Abstract:Catalytic conversion of CO2 including hydrogenation has attracted great attention as a method for chemical fixation of CO2 in combination with other techniques such as CO2 capture and storage. Potassium is a well-known promotor for many industrial catalytic processes such as in Fischer-Tropsch synthesis. In this work, we performed density functional theory (DFT) calculations to investigate the effect of potassium on the adsorption, activation, and dissociation of CO2 over Fe(100), Fe5C2(510) and Fe3O4(111) sur… Show more
“…The addition of K to Fe–Cu/Al 2 O 3 catalysts can further inhibit methanation and enhance the production of olefin-rich C 2 –C 4 hydrocarbons by increasing the surface coverage of carbon 85 . DFT calculations show that the presence of K on Fe-based surfaces can enhance the CO 2 adsorption strength and reduce the CO 2 dissociation barrier (e.g., 2.36 eV for oct2-Fe 3 O 4 (111) versus 1.13 eV for K/oct2-Fe 3 O 4 (111)) 109 . Therefore, the introduction of promoters can modify the surface electronic features.Fig.…”
Section: Fischer–tropsch Synthesis (Fts)-based Co2 Hydrogenationmentioning
Recently, carbon dioxide capture and conversion, along with hydrogen from renewable resources, provide an alternative approach to synthesis of useful fuels and chemicals. People are increasingly interested in developing innovative carbon dioxide hydrogenation catalysts, and the pace of progress in this area is accelerating. Accordingly, this perspective presents current state of the art and outlook in synthesis of light olefins, dimethyl ether, liquid fuels, and alcohols through two leading hydrogenation mechanisms: methanol reaction and Fischer-Tropsch based carbon dioxide hydrogenation. The future research directions for developing new heterogeneous catalysts with transformational technologies, including 3D printing and artificial intelligence, are provided.
“…The addition of K to Fe–Cu/Al 2 O 3 catalysts can further inhibit methanation and enhance the production of olefin-rich C 2 –C 4 hydrocarbons by increasing the surface coverage of carbon 85 . DFT calculations show that the presence of K on Fe-based surfaces can enhance the CO 2 adsorption strength and reduce the CO 2 dissociation barrier (e.g., 2.36 eV for oct2-Fe 3 O 4 (111) versus 1.13 eV for K/oct2-Fe 3 O 4 (111)) 109 . Therefore, the introduction of promoters can modify the surface electronic features.Fig.…”
Section: Fischer–tropsch Synthesis (Fts)-based Co2 Hydrogenationmentioning
Recently, carbon dioxide capture and conversion, along with hydrogen from renewable resources, provide an alternative approach to synthesis of useful fuels and chemicals. People are increasingly interested in developing innovative carbon dioxide hydrogenation catalysts, and the pace of progress in this area is accelerating. Accordingly, this perspective presents current state of the art and outlook in synthesis of light olefins, dimethyl ether, liquid fuels, and alcohols through two leading hydrogenation mechanisms: methanol reaction and Fischer-Tropsch based carbon dioxide hydrogenation. The future research directions for developing new heterogeneous catalysts with transformational technologies, including 3D printing and artificial intelligence, are provided.
