Rational construction of thermally stable single atom catalysts: From atomic structure to practical applications

doi:10.1016/S1872-2067(21)63888-3

Abstract

Abstract:

As a new frontier in catalysis field, single-atom catalysts (SACs) hold unique electronic structure and high atom utilization, which have displayed unprecedented activity and selectivity toward a wide range of catalytic reactions. However, many reported SACs are susceptible to Ostwald ripening process in high temperature environment or long-term catalytic application, which will cause sintering and deactivation. This is due to the weak interaction between the metal atom and supports. The regeneration and recycling of deactivated catalysts will greatly increase the time and economic cost of industrial production. Therefore, it is necessary to develop SACs with excellent thermal stability to meet the industrial demands. Here, we discuss the fundamental comprehension of the stability of thermally stable SACs obtained from different synthesis methods. The influences of the speciation of metal centers and coordination environments on thermal stability are summarized. The importance of using novel in situ and operando characterizations to reveal dynamic structural evolution under synthesis and reaction conditions and to identify active sites of thermally stable SACs is highlighted. The mechanistic understanding of the unique role of thermally stable SACs in thermocatalytic application is also discussed. At last, a brief perspective on the remaining challenges and future directions of thermally stable SACs is presented.

Key words: Thermal stability, Single-atom catalyst, Sintering and deactivation, Synthesis method, Thermocatalytic application

Hongwei Lv, Wenxin Guo, Min Chen, Huang Zhou, Yuen Wu. Rational construction of thermally stable single atom catalysts: From atomic structure to practical applications[J]. Chinese Journal of Catalysis, 2022, 43(1): 71-91.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63888-3

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Figures/Tables 10

Scheme 1. Illustration of timeline of milestones in the research and development of single-atom catalysts.

Fig. 1. Synthesis of thermally stable SACs by high temperature pyrolysis. (a) The synthesis of Co SAs/N-C. Adapted with permission from Ref. [29]. Copyright 2016, Wiley-VCH. (b) Schematic of the formation of FePc-20@ZIF-8 composite. Adapted with permission from Ref. [57]. Copyright 2018, American Chemical Society. (c) Schematic of atomically dispersed MnN4 site catalyst synthesis. Adapted with permission from Ref. [36]. Copyright 2018, Springer Nature. (d) Schematic illustration of synthetic route of Pd1@ZrO2. Adapted with permission from Ref. [58]. Copyright 2019, American Chemical Society. (e) The synthesis of Co-N5/HNPCSs. Adapted with permission from Ref. [59]. Copyright 2018, American Chemical Society. (f) Scheme illustrating the formation mechanisms of Cu SAC/S-N. Adapted with permission from Ref. [60]. Copyright 2020, American Chemical Society.

Fig. 2. Synthesis of thermally stable SACs by impregnation /Co-precipitation-calcination. (a) Synthesis process of the 0.2Pt/m-Al2O3-H2. Adapted with permission from Ref. [80]. Copyright 2017, Springer Nature. (b) The evolution of Pt species on Fe2O3 in different conditions. Adapted with permission from Ref. [81]. Copyright 2019, Springer Nature.

Fig. 3. Synthesis of thermally stable SACs by high temperature migration. (a) Thermal migration and evolution process of Pt species on the surface of different supports. Adapted with permission from Ref. [85]. Copyright 2016, American Association for the Advancement of Science. The preparation of Cu-SAs/N-C via high temperature migration; (b) Apparatus diagram; (c) Proposed reaction mechanism. (b,c) Adapted with permission from Ref. [37]. Copyright 2018, Springer Nature. (d) Schematic diagram of preparation for Co-SAs/N-C, Co-NPs/N-C and N-C catalysts. Adapted with permission from Ref. [86]. Copyright 2020, Springer Nature. (e) Schematic illustration of the fabrication of H-CPs. Adapted with permission from Ref. [87], Copyright 2019, Elsevier Inc.

Fig. 4. Synthesis of thermally stable SACs by nitrogen-doped thermal atomization. (a) The evolution of Pd nanoparticles to Pd single atoms in CN matrix. Adapted with permission from Ref. [35]. Copyright 2018, Springer Nature. (b) The proposed formation mechanisms of CNT@PNC/Ni SAs. Adapted with permission from Ref. [90]. Copyright 2019, Wiley-VCH. (c-g) Schematic illustrations and TEM images for the preparation of Pd SAs/TiO2. Adapted with permission from Ref. [42]. Copyright 2020, Springer Nature. (h) Schematic illustration of the synthesis of the hollow carbon decorated with cobalt nanoparticles. Adapted with permission from Ref. [91]. Copyright 2018, Springer Nature. (i,j) Schematic illustration and structure images presenting the transformation of Pt nanoparticles to Pt single atoms. Scale bar: 2 nm. Adapted with permission from Ref. [39]. Copyright 2019, Wiley-VCH.

