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Progress in Chemistry 2011, Vol. 23 Issue (12): 2417-2441 Previous Articles   Next Articles

• Review •

Molecular Design and XAFS Characterization of Active Centers of Solid-State Catalysts

Long Jinlin, Gu Quan, Zhang Zizhong, Wang Xuxu*   

  1. State Key Laboratory Breeding Base of Photocatalysis, Fuzhou University, Fuzhou 350002, China
  • Received: Revised: Online: Published:
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Surface organometallic chemistry (SOMC) is an effective route to design and prepare surface metal species with well-defined composition and molecular structure. Synchrotron radiation X-ray absorption fine structure spectroscopy (XAFS) technique is currently a powerful tool to characterize geometrical structure of active sites of solid-state catalysts. Their combination provided a method to design and construct in molecular level catalytic active centres, which was established to be one of the important goals in the field of heterogeneous catalysis. This article reviews the recent advancements in construction of single-site active metallic centre in the channels and cages of zeolite molecular sieves by the SOMC method and in characterizing geometrical structure of active sites of heterogeneous catalytic materials with XAFS, the physical fundament, experimental methods, and data analysis of XAFS technique and its merits and demerits in characterization of catalytic materials, the chemical fundament of SOMC. Single-site mononuclear or polynuclear Ti, Cu, and Fe active centers were successfully constructed in molecular level in the channels and cages of zeolite molecular sieves by the SOMC method. Their micro-structures were characterized in detail with XAFS combined other spectroscopic techniques and their catalytic properties were evaluated. The catalytic nature of these metallic centers was elucidated by establishing the inherent relationship among structure, activity, and composition. The study results revealed in molecular level the pyrolysis mechanism of Cu 2 over the MCM-41 surface, and showed a novel route to prepare CuO, Cu2O and Cu(0)/MCM-41 materials with well-defined composition and micro-structure, clarifying the hydroxylation mechanism of phenol over copper active sites and the nuclearity-dependent catalytic function of iron-oxo species; based on the binuclear diiron clusters with well-defined structure and composition constructed in molecular level by SOMC, a novel selective catalytic reduction pathway for the iron-catalyzed NO-HC reaction was proposed; a novel concept of “surface photoexcited catalysis model” for Fe, Ti contained zeolite molecular sieve photocatalysts and N-doped TiO2 visible-light photocatalyst was proposed in terms of the local structure of photoactive species identified clearly by XAFS technique. Contents 1 Introduction 2 Chemical fundament of surface organometallic chemistry 3 Basic fundament of XAFS 3.1 Physical fundament of XAFS 3.2 Data analysis of XAFS 3.3 Main experimental methods of XAFS and its merits and demerits in characterization of catalytic materials 4 Chemical construction and characterization of catalytic active centers of solid-state catalysts 4.1 Molecular construction of photoactive Ti centers on the surface of MCM-41 molecular sieves 4.2 Molecular construction of highly-dispersed copper active centers on the surface of MCM-41 molecular sieves 4.3 Spectroscopic identification of photoactive centers of HZSM-5 zeolite with trace iron impurity 4.4 Molecular construction of iron active centers confined in the supercages of HY zeolite 4.5 Brief summary on the construction of active centers with surface organometallic chemistry 4.6 Identifying the photoactive N species of N-doped TiO2 visible-iight photocatalyst with NEXAFS 5 Conclusions and outlook
Key words: surface organometallic chemistry, X-ray absorption fine structure spectroscopy, heterogeneous catalysis, active center

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