CeZr both demonstrated favourable activity for CO2 methanation, with NiRu/CeAl approaching equilibrium conversion at 350 °C with 100% CH4 selectivity. Its stability under high space velocity (400 L·g-1·h-1) was also commendable. By adding an adsorbent, potassium, the CO2 adsorption capability of NiRu/CeAl was boosted, allowing it to function as a dual-function material (DFM) for integrated CO2 capture and utilisation, producing 0.264 mol of CH4/kg of sample from captured CO2. Furthermore, time-resolved operando DRIFTS-MS measurements were performed to gain insights into the process mechanism. The obtained results demonstrate that CO2 was captured on basic sites and was also dissociated on metallic sites in such a way that during the reduction step, methane was produced by two different pathways. This study reveals that by adding an adsorbent to the formulation of an effective NiRu methanation catalyst, advanced dual-function materials can be designed.

Insights on Guerbet Reaction: Production of Biobutanol From Bioethanol Over a Mg-Al Spinel Catalyst.

The production of biobutanol from bioethanol by the Guerbet reaction is an alternative pathway to renewable sources. The commercial viability of this green route requires improvements in the process development. This study experimentally examines the influence of operating conditions on the performance of a Mg-Al spinel catalyst prepared from hydrotalcite precursors. This catalyst demonstrates an exceptional performance in the Guerbet reaction with a promising activity/butanol selectivity balance, excellent long-term stability, and very-low-carbon footprint (CO2 generation as by-products is minimal). This study showcases a systematic strategy to optimize the reaction parameters in the Guerbet reaction for biobutanol production using an advanced spinel catalyst. Upon carefully adjusting temperature, pressure, space velocity, and reactants co-feeding, very promising conversion (35%) and butanol selectivity values (48%) were obtained.

Emerging natural and tailored perovskite-type mixed oxides-based catalysts for CO2 conversions.

The rapid economic and societal development have led to unprecedented energy demand and consumption resulting in the harmful emission of pollutants. Hence, the conversion of greenhouse gases into valuable chemicals and fuels has become an urgent challenge for the scientific community. In recent decades, perovskite-type mixed oxide-based catalysts have attracted significant attention as efficient CO2 conversion catalysts due to the characteristics of both reversible oxygen storage capacity and stable structure compared to traditional oxide-supported catalysts. In this review, we hand over a comprehensive overview of the research for CO2 conversion by these emerging perovskite-type mixed oxide-based catalysts. Three main CO2 conversions, namely reverse water gas shift reaction, CO2 methanation, and CO2 reforming of methane have been introduced over perovskite-type mixed oxide-based catalysts and their reaction mechanisms. Different approaches for promoting activity and resisting carbon deposition have also been discussed, involving increased oxygen vacancies, enhanced dispersion of active metal, and fine-tuning strong metal-support interactions. Finally, the current challenges are mooted, and we have proposed future research prospects in this field to inspire more sensational breakthroughs in the material and environment fields.

Biogas Conversion to Syngas Using Advanced Ni-Promoted Pyrochlore Catalysts: Effect of the CH4/CO2 Ratio.

Biogas is defined as the mixture of CH4 and CO2 produced by the anaerobic digestion of biomass. This particular mixture can be transformed in high valuable intermediates such as syngas through a process known as dry reforming (DRM). The reaction involved is highly endothermic, and catalysts capable to endure carbon deposition and metal particle sintering are required. Ni-pyrochlore catalysts have shown outstanding results in the DRM. However, most reported data deals with CH4/CO2 stoichiometric ratios resulting is a very narrow picture of the overall biogas upgrading via DRM. Therefore, this study explores the performance of an optimized Ni-doped pyrochlore, and Ni-impregnated pyrochlore catalysts in the dry reforming of methane, under different CH4/CO2 ratios, in order to simulate various representatives waste biomass feedstocks. Long-term stability tests showed that the ratio CH4/CO2 in the feed gas stream has an important influence in the catalysts' deactivation. Ni doped pyrochlore catalyst, presents less deactivation than the Ni-impregnated pyrochlore. However, biogas mixtures with a CH4 content higher than 60%, lead to a stronger deactivation in both Ni-catalysts. These results were in agreement with the thermogravimetric analysis (TGA) of the post reacted samples that showed a very limited carbon formation when using biogas mixtures with CH4 content <60%, but CH4/CO2 ratios higher than 1.25 lead to an evident carbon deposition. TGA analysis of the post reacted Ni impregnated pyrochlore, showed the highest amount of carbon deposited, even with lower stoichiometric CH4/CO2 ratios. The later result indicates that stabilization of Ni in the pyrochlore structure is vital, in order to enhance the coke resistance of this type of catalysts.

