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WIREs Comput Mol Sci
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Review of two‐dimensional materials for electrochemical CO2 reduction from a theoretical perspective

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The massive use of fossil fuels emits a large amount of carbon dioxide gas, which brings inevitable damage to the ecological environment. The conversion of carbon dioxide (CO2) into organic fuel molecules or other industrial raw materials by electrochemical reduction is an important means to reduce the CO2 content in the atmosphere and establish a new carbon resource balance system. However, the currently used catalysts for electrochemical CO2 reduction are still unsatisfactory because of several serious problems, such as high overpotential, low selectivity, and high cost. Compared to conventional three‐dimensional (3D) catalysts, it is expected that two‐dimensional (2D) catalysts with ultra‐large surface area, abundant surface atoms, and excellent electrical conductivity along 2D channels could be more beneficial toward CO2 electrochemical reduction. Recently, the application of 2D materials in the field of CO2 electrocatalytic conversion has just begun to receive attention. In this overview, we summarized the latest advances on developing novel 2D materials as catalysts for CO2 electrochemical reduction and highlighted the important role of theoretical simulation in this emerging field. We hope that this overview could provide some guidance for both theoretical and experimental communities to further designing 2D electrocatalysts for CO2 reduction and understanding the corresponding mechanisms. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Structure and Mechanism > Computational Materials Science
Potential electrical carbon dioxide reduction pathways to form the C1 products of CO, HCOOH, CH4, and the C2 products of C2H4, C2H5OH
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Density functional theory (DFT) stimulated minimum energy path for the CO2 conversion into CH4 on Mo3C2 surface. Gray, lilac, red, and white spheres refer to C, Mo, O, and H atoms, respectively. The blue numbers demonstrate the energy released by each elementary reaction, while the red numbers are the energy required to carry out an elementary reaction. (Reprinted with permission from Reference from ). Copyright 2017 American Chemical Society)
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Computed free energy profiles for the electrochemical reduction of CO2 to formate on the Co3O4 single‐unit‐cell layers with oxygen vacancies (a) and the intact Co3O4 single‐unit‐cell layers (b), respectively. The first step is the formation of CO2* anion via a electron transfer while the second step involves a simultaneous proton/electron transfer. The final step is the desorption of HCOO into solvent. (Reprinted with permissions from Reference . Copyright 2017 Springer Nature)
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Density functional theory (DFT) simulations of the CO2RR process on a CoPPc. The initial structure of CoPPc were presented in (a).The main intermediates along the reaction path for CO2 reduction to CO were listed in (b)–(e) (CoPPc, CO2*, COOH*, and CO*) Co, N, O, C, and H atoms are presented by orange, blue, red, gray, and green spheres, respectively. The binding length for CoN and CoC were marked on figures. For CoPPc and CO2*, the electron density differences caused by electron injection and CO2 adsorption are also plotted. Cyan and purple correspond to electron accumulation and depletion regions, respectively. (f) Proposed mechanism for electrochemical CO2 reduction on 2D CoPPc. (Reprinted with permissions from Reference . Copyright 2017 Elsevier)
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Density functional theory (DFT) simulation of the electrochemical CO2 reduction process on Bi (001) plane. (a)–(c) Optimized structure of (a) CO2, (b) OCHO* adsorbate and (c) HCOO, where Bi, C, O, and H atoms were presented by purple, gray, red, and green balls, respectively; (d) free‐energy diagrams for HCOO, CO, and H2 formation on Bi (001) plane were listed to show the products selectivity; (e) projected p‐orbital DOS of the Bi site with OCHO*, COOH*, or H* adsorbate, the Fermi level (EF) locates at 0 eV, the Ep in OCHO*, and COOH* and H* were colored with yellow, blue, and green dashed lines for catalytic activity comparison. (Reprinted with permissions from Reference . Copyright 2018 Springer Nature)
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(a) Geometric structures of Nb‐doped MoS2 with different position of dopant. (b) Free energy profiles for CO2 electrochemical reduction to CO on MoS2, NbS2, and Nb‐doped MoS2 edges. Two different kinds of Nb‐doped MoS2 were constructed by replacing the second and third row of Mo atoms from the edge, respectively. (c) Trends of COOH* formation energies and CO desorption energies on the bare metal edge of different systems. (Reprinted with permissions from Reference . Copyright 2017 American Chemical Society)
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(a) Optimized geometry structures of M − N4 − C10 and M − N2 + 2 − C8 (M = Fe or Co) active sites. (b) Computed free energy profile of CO2 electrochemical reduction to CO on M − N2 + 2 − C8 sites under an external electrode potential (U) of 0 V and − 0.6 V. (c) The initial and final states for the COOH dissociation on M − N4 − C10 and M − N2 + 2 − C8 sites. In the figure, the gray, blue, yellow, red, and white balls represent C, N, M, O, and H atoms, respectively. (Reprinted with permissions from Reference . Copyright 2017 American Chemical Society)
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Density functional theory (DFT) modeling of electro‐reduction process of CO2 reduction on N‐doped graphene. (a) Free energy diagram of CO2 conversion process on N–doped graphene. (b) Schematic of N configuration and CO2 reduction pathway. (Reprinted with permission from Reference . Copyright 2016 American Chemical Society)
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