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WIREs Comput Mol Sci
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Theoretical study of crystal phase effect in heterogeneous catalysis

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Density functional theory (DFT) is a powerful tool to study heterogeneous catalysis nowadays. In past decades, numerous DFT calculations have been conducted to investigate the mechanism of catalytic reaction from which the rationale of catalyst design can be revealed. Because the catalyst electronic and geometric structures determine the intrinsic activity, corresponding composition, size, and morphology have been explored extensively to tune the structure–activity relationship for higher activity and selectivity. In this review, we focus on the recent theoretical progress of the crystal phase effect on catalysis. Catalysts with different crystal phases have different symmetries, and could expose very different facets with distinct electronic and geometrical properties, which would have significant influential on the activity and selectivity of the active sites as well as the site density. Exploration of the dependence of catalysis on the crystal phases provides a new rationale of catalysts design toward a high‐specific activity. WIREs Comput Mol Sci 2016, 6:571–583. doi: 10.1002/wcms.1267 This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis
The crystal structures (under standard conditions) of transition metal in the periodic table of element. The point groups are indicated for the three typical crystal structures.
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CO conversion versus time over Fe, Fe2C, Fe7C3, and Fe5C2 catalysts (reaction condition: 270°C, 30 bar, 20 ml/min syngas) (a); the scheme for CO hydrogenation on Fe and Fe5C2 (b).
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(a) Apparent barriers for CO activation, C2 and CH4 formation on Fe5C2 (100) and Fe (310) surfaces. (b) The transition states for CO activation on Fe5C2 (100) and Fe (310) surfaces.
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Scheme for the high alcohol formation at interface between Co and Co2C. (Reproduced with permission from Ref . Copyright 2015 American Chemical Society.)
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Energetic and geometric information for direct CO activation on Co2C (111) (red) and Co (100) (blue) surfaces. The corresponding CO adsorption, transition state, and C adsorption geometries are shown in (b)–(e). (Reproduced with permission from Ref . Copyright 2015 American Chemical Society.)
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The crystal structures and the corresponding density of state of bulk Co, Co2C, and Rh.
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Analysis of the interface between Ru and FCC noble metals. (a) and (b) are the formation of the interfaces between the Ru and other transition metals with FCC structure. (c) DFT calculated formation energies of (111) and (100) interfaces between FCC Pt, Pd, Rh, and Ru. (d) HRTEM images and 3D models of FCC Pt seeds with cubooctahedral morphology from (left) [01] and (right) [001] zone axes. Red and blue surfaces in these models represent {100} and {111} facets, respectively. The scale bars indicate 2 nm. (Reproduced with permission from Ref . Copyright 2015 American Chemical Society.)
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Size dependence of the temperature for 50% conversion of CO to CO2 (T50) for FCC (blue) and HCP (red) Ru nanoparticles. (Reproduced with permission from Ref . Copyright 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)
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Calculated potential energy (in eV) for CO activation at the transition states for breaking the CO bond via the direct route (CO* + H* → C* + O* + H*) (red) and the H‐assisted route (CO* + H* → CHO* → CH* + O*) (blue) on HCP and FCC Co surfaces. The zero energy reference is CO + 1/2 H2 in the gas phase. (Reproduced with permission from Ref . Copyright 2013 American Chemical Society.)
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Top and side view of optimized transition states for CO dissociation on FCC and HCP Co surfaces. Blue, red, and gray balls represent Co, O, and C atoms, respectively. (Reproduced with permission from Ref . Copyright 2013 American Chemical Society.)
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Equilibrium morphology of HCP and FCC Co based on the Wulff construction and calculated reaction rates r for CO dissociation on exposed HCP and FCC Co facets at the low coverage. All rates are normalized by that of HCP (0001) with units of s−1 site−1. (Reproduced with permission from Ref . Copyright 2013 American Chemical Society.)
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