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Nickel phosphide catalysts show a high level of selectivity for the reverse water-gas shift (RWGS) reaction, inhibiting the competing methanation reaction. This work investigates the extent to which suppression of methanation can be controlled by phosphidation and tests the stability of phosphide phases over 24-hour time on stream. Herein the synthesis of different phosphide crystal structures by varying Ni/P atomic ratios (from 0.5 to 2.4) is shown to affect the selectivity to CO over CH4 in a significant way. We also show that the activity of these catalysts can be fine-tuned by the synthesis Ni/P ratio and identify suitable catalysts for low temperature RWGS process. Ni12P5-SiO2 showed 80–100% selectivity over the full temperature range (i.e., 300–800 °C) tested, reaching 73% CO2 conversion at 800 °C. Ni2P-SiO2 exhibited CO selectivity of 93–100% over a full temperature range, and 70% CO2 conversion at 800 °C. The highest CO2 conversions for Ni12P5-SiO2 at all temperatures among all catalysts showed its promising nature for CO2 capture and utilisation. The methanation reaction was suppressed in addition to RWGS activity improvement through the formation of nickel phosphide phases, and the crystal structure was found to determine CO selectivity, with the following order Ni12P5 >Ni2P > Ni3P. Based on the activity of the studied catalysts, the catalysts were ranked in order of suitability for the RWGS reaction as follows: Ni12P5-SiO2 (Ni/P = 2.4) > Ni2P-SiO2 (Ni/P = 2) > NiP-SiO2 (Ni/P = 1) > NiP2-SiO2 (Ni/P = 0.5). Two catalysts with Ni/P atomic ratios; 2.4 and 2, were selected for stability testing. The catalyst with Ni/P ratio = 2.4 (i.e., Ni12P5-SiO2) was found to be more stable in terms of CO2 conversion and CO yield over the 24-hour duration at 550 °C. Using the phosphidation strategy to tune both selectivity and activity of Ni catalysts for RWGS, methanation as a competing reaction is shown to be no longer a critical issue in the RWGS process for catalysts with high Ni/P atomic ratios (2.4 and 2) even at lower temperatures (300–500 °C). This opens up potential low temperature RWGS opportunities, especially coupled to downstream or tandem lower temperature processes to produce liquid fuels.

Introduction: Innovating technologies to efficiently reduce carbon dioxide (CO2) emission or covert it into useful products has never been more crucial in light of the urgent need to transition to a net-zero economy by 2050. The design of efficient catalysts that can make the above a viable solution is of essence. Many noble metal catalysts already display high activity, but are usually expensive. Thus, alternative methods for their production are necessary to ensure more efficient use of noble metals.Methods: Exsolution has been shown to be an approach to produce strained nanoparticles, stable against agglomeration while displaying enhanced activity. Here we explore the effect of a low level of substitution of Ni into a Rh based A-site deficienttitanate aiming to investigate the formation of more efficient, low loading noblemetal catalysts.Results: We find that with the addition of Ni in a Rh based titanate exsolution is increased by up to ∼4 times in terms of particle population which in turn results in up to 50% increase in its catalytic activity for CO2 conversion.Discussion: We show that this design principle not only fulfills a major research need in the conversion of CO2 but also provides a step-change advancement in the design and synthesis of tandem catalysts by the formation of distinct catalytically active sites.

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.

Torrefaction is a key process for biomass energy densification ahead of its utilisation in pyrolysis, gasification or combustion, and therefore the changes it originates have been the subject of multiple studies. Most of them employ low heating rates, in the range of thermogravimetric analysers (TGA), typically below 1 °C s−1 or high rates (100–1000 °C s−1) in reactors where tars undergo considerable secondary reactions following release from a particle and the temperature history of the sample is not well defined, such as entrained flow or fluidised beds. This study aims to analyse the behaviour of torrefied lignocellulosic biomass (oak) under fast pyrolysis in with very controlled temperature history and absence of secondary reactions between evolving volatiles and chars in a wire mesh reactor (WMR), which allows determination of primary products. To this end, oak was firstly torrefied in a grey-King reactor to provide samples from mild to severe torrefaction (210–300 °C). The raw and torrefied oaks were pyrolyzed/gasified, at 1000 °C s−1 and 850 °C in the WMR using He and CO2 atmospheres. All samples showed high volatile production, in excess of 80 wt.%, but with a clear drop with increasing torrefaction temperature. The char yields from the WMR in CO2 were lower than in He, reflecting a degree of char gasification. However, char deactivation at the higher torrefaction temperatures caused a sharp decrease in the extent of gasification from 32 wt.% for Raw Oak to 6 wt.% for oak torrefied at 300 °C (Oak-300). This is a consequence of the predominance of chemical effects such as enrichment of carbon, which increased from 46.5 wt.% for Raw Oak to 54.3 wt.% in Oak-300 and depletion of oxygen, which led to greater aromaticity and structural order in the char with torrefaction temperature, over physical changes observed by scanning electron microscopy (SEM) revealing increasing porosity.

