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Progress in Chemistry 2020, Vol. 32 Issue (8): 1060-1075 DOI: 10.7536/PC200429 Previous Articles   Next Articles

• Review •

Condensed State Chemistry in the Synthesis of Inorganic Nano- and Porous Materials

Jianlin Shi1,**(), Zile Hua1   

  1. 1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
  • Received: Revised: Online: Published:
  • Contact: Jianlin Shi
  • About author:
    ** e-mail:
  • Supported by:
    the National Natural Science Foundation of China(21835007); the National Natural Science Foundation of China(21776297)
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Condensed state chemistry, as we know, means diverse chemical processes taking place in liquids and solids. Actually, condensed state chemistry is present throughout the synthesis and preparation of inorganic materials, especially the nano- and porous solid materials. In the material synthesis, obtaining target solids with desired chemical compositions and phase structures, is probably one of the most fundamental issues of condensed state chemistry. While in the synthesis of porous solid materials such as microporous zeolites or mesoporous oxides, the regulations of pore structures along with the chemical compositions and phase structures become important. Moreover, aiming at the applications in, e.g., catalysis and drug delivery, key factors such as the active sites and defects, and the geometric/physical features such as the dimensions, dispersity and morphologies, should be taken into considerations in addition to the issues mentioned above. In this feature article, by focusing on the inorganic oxides, we discuss several aspects of condensed state chemistry in the chemical syntheses of nanoparticles and superfine powders, pore structural regulations of mesoporous materials and composites, and the synthesis and catalytic properties of hierarchically porous structured zeolite, so as to acquire further in-depth understanding of condensed state chemistry in the materials synthesis and promote the development of nano-/porous inorganic solids under the guidance of condensed state chemistry.

Contents

===1 Introduction

===2 Condensed state chemistry for the preparation of nanoparticles and ultrafine powders

===2.1 Brief description about inorganic nanoparticles and ultrafine powders

===2.2 Characteristics of condensed state chemistry of inorganic nanoparticles and ultrafine powders

===2.3 General chemical methods for preparation of inorganic nanoparticles and ultrafine powders

===3 Condensed state chemistry for the preparation of nanomaterials and mesostructured nanocomposites

===3.1 Descriptions of condensed state chemistry routes for the preparation of nanocomposites

===3.2 Soft-templating preparation of mesoporous and mesostructured nanocomposites

===3.3 Inverse-replication preparation of crystallized mesoporous oxides and bicomponent mesoporous composites

===3.4 Template-free preparation of mesoporous metal oxides and composites

===3.5 Post-incorporation strategy for the preparation of mesoporous host-guest nanocomposites

===4 Condensed state chemistry in the preparation of hierarchically structured zeolites

===4.1 Etching preparation of hierarchically structured zeolites

===4.2 Templating preparation of hierarchically structured zeolites

===4.3 Template-free and self-templating preparation of hierarchically structured zeolites

===4.4 Perspectives on condensed state chemistry synthesis and applications of hierarchically structured zeolites

===5 Conclusion and remarks

Key words: condensed state chemistry, oxide nanoparticles, zeolites, mesoporous materials, nanostructured composites
Table 1 Chemical agents and synthetic procedures for the preparation of oxide nanoparticles
Polycrystalline ceramicsBoehmite, Ammonia aluminum sulfate, Aluminum organic salts Chemical agentsPrecipitation + pyrolysis Synthesis proceduresAlumina
(Al2O3)
Zirconia
(ZrO2)		 Zirconium oxychloride, Zirconium sulfate, Zirconium organic salts Precipitation + pyrolysis; Hydrolysis; Hydrothermal
Yttria
(Y2O3)		 Yttrium chloride, Yttrium sulfate, Yttrium nitrate, Yttrium organic salts Precipitation + pyrolysis; Hydrolysis
Barium titanate
(BaTiO3)		 Barium oxalate, Barium oxide, Titanium oxide, Titanate, Metal organic salts Solid state reaction, Precipitation + pyrolysis; Hydrolysis
Lead zirconium titanate(PZT, PLZT) Related oxides, carbonates, oxalates, Metal organic salts Solid state reaction, Precipitation + pyrolysis; Hydrolysis
Spinels Oxides, carbonates, oxalates, Nitrates, Metal organic salts Solid state reaction, Precipitation + pyrolysis; Hydrolysis
Aluminum silicate
(Mullite)		 Alumina, silica, other inorganic or organic salts Solid state reaction, Precipitation + pyrolysis; Hydrolysis
Silicon Nitrides or other nitrides Silicon(metal, oxide) powders + nitrogen sources(nitrogen, ammonia) Solid state nitridation
Silicon carbides and other carbides Silicon(metal, oxide) powders +carbon sources, Si-containing organics Solid state reaction, Pyrolysis
Fig.1 Schematics of the general physical/chemical synthetic strategies for nanocomposites by(a) “post-deposition” approach and(b) “one-pot” or “one-step” approach[20]. Copyright 2013, American Chemical Society
Fig.2 Schematics of mesostructured materials/composites with(a) amorphous framework,(b) crystallized framework composed of numerous nanosized polycrystallites,(c) guest species homogeneously doped or dispersed in the crystallized host framework(small and round dots present the guest ions and/or ultrasmall crystallites), and (d) guests(crystallites/clusters/nanoparticles) loaded/dispersed in the pore channels attaching on the pore surface[20]. Copyright 2013, American Chemical Society
Fig.3 SEM images of(a) nickel oxalate dihydrate and(b) NiO calcined at 300 ℃; TEM images of(c) nanoporous NiO calcined at 300 ℃ and(d) 340℃[50]. Copyright 2008, Wiley
Fig.4 Schematics of loading guest species in the mesopore channels of mesoporous hosts by employing the mesopores as the microreactors:(a) Reactant A is first introduced by pore surface modification, followed by the introduction of reactant B via a certain kind of interaction(e.g., complexing);(b) A and B are co-introduced simultaneously into the pore channels, and subsequent in situ reaction between the reactants A and B results in the formation of product C within the pore channels[20]. Copyright 2013, American Chemical Society
Fig.5 Schematics of a co-nanocasting strategy for preparation of metal oxides-incorporated mesoporous nanocomposites[20]. Copyright 2013, American Chemical Society
Fig.6 Proposed evolution process of single-crystalline and defect-free hierarchical nanozeolites by amino acid-assisted crystallization[104]. Copyright 2019, American Chemical Society
Fig.7 Preparation procedure of hierarchical full-zeolitic monolith[108]. Copyright 2016, Elsevier
Fig.8 Schematics of the crystallization process of hierarchical porous ZSM-5 single crystals in a quasi-solid-state system[109]. Copyright 2016, Wiley
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Lv Yongjun|Li Peijin|Guo Yanglong|Wang Yanqin|Lu Guanzhong**

. Immobilization of Enzymes on Mesoporous Materials [J]. Progress in Chemistry, 2008, 20(0708): 1172-1179.
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[15] Yan Wang**,Xuhan Zheng,Zhaohua Jiang. Ordered Mesoporous Materials for Biology and Medicine [J]. Progress in Chemistry, 2006, 18(10): 1345-1351.