UV- and visible-light photocatalysis using Ni-Co bimetallic and monometallic hydrotalcite-like materials for enhanced CO2 methanation in sabatier reaction.

The CO2 catalytic reduction activities of four different Co-modified Ni-based catalysts derived from hydrotalcite-like materials (HTCs) prepared by co-precipitation method were investigated under thermal and photocatalytic conditions. All catalysts were tested from 473 to 723 K at 10 bar (abs). The light intensity for photocatalytic reactions was 2.4 W cm-2. The samples were characterized to determine the effect of morphological and physicochemical properties of mono-bimetallic active phases on their methanation activity. The activity toward CO2 methanation followed the next order: Ni > Co-Ni > Co. For the monometallic Ni catalyst an increase of a 72% was achieved in the photo-catalytic activity under UV and vis light irradiation at temperatures lower by > 100 K than those in a conventional reaction. Co-modified Ni based hydrotalcite catalysts performed with stability and no deactivation for the 16 h studied under visible light for methanation at 523 K due to the presence of basic sites.

Development of High Temperature Water Sorbents Based on Zeolites, Dolomite, Lanthanum Oxide and Coke.

Methanation is gaining attention as it produces green methane from CO2 and H2, through Power-to-Gas technology. This process could be improved by in situ water sorption. The main difficulty for this process intensification is to find effective water sorbents at useful reaction temperatures (275-400 °C). The present work comprises the study of the water sorption capacity of different materials at 25-400 °C. The sorption capacity of the most studied solid sorbents (zeolites 3A & 4A) was compared to other materials such as dolomite, La2O3 and cokes. In trying to improve their stability and sorption capacity at high temperatures, all these materials were modified with alkaline-earth metals (Ba, Ca & Mg). Lanthana-Ba and dolomite sorbents were the most promising materials, reaching water sorption values of 120 and 102 mgH2O/gsorbent, respectively, even at 300 °C, i.e., values 10-times higher than the achieved ones with zeolites 3A or 4A under the same operating conditions. At these high temperatures, around 300 °C, the water sorption process was concluded to be closer to chemisorption than to physisorption.

Graphene-based versus alumina supports on CO2 methanation using lanthanum-promoted nickel catalysts.

The valorization of CO2 as a biofuel, transforming it through methanation as part of the power-to-gas (P2G) process, will allow the reduction of the net emissions of this gas to the atmosphere. Catalysts with 13 wt.% of nickel (Ni) loading incorporated into alumina and graphene derivatives were used, and the effect of the support on the activity was examined at temperatures between 498 and 773 K and 10 bar of pressure. Among the graphene-based catalysts (13Ni/AGO, 13Ni/BGO, 13Ni/rGO, 13Ni-Ol/GO, 13Ni/Ol-GO, and 13Ni/Ol-GO Met), the highest methane yield was found for 13Ni/rGO (78% at 810 K), being the only system comparable to the catalyst supported on alumina 13Ni/Al2O3 (89.5% at 745 K). The incorporation of 14 wt.% of lanthanum (La) into the most promising supports, rGO and alumina, led to nickel-support interactions that enhanced the catalytic activity of 13Ni/Al2O3 (89.5% at lower temperature, 727 K) but was not effective for 13Ni/rGO. The resistance against deactivation by H2S poisoning was also studied for these catalysts, and a fast deactivation was observed. In addition, activity recovery was impossible despite the regeneration treatment carried out over catalysts. The resistance against deactivation by H2S poisoning was also studied for these catalysts, observing that both suffered a rapid/immediate deactivation and which in addition/unfortunately was impossible to solve despite the regeneration treatment carried out over catalysts.

A study of deactivation by H2S and regeneration of a Ni catalyst supported on Al2O3, during methanation of CO2. Effect of the promoters Co, Cr, Fe and Mo.

Energy storage from renewable sources is possible by chemical procedures, power to gas technology being a possible solution for long-term storage. In this work, CO2 methanation from a sulphur containing gas was studied, taking into account deactivation of the catalysts and a regeneration process. In order to improve the sulphur resistance of a standard nickel (13%) catalyst supported on alumina, transition metals like molybdenum (Mo), iron (Fe), cobalt (Co) or chromium (Cr), in different proportions (from 4 to 8 wt%) were added to the catalyst formulation. The catalyst activity, between 573 and 773 K, at 10 bar, increased when transition metals were added except for Mo in the highest proportion. These bimetallic catalysts presented a similar deactivation resistance than the monometallic catalyst when sulphur was present in the feed. Once H2S was removed from the feed, and the catalysts regenerated with oxygen, only the catalyst containing cobalt recovered up to a 13% methane yield.

Heterogeneous Catalyzed Thermochemical Conversion of Lignin Model Compounds: An Overview.

Thermochemical lignin conversion processes can be described as complex reaction networks involving not only de-polymerization and re-polymerization reactions, but also chemical transformations of the depolymerized mono-, di-, and oligomeric compounds. They typically result in a product mixture consisting of a gaseous, liquid (i.e., mono-, di-, and oligomeric products), and solid phase. Consequently, researchers have developed a common strategy to simplify this issue by replacing lignin with simpler, but still representative, lignin model compounds. This strategy is typically applied to the elucidation of reaction mechanisms and the exploration of novel lignin conversion approaches. In this review, we present a general overview of the latest advances in the principal thermochemical processes applied for the conversion of lignin model compounds using heterogeneous catalysts. This review focuses on the most representative lignin conversion methods, i.e., reductive, oxidative, pyrolytic, and hydrolytic processes. An additional subchapter on the reforming of pyrolysis oil model compounds has also been included. Special attention will be given to those research papers using "green" reactants (i.e., H2 or renewable hydrogen donor molecules in reductive processes or air/O2 in oxidative processes) and solvents, although less environmentally friendly chemicals will be also considered. Moreover, the scope of the review is limited to those most representative lignin model compounds and to those reaction products that are typically targeted in lignin valorization.

Multicatalysis Combining 3D-Printed Devices and Magnetic Nanoparticles in One-Pot Reactions: Steps Forward in Compartmentation and Recyclability of Catalysts.

A tricatalytic compartmentalized system that immobilizes metallic species to perform one-pot sequential functionalization is described: a three-dimensional (3D)-printed palladium monolith, ferritic copper(I) magnetic nanoparticles, and a 3D-printed polypropylene capsule-containing copper(II) loaded onto polystyrene-supported 1,5,7-triazabicyclo[4.4.0]dec-5-ene (PS-TBD) allowed the rapid synthesis of diverse substituted 1-([1,1'-biphenyl]-4-yl)-1H-1,2,3-triazoles. The procedure is based on the Chan-Lam azidation/copper alkyne-azide cycloaddition/Suzuki reaction strategy in the solution phase. This catalytic system enabled the efficient assembly of the final compounds in high yields without the need for special additives or intermediate isolation. The monolithic catalyst-containing immobilized palladium species was synthesized by surface chemical modification of a 3D-printed silica monolith using a soluble polyimide resin as a key reagent, thus creating an extremely robust composite. All three immobilized catalysts described here were easily recovered and reused in numerous cycles. This work exemplifies the role of 3D printing in the design and manufacture of devices for compartmented multicatalytic systems to carry out complex one-pot transformations.