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.

MIL-100(Fe)-derived catalysts for CO2 conversion via low- and high-temperature reverse water-gas shift reaction.

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.

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.

Sustainable routes for acetic acid production: Traditional processes vs a low-carbon, biogas-based strategy.

The conversion of biogas, mainly formed of CO2 and CH4, into high-value platform chemicals is increasing attention in a context of low-carbon societies. In this new paradigm, acetic acid (AA) is deemed as an interesting product for the chemical industry. Herein we present a fresh overview of the current manufacturing approaches, compared to potential low-carbon alternatives. The use of biogas as primary feedstock to produce acetic acid is an auspicious alternative, representing a step-ahead on carbon-neutral industrial processes. Within the spirit of a circular economy, we propose and analyse a new BIO-strategy with two noteworthy pathways to potentially lower the environmental impact. The generation of syngas via dry reforming (DRM) combined with CO2 utilisation offers a way to produce acetic acid in a two-step approach (BIO-Indirect route), replacing the conventional, petroleum-derived steam reforming process. The most recent advances on catalyst design and technology are discussed. On the other hand, the BIO-Direct route offers a ground-breaking, atom-efficient way to directly generate acetic acid from biogas. Nevertheless, due to thermodynamic restrictions, the use of plasma technology is needed to directly produce acetic acid. This very promising approach is still in an early stage. Particularly, progress in catalyst design is mandatory to enable low-carbon routes for acetic acid production.