“…In the specific case of the gaseous CO 2 , single‐crystal surfaces have been found to be less interesting since, on most metal surfaces, CO 2 simply physisorbs with a concomitant lack of activation, especially in the case of the highly stable Miller low‐index surfaces. The picture is slightly different in the case of stepped surfaces or surfaces incorporating promoter species as Li, Na, or K, 197 or in the electrochemical CO 2 reduction reaction (CO2RR) where single‐crystal metal electrodes, in special based on copper, have been heavily studied in the literature, both experimentally and computationally 198,199 …”
Section: Representative Examples Of Computational Studies For Co2 Conversionmentioning
confidence: 99%
“…The promoter effect of potassium on the CO 2 activation was studied by Nie et al 197 by comparing PBE + U ( U Fe = 3.8 eV) calculated results for the adsorption and dissociation of CO 2 on the clean and K‐covered Fe(100) surfaces. These authors found that potassium prefers to adsorb at fourfold sites rather that at top or bridge locations.…”
Section: Representative Examples Of Computational Studies For Co2 Conversionmentioning
confidence: 99%
“…In the specific case of the gaseous CO 2 , single-crystal surfaces have been found to be less interesting since, on most metal surfaces, CO 2 simply physisorbs with a concomitant lack of activation, especially in the case of the highly stable Miller low-index surfaces. The picture is slightly different in the case of stepped surfaces or surfaces incorporating promoter species as Li, Na, or K, 197 or in the electrochemical CO 2 reduction reaction (CO2RR) where single-crystal metal electrodes, in special based on copper, have been heavily studied in the literature, both experimentally and computationally. 198,199 Recently, Ko et al 200 performed a comparative computational study of the activation of CO 2 upon adsorption on several low-index metal surfaces including Fe(110), Co(0001), Ni (111), Ru(0001), Rh(111), Pd(111), Ir(111), Pt(111), Cu (111), Ag (111), and Au(111), using the PBE density functional and adding dispersion by means of the D2 method.…”
Section: Single-crystal Metal Surfacesmentioning
confidence: 99%
“…Correlations were found only when plotting the activation energies against the calculated reaction energies or the sum of the adsorption energies of the products of the dissociation reaction, see Figure 3(c), with R 2 values of 0.79 and 0.72, respectively, nicely following the Brønsted-Evans-Polanyi (BEP) earlier introduced by Neurock and Pallassana, 201 and broadly exploited by other groups. 162,202,203 The promoter effect of potassium on the CO 2 activation was studied by Nie et al 197 by comparing PBE + U (U Fe = 3.8 eV) calculated results for the adsorption and dissociation of CO 2 on the clean and K-covered Fe(100) surfaces. These authors found that potassium prefers to adsorb at fourfold sites rather that at top or bridge locations.…”
Theoretical investigations and computational studies have notoriously contributed to the development of our understanding of heterogeneous catalysis during the last decades, when powerful computers have become generally available and efficient codes have been written that can make use of the new highly parallel architectures. The outcomes of these studies have shown not only a predictive character of theory but also provide inputs to experimentalists to rationalize their experimental observations and even to design new and improved catalysts. In this review, we critically describe the advances in computational heterogeneous catalysis from different viewpoints. We firstly focus on modeling because it constitutes the first key step in heterogenous catalysis where the systems involved are tremendously complex. A realistic description of the active sites needs to be accurately achieved to produce trustable results. Secondly, we review the techniques used to explore the potential energy landscape and how the information thus obtained can be used to bridge the gap between atomistic insight and macroscale experimental observations. This leads to the description of methods that can describe the kinetic aspects of catalysis, which essentially encompass microkinetic modeling and kinetic Monte Carlo simulations. The puissance of computer simulations in heterogeneous catalysis is further illustrated by choosing CO2 conversion catalyzed by different materials for most of which a comparison between computational information and experimental data is available. Finally, remaining challenges and a near future outlook of computational heterogeneous catalysis are provided.
This article is categorized under:
Structure and Mechanism > Computational Materials Science
Structure and Mechanism > Reaction Mechanisms and Catalysis
Carbon dioxide (CO2) valorization to light olefins via sustainable energy input poses great industrial significance for the synthesis of key chemical feedstocks and reduces emission of this potent greenhouse gas. Solar energy, harnessed using light‐capturing catalytic materials, can negate external heat requirements for the energy‐intensive reaction. Presently, photothermal CO2‐Fischer–Tropsch synthesis (FTS)‐dedicated studies remain limited and are focused on the nonselective synthesis of C2+ hydrocarbons. A possible extension in catalyst design may be leveraged upon re‐examination of the better‐established thermal CO2‐FTS in conjunction with studies on photothermal FTS. To this end, herein, a narrative on the prominent chemical mechanisms and existing strategies for Fe‐based catalyst design within thermal CO2‐FTS as a foundation is established. Then, with the intent of regulating product selectivity, a gap in the adaptation of encapsulated structures involving zeolitic frameworks for CO2‐FTS is discussed. Next, current photothermal studies on C2+ hydrocarbon synthesis via FTS, CO2‐FTS, and relevant thermal‐assisted photocatalytic systems involving CO2 conversion are examined. Finally, the possible applications of structures encapsulated by porous media for boosting light utilization for photothermal CO2‐FTS are considered. Overall, the potential for the uptake of strategies aimed at producing multifunctional, light‐responsive future catalysts suitable for CO2‐FTS is explored.
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