Metal–Organic Framework-Derived Synthesis of Cobalt Indium Catalysts for the Hydrogenation of CO₂ to Methanol

Abstract

Methanol synthesis by means of direct CO 2 hydrogenation has the potential to contribute to climate change mitigation by turning the most important greenhouse gas into a commodity. However, for this process to become industrially relevant, catalytic systems with improved activity, selectivity and stability are required. Here we explore the potential of metal-organic frameworks (MOF) as precursors for synthesis of Co 3 O 4 -supported In 2 O 3 oxide composites for the direct CO 2 hydrogenation to methanol. Stepwise pyrolytic-oxidative decomposition of indium-impregnated ZIF-67(Co) MOF affords the formation of a nanostructured In 2 O 3 @Co 3 O 4 reticulated shell composite material able to reach a maximum methanol production rate of 0.65 g MeOH •g cat -1 •h -1 with selectivity as high as 87% over 100 h on stream. Textural characteristics of the sacrificial ZIF-67(Co) matrix and In-loading were found to be important variables for optimizing the catalyst performance such as induction time, methanol productivity and selectivity. The structural investigation on the catalytic system reveals that the catalyst undergoes reorganization under reaction conditions, transforming from a Co 3 O 4 with amorphous In 2 O 3 shell into Co 3 InC 0.75 covered by a layer consisting of a mixture of amorphous CoO x and In 2 O 3 oxides. Structural reorganization is responsible for the observed induction period, while the amorphous mixed cobalt indium oxide shell is responsible for the high methanol yield and selectivity. Additionally, these results demonstrate the tunable performance of MOF-derived In 2 O 3 @Co 3 O 4 catalyst as a function of the reaction conditions which allows to establish a reasonable trade-off between high methanol yield and selectivity in a wide temperature and pressure window.

Advances in the Design of Heterogeneous Catalysts and Thermocatalytic Processes for CO2 Utilization

“…Similarly, after the discovery of excellent methanol selectivity and remarkable stability of indium oxide (In2O3), 161 different bimetallic indium catalysts were also studied. 147,150,151,153,[162][163][164][165][166][167][168][169] A second metal is usually required because the H2-splitting ability of In is limited. Among recent examples, Pd-In bimetallic system showed that intermetallic Pd-In nanoparticles were able to produce methanol at around 70% higher rates as compared to Cu/ZnO/Al2O3 catalyst at 210 °C.…”

Monoclinic Scheelite Bismuth Vanadate Derived Bismuthene Nanosheets with Rapid Kinetics for Electrochemically Reducing Carbon Dioxide to Formate

“…[ 2 ] Above challenges originate from intrinsically sluggish reaction kinetics caused by multiple CO 2 reduction pathways and competition of hydrogen evolution reaction (HER). In general, the products from CO 2 RR can be divided into two categories: 1) C 1 products such as CO, [ 3,4 ] methanol, [ 5,6 ] formate (or formic acid), [ 7,8 ] etc. ; 2) multi‐carbon (C 2+ ) products including ethylene, [ 9,10 ] ethanol, [ 11 ] etc.…”

Direct Synthesis of Dimethyl Ether from CO2: Recent Advances in Bifunctional/Hybrid Catalytic Systems

“…Various non-noble intermetallic compounds (Ni-Ga [84], In-Co [85], and In-Ni [86] have also been studied as new formulations for the synthesis of methanol from CO 2 . Among these, Ni-Ga intermetallic catalysts (Ni 5 Ga 3 ) supported on SiO 2 were reported as more active and selective for the hydrogenation of CO 2 at ambient pressure than conventional Cu/ZnO/Al 2 O 3 catalysts [84].…”