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Progress in Chemistry 2020, Vol. 32 Issue (8): 1172-1183 DOI: 10.7536/PC200434 Previous Articles   Next Articles

• Review •

Defect with Catalysis

Chao Xie1, Bo Zhou1, Ling Zhou1, Yujie Wu1, Shuangyin Wang1,**()   

  1. 1. State Key Laboratory of Chem/Bio-Sensing and Chemometrics, Hunan Provincial Key Laboratory for Graphene Materials and Devices, School of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China
  • Received: Revised: Online: Published:
  • Contact: Shuangyin Wang
  • About author:
    ** e-mail:
  • Supported by:
    the National Natural Science Foundation of China(51402100); the National Natural Science Foundation of China(21573066); the National Natural Science Foundation of China(U19A2017); the National Natural Science Foundation of China(21825201); Provincial Natural Science Foundation of Hunan(2016JJ1006); Provincial Natural Science Foundation of Hunan(2016TP1009)
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Catalysis plays a significant role in modern industrial production and daily life and the exploration of efficient catalysts is an important issue of catalysis research. In recent decades, many researchers found the important effect of catalyst defects for their catalytic activity and various defective catalysts are prepared. Nevertheless, the relationship between defect and catalysis still needs clarification. In this review, we mainly introduce solid defect chemistry fundamental, defect types in catalysts, characterization and controllable construction of defects, the roles and the dynamic evolution of defects in catalysis. Finally, the summary and outlook for “defect with catalysis” are demonstrated. We hope this review can reveal the origin and development of catalyst defect chemistry, emphasize the importance of defect for catalysis and provide some guidance for exploration and mechanism researches of defect catalysts.

Contents

1 Introduction

2 Solid defect chemistry fundamental

2.1 Classification of solid defects

2.2 Symbols and chemical reaction of solid defect

3 Types, characterization and synthesis of defects in catalysts

3.1 Defect types in catalysts

3.2 Characterization of catalyst defects

3.3 Controllable synthesis of catalyst defects

4 Relationship between defects and activity of catalysts

5 Conclusion and outlook

Key words: defect, catalysis, activity sites, adsorption energy, condensed state chemistry, in-situ characterization
Table 1 Kröger-Vink symbolic notation of crystal defects[20]
Defect types Symbols Defect types Symbols
Metal ions M vacancy VM Non-metal vacancy on the position of non-metal Y VY
Doped metal A on metal M AM Doped non-metal vacancy Z on the position of non-metal Y ZY
Interstitial metal M Mi Interstitial non-metal Y Yi
Electroneutral metal ions M vacancy Electroneutral non-metal ions Y vacancy
Metal ions M vacancy with effective negative charge V'M Non-metal ions Y vacancy with effective positive charge
Metal ions M vacancy with effective positive charge Non-metal ions X vacancy with effective negative charge X'i
Interstitial metal M with n effective positive charge Interstitial non-metal Y with n effective positive charge
Free electron b e' Free hole b h·
Associated defect(vacancies pair) (VMVY) Associated defect with effective positive charge (VMVY) ·
Fig.1 (a) EPR spectra of TiO2/b-Si samples with different defects[40]; (b) Positron lifetime spectrum of the two CoSe2 samples[42]; (c) R space data of the Ni K-edge XANES spectra for the Mono-NTi-MMO and control samples[30]; (d) R space data of the Fe K-edge XANES spectra for CoFe LDHs[43]
Fig.2 (a) STM image of CeO2 with defects[46]; (b) STM image of TiO2(111) with CO adsorption[47]; (c) STEM image of defective graphene[49]; (d) STEM image of WS2 with sulfur vacancies[51]
Fig.3 (a) Schematic diagram of the role of oxygen vacancy in catalyzing CO oxidation[86]; (b) Volcano relationships of surface charge and catalytic activities[96]
Fig.4 (a) Catalytic performance of Au-SA/Def-TiO2 and control for CO oxidation; (b) Schematic diagram of active site structure and the catalytic stability of Au-SA/Def-TiO2[107]
Fig.5 Schematic of Pd nanoparticles/black TiO2/b-Si photocathode for water reduction, graded oxygen defects of b-TiO2 improve the separation efficiency of electron-hole pair[40]
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Abstract

Defect with Catalysis