Fig. 5. Synthesis of thermally stable SACs by other ingenious methods. (a) Microwave-assisted synthesis for preparation of Co SACs. Adapted with permission from Ref. [94]. Copyright 2018, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) shockwave method for synthesizing and stabilizing single atoms; (c) Temperature evolution during the shockwave synthesis; (d) A ten-pulse shock heating pattern in each cycle with a high-temperature on state and a low temperature off state. (b-d) Adapted with permission from Ref. [41]. Copyright 2019, Springer Nature. (e) Preparation of SACs with the protection of ionic liquids. Adapted with permission from Ref. [95]. Copyright 2019, Elsevier Inc. (f) electric flash strategy for synthesis of Co SACs. (I) Plasma arc formed by a 20 kV DC supply module. (II) Spark pulse generated by a multistage Marx circuit. Adapted with permission from Ref. [96]. Copyright 2021 Wiley-VCH GmbH.

Fig. 6. Catalytic performance of thermally stable SACs for CO oxidation reaction. (a) CO conversion ability of the 0.09Au/FeOx and 0.03Au1/FeOx catalysts. Adapted with permission from Ref. [101]. Copyright 2015, Tsinghua University Press and Springer-Verlag Berlin Heidelberg. (b) CO oxidation performance of different catalysts; (c) Proposed CO oxidation mechanism on Pt/CeO2. (b,c) Adapted with permission from Ref. [102]. Copyright 2017, American Association for the Advancement of Science. (d) CO oxidation performance of Au-SA/Per-TiO2 and Au-SA/Def-TiO2; (e) Local atomic structure of the catalysts. (d,e) Adapted with permission from Ref. [78]. Copyright 2018, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (f) CO conversion over different Pt/CeO2 catalysts. Adapted with permission from Ref. [103]. Copyright 2018, American Chemical Society. (g) CO oxidation ability of (Fe,Co)/N-C, Co SAs/N-C, and Fe SAs/N-C; (h) The band decomposed charge density of HOMO and LUMO levels. (isosurface: 0.02 e/Å3). (g,h) Adapted with permission from Ref. [104]. Copyright 2020, American Chemical Society.

Fig. 7. Catalytic performance of thermally stable SACs for CH4 oxidation reaction. (a) CH4 oxidation performance of different catalysts; (b) Reaction pathway of methane conversion to CH3OH, CH3OOH, HOCH2OOH, and HCOOH and the activation energy of each step (unit, eV). (a,b) Adapted with permission from Ref. [34]. Copyright 2018, Elsevier Inc. (c) Dynamic formation of a Pt SAC during methane oxidation. STEM images of catalyst before (left-inset) and after (right-inset) reaction (scale bars, 2 nm). Adapted with permission from Ref. [81]. Copyright 2019, Springer Nature. (d) CH4 oxidation performance of the 1 wt% Cr/TiO2 catalysts for with different reaction time. Adapted with permission from Ref. [107]. Copyright 2020, Springer Nature. (e) The yield of CH4 oxidation for the prepared catalysts; (f) EXAFS fitting curve. Inset: proposed Ni-N4 architectures. (e,f) Adapted with permission from Ref. [90]. Copyright 2019, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fig. 8. Catalytic performance of thermally stable SACs for hydrogenation reaction. (a) hydrogenation of 1,3-butadiene on catalyst loaded with Pd NPs and SAs. Adapted with permission from Ref. [25]. Copyright 2015, American Chemical Society. (b) Acetylene conversion for graphene loaded with Pd SAs and NPs in the selective hydrogenation of acetylene. Adapted with permission from Ref. [111]. Copyright 2019, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (c) Performance for hydrogenation of quinoline of Ru SAs/N-C and Ru NCs/C; (d) Catalytic activity and chemoselectivity of Ru SAs/N-C. Adapted with permission from Ref. [112]. Copyright 2017, American Chemical Society. (e) Styrene hydrogenation performance of Pd NPs/TiO2, Pd NPs/TiO2-900 and Pd NPs/TiO2-900 after treatment by N-doped C atomization process. Adapted with permission from Ref. [42]. Copyright 2020, Springer Nature. (f) Hydrogenation of 4-chloronitrobenzene performance of 0.1Pt loaded on various supports at elevated reduction temperatures. Adapted with permission from Ref. [113]. Copyright 2020, Springer Nature.

Fig. 9. Catalytic performance of thermally stable SACs for NOx decomposition. (a) Catalytic performances of Rh1/Co3O4 for NO reduction to N2. Adapted with permission from Ref. [21]. Copyright 2013, American Chemical Society. (b) NO conversion (black symbols) and N2 selectivity (red symbols) of the Pt-SAC (Solid symbols), Pt-Nano (Hollow symbols) in the reduction of NO with H2 at 200 °C. Adapted with permission from Ref. [128]. Copyright 2015, The Royal Society of Chemistry. (c) Optimized structure of Rh1/SiO2; (d) Calculated energy profile of the reduction of NO with CO on Rh1/SiO2 and optimized structures of the intermediates and the transition states. (c,d) Adapted with permission from Ref. [129]. Copyright 2017, American Chemical Society. (e) N2O conversion on Ru/MAFO samples; (f) Normalized Ru K-edge XANES of Ru/MAFO samples and references; (g) Fourier transforms of k3-weighted Ru K-edge EXAFS spectra of Ru/MAFO samples and references (without phase correction). (e-g) Adapted with permission from Ref. [82]. Copyright 2020, Springer Nature.

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