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

Abstract

Utilization of CO2 as feedstock to produce fine chemicals and renewable fuels is a highly promising field, which presents unique challenges in its implementation at scale. Heterogeneous catalysis with its simple operation and industrial compatibility can be an effective means of achieving this challenging task. This review summarizes the current developments in heterogeneous thermal catalysis for the production of carbon monoxide, alcohols and hydrocarbons from CO2. A detailed discussion is provided regarding structure-activity correlations between catalyst surface and intermediate species which can aid in rational design of future generation catalysts. Effects of active metal components, catalyst supports, and promoters are discussed in each section, which will guide researchers to synthesize new catalysts with improved selectivity and stability. Additionally, a brief overview regarding process design considerations has been provided. Future research directions are proposed with special emphasis on the application scope of new catalytic materials and possible approaches of increasing catalyst performance.

Multifunctional Catalyst Combination for the Direct Conversion of CO2 to Propane

“…The results are summarized in Figure 1 a. CO 2 conversion is similar for the three systems (filled symbols, left axis) and it increases with pressure and temperature, in agreement with the process thermodynamics. 11 On the other hand, selectivity follows a completely different trend (empty symbols, right axis). For the stand-alone PdZn/ZrO 2 catalysts, MeOH selectivity also follows the process thermodynamics, increasing with pressure and decreasing with temperature.…”

“…To the best of our knowledge, this is the highest total selectivity per pass ever reported for a single C 2+ hydrocarbon during CO 2 valorization. 11 We attribute these results to the intimate contact between the PdZn/ZrO 2 and SAPO-34 components that shifts the overall reaction equilibrium, ultimately boosting CO 2 conversion and minimizing CO selectivity. Kinetic modeling of the catalytic data alongside with thermodynamic equilibrium calculations fully support this hypothesis.…”

Rhenium – A Tuneable Player in Tailored Hydrogenation Catalysis

“…The FTS process can be made even greener by first converting CO 2 into CO, and in this way, using CO 2 as a feedstock to produce fuels, meaning the life‐cycle assessment of the FT fuel would outperform traditional fuel in all environmental aspects [82] . In spite of being very stable thermodynamically, CO 2 can also be directly hydrogenated into hydrocarbons, methane, and methanol, among other products, given a highly efficient catalyst is employed [83] …”

Two-dimensional molybdenum carbide 2D-Mo2C as a superior catalyst for CO2 hydrogenation

“…This property has been exploited for various catalytic processes including Fischer–Tropsch (FT) synthesis 3 , 4 , methane dry reforming 5 , water-gas shift (WGS) reaction 6 , 7 , and CO/CO 2 hydrogenation 8 , 9 . Currently, the conversion of captured CO 2 into value-added chemicals or fuels is considered a key strategy to mitigate the yet increasing anthropogenic CO 2 emissions 10 , 11 , in particular when combined with H 2 obtained using renewable energy 12 , 13 . Depending on the catalyst and the reaction conditions used, thermocatalytic CO 2 hydrogenation can give CO, methanol, dimethyl ether (DME), methane, or heavier hydrocarbons 12 , 14 .…”