Molten Salt-Promoted MgO Adsorbents for CO2 Capture: Transient Kinetic Studies.

Optimization of MgO adsorbents is predominantly focused on the regulation of appropriate adsorption sites for CO2 associated with Mg2+-O2- sites of low coordination. Here, for the first time, we conducted transient kinetic experiments to identify and characterize changes of the CO2 molecular path in MgO-based CO2 adsorbents upon the addition of molten salt modifiers. Among the optimized samples, addition of 10 mol % NaNO2 on the surface of MgO exhibited the highest CO2 uptake (15.7 mmol g-1) at 350 °C compared to less than 0.1 mmol g-1 for the unpromoted MgO. Kinetic modeling showed that the interaction of molten salt-promoted MgO with CO2 at 300 °C involves three different processes, namely, fast surface adsorption associated with surface-active basic sites, chemical reaction associated with MgCO3 formation, and a slow diffusion step being the rate-limiting step of the carbonation process. Furthermore, transient kinetic studies coupled with mass spectrometry under low CO2 partial pressure agreed well with the kinetic simulation results based on TGA measurements, demonstrating an in-depth understanding of the CO2-capturing performance gained and its considerable significance for future practical designs of precombustion CO2 capture.

Carbon Supported Gold Nanoparticles for the Catalytic Reduction of 4-Nitrophenol.

This work is a detailed study on how to optimize gold colloids preparation and their deposition to very different in nature carbon materials. The change of the continuous phase and its dielectric constant is used to assure the good dispersion of the hydrophilic/hydrophobic carbons and the successful transfer of the preformed small size colloids to their surface. The sintering behavior of the particles during the calcination step is also studied and the optimal conditions to reduce to a minimum the particle size increase during the protecting agent removal phase are found. The as prepared catalysts have been tested in a relevant reaction in the field of environmental catalysis such as the reduction of 4-nitrophenol leading to promising results. Overall, this work proposes an important methodology to follow when a carbonaceous material are selected as catalyst supports for green chemistry reactions.

Au/CeO2-ZnO/Al2O3 as Versatile Catalysts for Oxidation Reactions: Application in Gas/Liquid Environmental Processes.

The present work showcases the versatility of nanogold systems supported on Zn-doped ceria when applied in two important environmental processes, the total CO oxidation, and the liquid phase oxidation of glucose to gluconic acid. In the CO oxidation the suitability of these materials is clearly demonstrated achieving full conversions even at sub-ambient conditions. Regarding the glucose oxidation our materials display high conversion values (always over 50%) and very importantly full or almost full selectivity toward gluconic acid-an added value platform chemical in the context of biomass upgrading routes. The key factors controlling the successful performance on both reactions are carefully discussed and compared to previous studies in literature. To our knowledge this is one of the very few works in catalysis by gold combining liquid and gas phase reactions and represents a step forward in the flexible behavior of nano gold catalysts.

Influence of Reaction Parameters on the Catalytic Upgrading of an Acetone, Butanol, and Ethanol (ABE) Mixture: Exploring New Routes for Modern Biorefineries.

Here we present a comprehensive study on the effect of reaction parameters on the upgrade of an acetone, butanol and ethanol mixture-key molecules and platform products of great interest within the chemical sector. Using a selected high performing catalyst, Fe/MgO-Al2O3, the variation of temperature, reaction time, catalytic loading, and reactant molar ratio have been examined in this reaction. This work is aiming to not only optimize the reaction conditions previously used, but to step toward using less energy, time, and material by testing those conditions and analyzing the sufficiency of the results. Herein, we demonstrate that this reaction is favored at higher temperatures and longer reaction time. Also, we observe that increasing the catalyst loading had a positive effect on the product yields, while reactant ratios have shown to produce varied results due to the role of each reactant in the complex reaction network. In line with the aim of reducing energy and costs, this work showcases that the products from the upgrading route have significantly higher market value than the reactants; highlighting that this process represents an appealing route to be implemented in modern biorefineries.