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Tecnologías Aplicadas a Nanomateriales:

ZEOLITES

100 nm

Zeolites

Los catalizadores ácidos más importantes por sus usos industriales

- natural aluminosilicate
What are? minerals. General formula for the composition of a
zeolite is
- Crystal three-dimensional Mx/n[(AlO2)x(SiO2)y] . mH2O
structure with nano-cavities where cations M of valence n+ neutralize the
negatively charged zeolite framework.
- Tetrahedral net of AlO4 and
SiO4 units & cations+

-Inorganic materials SiO2 tetrahedrals are electrically

neutral (e.g., quartz)
- Chemical and Thermally Substitution of Si(IV) by Al(III)
stable creates an electrical unbalance and
neutrality is provided by an
- High specific surface area
exchangeable cation (Na+, Ag+,..)
(400 m2/gr)

- High porosity: sistema de poros/cavidades ordenados y de

Na+ Na+
tamaño Nanométrico:  large ions and water molecules:
GAS SENSING
Si
-
-La acidez es debida a los iones Al.
Al

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What is a Zeolite?

• This connection between SiO4 and AlO4, give to the zeolite a framework, with
pore and internal cavity.

The Si/Al ratio has an important effect on the

behaviour of the zeolite.

ZSM-5

Tecnologías de los Nanomateriales

Inner structure

+ + =

Tecnologías de los Nanomateriales

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Examples of
Structure 4 & 8 membered Sodalite
Building rings (SOD or -cage)
Poros ~3Å

[SiO4 ]4-
[AlO4]5- Sodalite unit
or -cage
[4668]
Zeolite - A
(LTA-type structure)
LTA -cages FAU
pores ~ 4,1Å

Faujasite
Zeolite - X, Y
(FAU-type strtucture)
A large cage (~ 12Å) pores ~ 7,4Å

Zeolite LTA-type structure, Si/Al = 1

Cations cause polarity → attract polar molecules (water, CO2)

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Zeolite FAU-type structure, Si/Al ≠1

+
+

(Na+, Ca++)

Xm+y/m [(SiO2)x (AlO2)-y ]. zH2O

Si 50% - Al 50%
Cations Na, Ca
LTA Polar
3-D straight channels Ring 8

Si 100%
MFI non-polar
Hydrophobic Ring 10
1-D channels

Si x% - Al y%
FAU Cations Na, Ca
Polar Ring 12
3-D entangled channels

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Zeolites: properties (I)

Na+ Na+

Si

Al

 hydrated cations are located inside/outside framework structure and weakly

bound with structure

 advantages of these natural minerals are their large deposits on the Earth, easiness
of exploitation and mostly unnecessary treatment for practical application

 the most important deposits are in the United States, Mexico, Ukraine, Slovakia, Italy,
Greece, Turkey, Russia, Serbia, Romania, Bulgaria, Georgia, Armenia, Cuba and Croatia
 discovered more than 260 years ago by the Swedish mineralogist A.A.F. Cronstedt,
commercial exploitation started ~30 years ago

 the end of 70-ties is proclaimed as "new discovery" of natural zeolites

 about 50 different minerals of zeolites are discovered in nature, but some of them
have commercial valuable

 currently, the world’s annual production of natural zeolite is about 4 million

tons Tecnologías de los Nanomateriales

Zeolites: Physical and chemical properties

 many natural zeolites are also synthesized in laboratory

 difference between natural zeolite minerals is manifested in:

 content of hydrated cations which occupied pores and channels,
 ratio of Si/Al in structure, and
 number of water molecules

 zeolites have different dimensions of pores and channels responsible for their
physical and chemical properties

 each sample is mineralogical heterogeneous, and quantification of its

mineralogical composition in mostly complex procedure.

