CO2 Hydrogenation on Metal-Organic Frameworks-Based Catalysts: A Mini Review

Abstract

Conversion of carbon dioxide (CO2) into value-added fuels and chemicals can not only reduce the emission amount of CO2 in the atmosphere and alleviate the greenhouse effect but also realize carbon recycling. Through hydrogenation with renewable hydrogen (H2), CO2 can be transformed into various hydrocarbons and oxygenates, including methanol, ethanol, methane and light olefins, etc. Recently, metal-organic frameworks (MOFs) have attracted extensive attention in the fields of adsorption, gas separation, and catalysis due to their high surface area, abundant metal sites, and tunable metal-support interface interaction. In CO2 hydrogenation, MOFs are regarded as important supports or sacrificed precursors for the preparation of high-efficient catalysts, which can uniformly disperse metal nanoparticles (NPs) and enhance the interaction between metal and support to prevent sintering and aggregation of active metal species. This work summarizes the recent process on hydrogenation of CO2 to methanol, methane and other C2+ products over various MOFs-based catalysts, and it will provide some dues for the design of MOFs materials in energy-efficient conversion and utilization.

Zr-Based MOF-545 Metal–Organic Framework Loaded with Highly Dispersed Small Size Ni Nanoparticles for CO2 Methanation

“…In the past decade, there has been a surge of interest in MOFs within the realms of CO 2 adsorption, gas separation, and catalysis owing to their remarkable attributes such as a large surface area, tunable porosity, strong metal binding sites, and the capacity for tailored metal–support interactions . In the field of CO 2 hydrogenation, MOFs have emerged as pivotal supports or sacrificial precursors, playing a promising role in the fabrication of efficient catalysts. − MOF-based catalysts may be specifically designed to ensure the uniform dispersion of metal nanoparticles (NPs) and augment the interplay between NPs and the support, effectively preventing the undesired phenomena of sintering and aggregation of active metal species. , In particular, a number of Ni-containing MOF catalysts have been reported in the past decade for CO 2 methanation, exploiting the high dispersion of small-size Ni NPs, including Ni@MOF-5, Ni@MIL-101-Cr, , and Ni@UiO-66. , Moreover, MOF-derived Ni-containing systems have been also reported as sacrificial precursors for the synthesis of efficient catalytic materials, via high temperature (>500 °C) pyrolysis. − Overall, these studies shed light on key features that determine the performances of these Ni-based catalysts, such as the impact of the metal immobilization methods, the nickel reduction conditions, or the Ni loading, in addition to the catalytic conditions themselves (temperature, reactants ratio,...). In parallel, the catalytic activities are also known to be strongly dependent on the support used (SiO 2 , CeO 2 , TiO 2 , ZrO 2, or MgO) .…”

Thermocatalytic Conversion of CO2 to Valuable Products Activated by Noble‐Metal‐Free Metal‐Organic Frameworks

“…Many important researches focused on hydrogenation, [42–45] reduction, [46–51] cycloaddition, [52–56] carboxylation, [57–59] and coupling reactions [60–63] have been reported in recent years. MOFs have become promising catalysts owing to the following reasons: 1) As a porous material, the pore sizes of MOFs can be tuned by regulating the sizes of organic ligands or guest template agents, thereby controlling the transfer rates of substrates and products and improving the reaction selectivity to different substrates [64–66] . 2) As heterogeneous catalysts, MOFs can be easily isolated from the reaction mixture and used in the next cycle [67–69] .…”

Theoretical Study on the Catalytic CO2 Hydrogenation over the MOF-808-Encapsulated Single-Atom Metal Catalysts

“…In the past few years, metal–organic framework (MOF)-supported or -encapsulated metal nanoparticles (MNPs) have been reported as one of promising strategies for the conversion of CO 2 into value-added fuels or chemicals. ,, It is largely due to the well-defined and diversified pore surface structures of MOFs that can stabilize the MNPs without sintering or even deactivation by providing a well-confined reactive environment. − For example, Zurrer et al used NiMg–MOF-74 as a template to disperse small Ni nanoclusters, and Ni II was selectively reduced to highly dispersed Ni nanoclusters. By changing the ratio of Ni/Mg in the parent MOF, the available surface area and crystallinity can be adjusted after the thermal treatment to improve CO 2 adsorption and hydrogenation selectivity.…”