Porous Metal/Metal Oxide

Nanomaterials
Nanochemistry of Metal Oxides CHM 721
 Why Highly Porous Nanomaterials?
Their specific size and morphology feature
• a high surface area to volume ratio,
• well-developed and accessible porosity for adsorbates and reactants,
• are non-toxic, biocompatible and thermally stable,
• suitable as synergetic supports for precious metal catalysts.

Complex porous non-silica metal oxide submicrospheres constitute an

important class of materials that fulfill all these qualities and in addition,
they are relatively easy to synthesize. These properties make them materials
of great importance for many advanced applications.
 Why Highly Porous Nanomaterials?
Complex porous non-silica metal oxide submicrospheres constitute an
important class of materials that fulfill all these qualities and in
addition, they are relatively easy to synthesize. These properties make
them materials of great importance for many advanced applications
such as
• energy conversion and storage,
• catalysis,
• biomedicine,
• and environmental remediation.
 Why Highly Porous Nanomaterials?
Furthermore, depending on the material used,
• the particle size,
• crystal size,
• surface area,
• pore size distribution,
• and morphology
can be tailored for specific applications by adjusting the chemical
composition and synthesis conditions.
 Why Nano/Microscale Metal/Metal Oxide
Products?
Metal oxides (MeO) exhibit several attractive features such as
• high mechanical strength,
• thermal stability,
• chemical inertness,
• non-toxicity,
• biocompatibility,
• oxygen vacancies,
• semiconductor properties
• high isoelectric point,
• and can act as supports for noble metals such as Au, Pt and Pd, or rare earth
metals to achieve synergistic catalytic activity toward specific chemical reactions.
 Why Nano/Microscale Metal/Metal Oxide
Products?
Furthermore, for nanosized crystals, quantum effects become
important as reflected by significantly different optical and electronic
properties from those observed for the bulk phases which can have
favorable outcomes for their application in catalysis and
photocatalysis; for example, new physicochemical phenomena such as
ferromagnetism and paramagnetism can be achieved for otherwise
antiferromagnetic systems, as in the case of NiO spheres.
Porous Metal/Metal Oxide Nanoparticles
The porous non-silica metal oxide submicrospheres can be designed to have large
surface areas and well-developed porosity to enhance interfacial interactions with
reactants and facilitate the transport and diffusion of reactants and products.
Also, the crystal size and growth directions need to be considered for specific
catalytic and semiconductor applications.
Furthermore, a proper balance between micropores, mesopores and macropores
that respectively act as reaction sites, distribution/evacuation pathways and
reservoirs is desired.
The spherical morphology is the most stable shape that is achieved in nature.
In the case of metal oxides, the advantages offered by spherical structures are high
mechanical strength, short pathways for diffusion of species, dispersion
enhancement due to the stabilization of electrostatic charges, high surface area to
volume ratios, easy coating with other species or metal oxides, minimization of
viscous effects and predictable hydrodynamics.
Porous Metal/Metal Oxide Nanoparticles
Typical spherical morphologies of metal oxides can be classified into
three groups:
• porous solid spheres,
• core–shell spheres
• and hollow spheres.
Synthesis of Metal Oxide Particles
• The main methods for the preparation of MeO particles with spherical
structures are
• hydrothermal synthesis at elevated temperatures (>100 °C),
• and low temperature solution precipitation synthesis (<100 °C).
• These methods include structure defining approaches such as
• hard templating,
• soft templating,
• hydrolysis,
• Ostwald ripening and
• the Kirkendall effect.
Hydrothermal Synthesis
• The hydrothermal/solvothermal synthesis of metal oxide particles involves the use of a
batch reactor at elevated temperatures (above 100 °C) and pressures. It offers a
controlled environment for interactions of the salts used as metal oxide with other
reactants in solution to form nanosized crystallites.
• The elevated pressure and temperature conditions facilitate dissolution of precursors
and recrystallization of materials that can be insoluble under ambient conditions.
• As a result, high purity, homogeneous, metastable and often crystalline products are
formed with unique properties and narrow particle size distribution.
• This synthesis method is flexible and well suited for the control of morphology and
crystallinity of the porous metal oxide spheres by varying experimental parameters such
as
• reaction temperature and time,
• type of reactants and solvents,
• and the chemical composition of the synthesis mixture.
Hydrothermal Synthesis
• During the hydrothermal process, the nanosized crystallites self-
assemble (with or without additives such as polymers and
surfactants) into more complex architectures with optimal stability
and lowest surface energy; hence, spherical shapes are favored. Also,
metal oxide spherical structures can be synthesized via solution
precipitation using milder conditions (i.e., temperature below 100 °C
and atmospheric pressure).
Hard Templating
Shell structures
Hard templating is the most common method for production of hollow
spheres. In hard templating, nanoparticles are attached to the surface
of a solid sphere and they aggregate to form a shell.
The commonly used hard templates for the creation of spherical shells
are
• carbon,
• silica
• polymer spheres or
• microorganisms
Hard Templating
• These templates have a large number of reactive oxygen functional
groups that are electron donors and therefore attract positively
charged metal cations.
• The size of the inner hollow space can be tailored by selecting solid
templates with appropriate sizes, while the thickness of the shell can
be adjusted by changing the concentration of the reactants or by
changing the hydrophilicity of the template's surface by alkaline or
acid treatment.
Hard templating method for synthesis of hollow metal oxide
spheres
Disadvantages of Hard Templating
• An additional synthesis step is required to remove the templates,
which is by either calcination in air for carbon-rich templates or
alkaline or HF etching for SiO2 templates.
• The use and subsequent removal of the solid templates represents a
waste in resources, which goes against “green” processing.
• calcination can lead to the partial or full collapse of the shell
architectures, while alkaline etching can implicate formation of
unwanted crystalline phases.
• whereas HF is a very toxic chemical to deal with.
Disadvantages of Hard Templating
• Hard templates could be environmentally friendly through the use of
biotemplates such as yeast and bacteria.
• The utilization of bacteria (Micrococcus lylae) as a template to synthesize
flower-like hierarchical Co3O4 hollow sphere with a uniform size of 1 μm, a
high surface area of 149 m2g-1, and a pore volume of 0.26 cm3g-1 was
achieved via a one-pot reduction/oxidation reaction at room temperature.
• The bacterial surface is naturally covered with carboxyl, ester, amine and
hydroxyl groups, which could readily capture cations. The bio-templating
method is very attractive as it is facile, scalable and cost effective and could
be extended to fabricate other materials and composites.