ABSTRACT
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.
ABSTRACT
A methodology is introduced for controlled postsynthetic thermal defect engineering (TDE) of precious group metal-organic frameworks (PGM-MOFs). The case study is based on the Ru/Rh analogues of the archetypical structure [Cu3(BTC)2] (HKUST-1; BTC = 1,3,5-benzenetricarboxylate). Quantitative monitoring of the TDE process and extensive characterization of the samples employing a complementary set of analytical and spectroscopic techniques reveal that the compositionally very complex TDE-MOF materials result from the elimination and/or fragmentation of ancillary ligands and/or linkers. TDE involves the preferential secession of acetate ligands, intrinsically introduced via coordination modulation during synthesis, and the gradual decarboxylation of ligator sites of the framework linker BTC. Both processes lead to modified Ru/Rh paddlewheel nodes. These nodes exhibit a lowered average oxidation state and more accessible open metal centers, as deduced from surface-ligand IR spectroscopy using CO as a probe and supported by density functional theory (DFT)-based computations. The monometallic and the mixed-metal PGM-MOFs systematically differ in their TDE properties and, in particular in the hydride generation ability (HGA). This latter property is an important indicator for the catalytic activity of PGM-MOFs, as demonstrated by the ethylene dimerization reaction to 1-butene.
