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WIREs Comput Mol Sci
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Theoretical modeling for interfacial catalysis

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Abstract Heterogeneous catalysis is vital in modern chemical industry. The development of next‐generation heterogeneous catalysts demands methodological shift from trial‐and‐error to theory‐guided design. However, heterogeneous catalysis usually involves complex surfaces/interfaces, which make it difficult to establish a reasonable model. Herein, we reviewed the recent progress in our group, and demonstrated a new research paradigm to successfully bridge the material gap between theory and experiment. Accordingly, three important interfacial effects of heterogeneous catalysts have been discussed in detail, that is, the support effect of oxide‐on‐metal catalysts, the coordination effect of atomically dispersed metal catalysts (ADCs) and the ligand effect of molecular modification. We addressed that the close cooperation of theory and experiment is essential to gain deep mechanistic insights and help to optimize heterogeneous catalysts in a more rational way. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis
Complexity of real‐world heterogeneous catalysts
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(a) “Invisible” organic layer by TEM. (b) Schematic illustration of surface density, the orientation of the ligands and possible phase transition induced by ligands. (c) Alkylamine‐capped Pt3Co models and possible catalytic functions. (Figure 7(a,c) were reproduced with permission from Ref. 78. Copyright 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim). (d) Selective hydrogenation of 2‐methyl‐3‐butyn‐2‐ene over Pd‐HHDMA and Pd‐Pb. (Reprinted with permission from Ref. 79. Copyright 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim). (e) Bare Pt NW and EDA‐Pt NW models. (Reprinted with permission from Ref. 88. Copyright 2016 Nature Publishing Group). (f) Adsorption energy of H2 on Pd clusters with different sizes. (Reprinted with permission from Ref. 89. Copyright 2020 Ruixuan Qin et al.) (g) Surface phase transition introduced by thiolate. (h) Energy profile of PhC≡CCH3 hydrogenation on the Pd4[email protected]2 surface. (Reprinted with permission from Ref. 93. Copyright 2018 Elsevier Inc)
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(a) STM evidence for spilled hydrogen atoms on Cu surface. (b) Potential energy diagram of dissociative adsorption of H2 on Pd(111), Pd atom, and Cu(111). (Figure 6(a,b) were reprinted with permission from Ref. 71. Copyright 2012 American Association for the Advancement of Science). (c) Possible reactive sites on the Pd1/Cu(111) surface. (d) Top and side views of the Pd1/Cu(111), Pd1/Cu(100), and Pd1/Cu(110) models. (e) The potential energy profiles for stepwise hydrogenation of PhC≡CH on the three low‐miller‐index Cu surfaces. (f) Comparison of barriers for TS1 over different active sites on different Pd1/Cu catalysts. (Figure 6(c)–(f) were reproduced with permission from Ref. 73. Copyright 2020, The Author[s], under exclusive license to Springer Nature Limited)
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(a) Electronic effect introduced by K atom. (Reprinted with permission from Ref. 65. Copyright American Physical Society). (b) Structural effect of K2O on size/morphology of Fe nanocrystals. (Reprinted with permission from Ref. 66. Copyright 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim). (c) Comparison of H2 activation and conversion on Ru(Na) and Ru(H). (d) Schematic diagram of the coulomb interaction between Na+(H+) and hydride species. (e) Comparison of the energy barriers for acetone hydrogenation over Ru(0001), Ru(1120), and Ru(Na). (f) The interaction between surface Na+ and O in substrates during the acetone hydrogenation. (Figure 5(c)–(f) were reproduced with permission from Ref. 67. Copyright 2020 Springer Nature)
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(a) The optimized structure of EG‐TiO2(B)(100). (b) DOS of EG‐TiO2(B)(100). (c) Spin densities of –CH2·CHOH species. (d) Formation mechanism of Pd1/TiO2. (e) Mechanisms of heterolytic H2 activation on Pd1/TiO2. (Figure 4(a)–(e) were reprinted with permission from Ref. 63. Copyright 2016 American Association for the Advancement of Science). (f) The experimental evidence for the formation of Ti3+ adjacent to Pd. (g) Energy profile for CO oxidation at the Pd–O–Ti3+ interface. (Figure 4(f,g) were reprinted with permission from Ref. 64. Copyright 2018 Science China Press. Published by Elsevier B.V. and Science China Press)
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Computational models for oxide‐on‐metal inverse catalysts. (a) Conventional supported metal catalyst. (b) Oxide‐on‐metal reverse catalyst. (c) Possible coordination structures of metal cations at the surfaces/interfaces. (d) Construction strategy for oxide‐on‐metal model. (e) Side and top views of FeO1 − x/Pt(111) model. (Reprinted with permission from Ref. 44. Copyright 2010 American Association for the Advancement of Science). (f) The model for FeO2/Pt(111) and the energy profile for CO oxidation. (Reprinted with permission from Ref. 45. Copyright 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim). (g) The model for Fe(OH)x/Pt(332) interface. (h) Energy profile for CO oxidation on Fe(OH)x/Pt(332). (i) 18O isotope‐labeling experiments. (Figure 2(g)–(i) were reprinted with permission from Ref. 46. Copyright 2014 American Association for the Advancement of Science). (j) The model for SiOx/Cu(111) interface. (k) Energy profile and key intermediate structures for the DMO hydrogenation on Cu(111) and SiOx/Cu(111). (l) Pre‐treatment of Na+ ions on Cu–O–Si interface deterred the hydrogenation. (Figure 2(j)–(l) were reprinted with permission from Ref. 59, Springer Nature Ltd.)
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The models of ADCs. (a) Atomic‐resolution STEM image of Pd1/TiO2. (b) Schematic representation of ADCs. (c) the possible coordination structures of active metal species. (d) Three possible ways of active metals bound with surfaces. Examples of ADCs: (e) Pd1/TiO2, (f) Pd1/Cu2O, and (g) Ru1‐Na/Al2O3. (Figure 3(a,e) were reproduced with permission from Ref. 63. Copyright 2016 American Association for the Advancement of Science. Figure 3(f) was reproduced with permission from Ref. 62. Copyright 2019 Chinese Chemical Society. Figure 3(g) was reproduced with permission from Ref. 67. Copyright 2020 Springer Nature)
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