Rising carbon dioxide (CO2) levels in the atmosphere from anthropogenic sources have led to the development of carbon capture, utilisation and storage (CCUS) technologies. In order to decarbonise chemical synthesis, a process intensification approach can be employed, wherein CO2 capture is coupled to a chemical reaction in a way that improves energy efficiency and product yields. In this review paper, we present advances in CO2 adsorbent development for process intensification, focusing on applications that have achieved a synergistic effect between CO2 adsorption and catalytic reactions that either consume or generate CO2. Firstly, we present a range of solid CO2 adsorbents of varying capability to capture CO2. Then we present a short introduction to the importance of developing CO2 adsorbents for process intensification. In order to improve the direction of research in the future, we emphasise the importance of developing compatible adsorbents and catalysts that operate synergistically and discuss the importance of cross cutting themes in process intensification and research opportunities for the future.

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.

CO2 hydrogenation to methanol and methanol steam reforming (MSR) are regarded as two critical reactions for transportation and on‐site production of hydrogen, but it still lacks of efficient catalysts for both reactions. Herein, the CuZnSi‐ammonia evaporation method (AEM) catalyst prepared by AEM with extremely low metal loading and highly dispersed Cu/Zn species, in particular, high concentration of Cu+ species, exhibits an optimum space‐time yield of methanol (1888.3 g kgCu−1 h−1) and an exceptional specific activity of 282.6 molCO2 kgCu−1 h−1, which is higher than a majority of the reported catalysts. Furthermore, the CuZnSi‐AEM catalyst is also active for MSR reaction with low CO selectivity. The results reveal that the morphology, exposed Cu+ species, and synergistic Cu–ZnOx interaction are the key guiding factors for the successful utilization of methanol as a hydrogen carrier.

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

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.

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.

Solid oxide fuel cells can operate with carbonaceous fuels, such as syngas, biogas, and methane, using either internal or external reforming, and they represent a more efficient alternative to internal combustion engines. In this work, we explore, for the first time, an alumina membrane containing straight, highly packed (461,289 cpsi), parallel channels of a few micrometers (21 µm) in diameter as a microreformer. As a model reaction to test the performance of this membrane, the dry reforming of methane was carried out using nickel metal and a composite nickel/ceria as catalysts. The samples with intact microchannels were more resistant to carbon deposition than those with a powdered sample, highlighting the deactivation mitigation effect of the microchannel structure. The coke content in the microchannel membrane was one order of magnitude lower than in the powder catalyst. Overall, this work is a proof of concept on the use of composite alumina membrane as microchannel reactors for high temperature reactions.

Converting CO2 to methane via catalytic routes is an effective way to control the CO2 content released in the atmosphere while producing value-added fuels and chemicals. In this study, the CO2 methanation performance of highly dispersed Ni-based catalysts derived from aqueous miscible organic layered double hydroxides (AMO-LDHs) was investigated. The activity of the catalyst was found to be largely influenced by the chemical composition of Ni metal precursor and loading. A Ni-based catalyst derived from AMO-Ni3Al1-CO3 LDH exhibited a maximum CO2 conversion of 87.9% and 100% CH4 selectivity ascribed to both the lamellar catalyst structure and the high Ni metal dispersion achieved. Moreover, due to the strong Ni metal–support interactions and abundant oxygen vacancy concentration developed, this catalyst also showed excellent resistance to carbon deposition and metal sintering. In particular, high stability was observed after 19 h in CO2/H2 reaction at 360 °C.

Increasing demand for CO2 utilization reactions and the stable character of CO2 have motivated interest in developing highly active, selective and stable catalysts. Precious metal catalysts have been studied extensively due to their high activities, but their implementation for industrial applications is hindered due to their elevated cost. Among the materials which have comparatively low prices, transition metal carbides (TMCs) are deemed to display catalytic properties similar to Pt-group metals (Ru, Rh, Pd, Ir, Pt) in several reactions such as hydrogenation and dehydrogenation processes. In addition, they are excellent substrates to disperse metallic particles. Hence, the unique properties of TMCs make them ideal substitutes for precious metals resulting in promising catalysts for CO2 utilization reactions. This work aims to provide a comprehensive overview of recent advances on TMCs catalysts towards gas phase CO2 utilization processes, such as CO2 methanation, reverse water gas shift (rWGS) and dry reforming of methane (DRM). We have carefully analyzed synthesis procedures, performances and limitations of different TMCs catalysts. Insights on material characteristics such as crystal structure and surface chemistry and their connection with the catalytic activity are also critically reviewed.

