CO₂ Methanation via Amino Alcohol Relay Molecules Employing a Ruthenium Nanoparticle/Metal Organic Framework Catalyst

Abstract

Methanation of carbon dioxide (CO2) is attractive within the context of a renewable energy refinery. Herein, we report an indirect methanation method that harnesses amino alcohols as relay molecules in combination with a catalyst comprising ruthenium nanoparticles (NPs) immobilized on a Lewis acidic and robust metal–organic framework (MOF). The Ru NPs are well dispersed on the surface of the MOF crystals and have a narrow size distribution. The catalyst efficiently transforms amino alcohols to oxazolidinones (upon reaction with CO2) and then to methane (upon reaction with hydrogen), simultaneously regenerating the amino alcohol relay molecule. This protocol provides a sustainable, indirect way for CO2 methanation as the process can be repeated multiple times.

Electronic Modulation Caused by Interfacial Ni‐O‐M (M=Ru, Ir, Pd) Bonding for Accelerating Hydrogen Evolution Kinetics

“…Ru 3p XPS spectrum of Ru@Ni‐MOF in Figure 2 a shows that the two peaks at 462.4 eV and 485.3 eV, are assigned to metallic Ru 3p 3/2 and 3p 1/2 , respectively [24, 37] . The other two peaks located at 464.6 eV and 487.1 eV correspond to the formation of Ru‐O linkages between the edge of the Ru NPs and the carboxyl groups of the Ni‐MOF [38] . Moreover, Ru@Ni‐MOF has a newly formed bond at 530.7 eV related to Ni‐O‐Ru (Figure 2 b).…”

Insights into the Structure–Activity Relationship in Aerobic Alcohol Oxidation over a Metal–Organic-Framework-Supported Molybdenum(VI) Catalyst

“…To better determine the structure of active species and achieve the goal of rationally designing supported catalysts, it is imperative to pursue a different strategy to obtain a comprehensive understanding of structure–activity relationships in heterogeneous catalytic systems. To this end, crystalline metal–organic frameworks (MOFs), a class of porous materials constructed from versatile inorganic nodes and tunable organic linkers, are promising as they provide uniform and well-defined supports for catalytic metal species. − Their high accessible porosity, facile functionalization, and exceptional structural diversity make MOFs ideal supports for investigating the structure–activity relationships of heterogeneous catalytic systems. − MOFs offer discrete and spatially isolated grafting sites, allowing for the preparation of single-atom or single-site catalysts and thereby preventing the agglomeration of active species during catalytic reactions. Similarly, MOF supports also improve metal-atom-utilization efficiency, enhance catalytic activities, and inhibit undesirable side reactions. ,, Owing to the support’s crystallinity, the atomically precise structural determination of anchored catalytic species becomes viable through crystallographic techniques, thereby providing a unique platform for directly probing structure–activity relationships.…”

Electronic Modulation Caused by Interfacial Ni‐O‐M (M=Ru, Ir, Pd) Bonding for Accelerating Hydrogen Evolution Kinetics

“…[24,37] The other two peaks located at 464.6 eV and 487.1 eV correspond to the formation of Ru-O linkages between the edge of the Ru NPs and the carboxyl groups of the Ni-MOF. [38] Moreover, Ru@Ni-MOF has a newly formed bond at 530.7 eV related to Ni-O-Ru (Figure 2 b). [16] The negative shifted Ni 2p 3/2 and Ni 2p 1/2 spin splitting peaks of the Ru@Ni-MOF also confirmed the chemical bonding (Figure 2 c and Table S2 in Supporting Information).…”

“…[24,37] The other two peaks located at 464.6 eV and 487.1 eV correspond to the formation of Ru-O linkages between the edge of the Ru NPs and the carboxyl groups of the Ni-MOF. [38] Moreover, Ru@Ni-MOF has a newly formed bond at 530.7 eV related to Ni-O-Ru (Figure 2 b). [16] The negative shifted Ni Additionally, the Fourier transform infrared spectroscopy (FT-IR) and Raman analysis also further reveal the formation of Ni-O-Ru bonds (Supporting Information, Figure S7).…”