Computational Approaches to the Chemical Conversion of Carbon Dioxide

Abstract

The conversion of CO₂ into fuels and chemicals is viewed as an attractive route for controlling the atmospheric concentration and recycling of this greenhouse gas, but its industrial application is limited by the low selectivity and activity of the current catalysts. Theoretical modeling, in particular density functional theory (DFT) simulations, provides a powerful and effective tool to discover chemical reaction mechanisms and design new catalysts for the chemical conversion of CO₂, overcoming the repetitious and time/labor consuming trial-and-error experimental processes. In this article we give a comprehensive survey of recent advances on mechanism determination by DFT calculations for the catalytic hydrogenation of CO₂ into CO, CH₄, CH₃OH, and HCOOH, and CO₂ methanation, as well as the photo- and electrochemical reduction of CO₂. DFT-guided design procedures of new catalytic systems are also reviewed, and challenges and perspectives in this field are outlined.

Electrolyte-less design of PEC cells for solar fuels: Prospects and open issues in the development of cells and related catalytic electrodes

“…Water oxidation [52][53][54][55][56][57][58][59] and CO 2 activation [60][61][62][63][64][65][66] have been widely studied. Water splitting by photosynthetic molecules or organisms occurs in nature with low productivity and overall efficiency in use of the light, although high in terms of efficiency of using the adsorbed photons [29].…”

Two-Dimensional Layered Double Hydroxide Derived from Vermiculite Waste Water Supported Highly Dispersed Ni Nanoparticles for CO Methanation

“…Since carbon oxide methanation was discovered by Sabatier and Senderens in 1902, it has been well developed and widely used due to its capability as a chemical storage for excess H 2 generated from renewable energy and a solution for greenhouse gas recycling [1][2][3]. Synthetic natural gas (SNG) via methanation can result in the clean utilization of coal and biomass, and this can prove to be an…”

Computational studies of electrochemical CO2 reduction on subnanometer transition metal clusters

“…Hori et al discovered experimentally that CO 2 is reduced to CH 4 , C 2 H 4 and alcohols at Cu electrodes, with overpotentials on the order of 1 V. 7,15 More importantly, the surface orientation of Cu crystals plays a significant role in the selectivity of the products. For instance, CH 4 formation is favored at Cu(111), while C 2 H 4 is more likely to form at Cu(100). 18 The reaction mechanisms of the formation of CH 4 and longer chain hydrocarbons at Cu electrodes were studied computationally by the Nørskov group 17 and the Koper group.…”

“…High thermodynamic stability of the CO 2 molecule requires substantial input of energy for its reduction and conversion. Studies of catalytic reduction of CO 2 to useful chemicals, such as CO, HCOOH, CH 3 OH, CH 4 and longer-chain hydrocarbons, have been focused on three major approaches: chemical, 1-4 electrochemical 2,5-10 and photochemical reductions. 2,11,12 During the last three decades, electrochemical reduction of CO 2 has gained increasing interest from both academia and industry.…”