The conversion of CO2 into CO via the Reverse Water⁻Gas Shift (RWGS) reaction is a suitable route for CO2 valorisation. Fe-based catalysts are highly active for this reaction, but their activity and selectivity can be substantially boosted by adding Cs as a promoter. In this work we demonstrate that Cs modifies the redox behaviour and the surface chemistry of the iron-based materials. The metallic dispersion and the amount of metallic Fe centres available for the reaction depends on Cs loading. 5 wt. % of Cs is an optimum amount of dopant to achieve a fair activity/selective balance. Nevertheless, depending on the RWGS reactor operational temperature, lower concentrations of Cs also lead to acceptable catalytic performance. Along with the excellent activity of the prepared materials this work showcases their robustness for long-term runs and the strong impact of H2/CO ratio in the overall catalytic performance.

The oil and gas sector produces a considerable volume of greenhouse gas emissions, mainly generated from flaring and venting natural gas. Herein, a techno-economic analysis has been performed of a switchable catalytic process to convert the CH4 and CO2 in flared/vented natural gas into syngas or methanol. Specifically, it was shown that depending on greenhouse gas composition, dry methane reforming (DRM), reverse water-gas shift (RWGS), and CO2 methanation could be chosen to valorise emissions in an overall profitable and flexible operation scenario. The switchable process produced methanol and synthetic natural gas as its products, resulting in an annual income of €687m and annual operating expenses of €452m. The pre-tax profit was calculated at €234m, and at the end of the project, the net present value was calculated as €1.9b with a profitability index of 4.7€/€. The expected payback time of this process was ca. 4 years, and with a 35% internal rate of return (IRR). Most importantly, this process consumed 42.8m tonnes of CO2 annually. The sensitivity analysis revealed that variations in operation time, green hydrogen price, and products' prices significantly impacted the profitability of the process. Overall, this techno-economic analysis demonstrated that switchable catalysis in greenhouse gas utilisation processes is profitable, and thus it could play an important role in achieving net zero emissions.

Fe-derived catalysts were synthesized by the pyrolysis of MIL-100 (Fe) metal-organic framework (MOF) and evaluated in the reverse water-gas shift (RWGS) reaction. The addition of Rh as a dopant by in-situ incorporation during the synthesis and wet impregnation was also considered. Our characterization data showed that the main active phase was a mixture of α-Fe, Fe3C, and Fe3O4 in all the catalysts evaluated. Additionally, small Rh loading leads to a decrease in the particle size in the active phase. Despite all three catalysts showing commendable CO selectivity levels, the C@Fe* catalyst showed the most promising performance at a temperature below 500 °C, attributed to the in-situ incorporation of Rh during the synthesis. Overall, this work showcases a strategy for designing novel Fe MOF-derived catalysts for RWGS reaction, opening new research opportunities for CO2 utilization schemes.

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.

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.

In this work, the WGS performance of a conventional Ni/CeO2 bulk catalyst is compared to that of a carbon-supported Ni-CeO2 catalyst. The carbon-supported sample resulted to be much more active than the bulk one. The higher activity of the Ni-CeO2/C catalyst is associated to its oxygen storage capacity, a parameter that strongly influences the WGS behavior. The stability of the carbon-supported catalyst under realistic operation conditions is also a subject of this paper. In summary, our study represents an approach towards a new generation of Ni-ceria based catalyst for the pure hydrogen production via WGS. The dispersion of ceria nanoparticles on an activated carbon support drives to improved catalytic skills with a considerable reduction of the amount of ceria in the catalyst formulation.

The urgent need for mitigating climate change necessitates a transformative shift in energy production and consumption paradigms. Amidst this challenge, bioenergy emerges as a pivotal contributor to the global energy transition, offering a diverse array of solid, liquid, and gaseous fuels derived from biomass. This mini review delves into the unique potential of bioenergy innovations, particularly renewable diesel, bio jet fuel, and ethanol, to reduce greenhouse gas emissions and transform various industries. The article highlights critical technological advancements, supportive policies, and cross-sector collaboration essential for a sustainable energy transition. Specific challenges such as ensuring a consistent biomass feedstock supply, decentralizing processing units, and navigating complex regulatory frameworks are examined. Innovative solutions like decentralized biomass processing and enhanced biomass logistics are discussed as pathways to overcome these barriers. The review provides specific recommendations for near-term policies and strategies to support decentralized facilities, showcasing bioenergy’s role in achieving a sustainable future.

In this comprehensive review, the main aspects of using Au/CeO2 catalysts in oxidation reactions are considered. The influence of the preparation methods and synthetic parameters, as well as the characteristics of the ceria support (presence of doping cations, oxygen vacancies concentration, surface area, redox properties, etc.) in the dispersion and chemical state of gold are revised. The proposed review provides a detailed analysis of the literature data concerning the state of the art and the applications of gold–ceria systems in oxidation reactions.