Tecnologías de los Nanomateriales

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Zeolites. Applications (I)

 Catalysis (as shape-selective catalyst): en reacciones orgánicas (refinamiento del

petroleo: craqueo, isomerización, síntesis de hidrocarburos, industria farmaceutica, …)
SELECTIVES:

Shape & Crystallinity Molecular Polarity Pore size of molecules

 the charge on outer and inner zeolitic surface, molecules with large
polarity or polarizability can be adsorbed preferentially under identical
conditions

Zeolites. Applications (II)

 Adsorption and related molecular sieving: Full reversible & purely physical nature
(without any change in the zeolitic structure)

to remove polar H2O, H2S, and CO2 from natural gas and
developed a zeolite-adsorption process for purifying methane
produced in a landfill

 Dehydration and rehydration

may hold water up to 60% of their weight due to a high porosity of the
crystalline structure. Water molecules in the pores could be easily
evaporated or reabsorbed without damage to such structures
 Biological activity

Improving the fertilizers behaviour by trapping and slowly releasing valuable nutrients

high cation exchange capacity for heavy metal (lead, silver, cadmium, cobalt,
zinc, copper, mercury, magnesium, iron, aluminium, chromium and others)
 Cation exchange

selectivity for ammonium cations (the natural zeolites lower the level of
ammonium in waste waters and sewages to non-toxic, acceptable levels. The
zeolite beds can be regenerated and recycled indefinitely)

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¿Why zeolites are interesting ?

 Estructura molecular perfectamente

definida
– Existen INFINITAS relaciones
Estructura-Propiedades (230)
– Predicción de propiedades según
Estructura

- Presentan importantes aplicaciones

medioambientales:
- Convertidores catalíticos (Diesel y
gasolina)
- Eliminación de compuestos orgánicos
volátiles (VOC removal)
- Reducción 90-95% las emisiones de
óxidos de nitrógeno en motores diesel
convencionales (NOx N2)
- otras aplicaciones, …

• SIN EMBARGO… Zeolite Mordenite

• Desorden es un hecho inevitable
• Relación entre Estructura-Propiedades no siempre es Fácil.

ademas

Applications of zeolites in biotechnology and medicine - a review.

Biomater Sci.2018 May 1;6(5):974-989. doi: 10.1039/c8bm00028j.

Synthetic zeolites as a new tool for drug delivery

J. Biomedical Materials Research A, December 2007, https://doi.org/10.1002/jbm.a.31763

Natural zeolite clinoptilolite: new adjuvant in anticancer therapy.

J Mol Med (Berl). 2001;78(12):708-20.

Natural Zeolites in Medicine (pp 317-334)

DOI: 10.2174/978160805261511201010317
eISBN: 978-1-60805-261-5, 2012
ISBN: 978-1-60805-446-6
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Example: Breakthrough in selective CO2 capturing materials

https://news.mongabay.com/bioenergy/2008/02/breakth
rough-in-selective-co2-capturing.html

• a class of new materials

known as zeolitic imidazolate
frameworks (ZIFs).

• Their findings could lead to

power plants efficiently
capturing the greenhouse gas
without using toxic materials,
after which it can be stored in
geological formations.

• The new materials make non-

carbon material capture less
energy demanding, and can
store up to five times as much
CO2 than porous carbon
materials being designed for
the same task.

• The selectivity of ZIFs to

carbon dioxide is unparalleled
by any other material

Tecnologías de los Nanomateriales

Is Zeolite a new CANCER Cure?

Zeolite or zeolites are a group of porous (aluminosilicate) minerals found
naturally in volcanic rock and ashes. These mineral compounds have been
studied for use as external dressings for wounds (granules of zeolite can help
stop bleeding and promote blood clotting) and as treatments for diarrhea and
for diabetes. In its natural setting, zeolite dust may be a cause of cancer: it has
Stay Connected been associated with a high incidence of malignant mesothelioma, a life-
With threatening disease also associated with inhalation of asbestos particles.
Dr. Weil

Zeolites are sold as dietary supplements and are aggressively promoted on the
internet as a means of removing heavy metals and toxins from the body as well as for
cancer treatment. Claims that zeolite can help the body fight cancer (supposedly by
removing cancer-causing substances in the stomach) have not been substantiated in
human studies.

A few lab studies have suggested that zeolites might increase levels of proteins known
to suppress tumor growth, and in animal studies, micronized zeolite has been shown
to reduce the spread of cancer and increase the effect of the chemotherapy drug
doxorubicin, but there’s no evidence that it prolongs survival in animals with cancer.
Animal studies have also suggested that zeolites have both immunosuppressive and
immunostimulating effects and that they may be useful as additives to animal feed. A
review by Memorial Sloan-Kettering Cancer Center (MSKCC) concluded that none of
the benefits seen in animals occurs in humans.

Because of their surface area and structure, zeolites can hamper absorption of some
medications including aspirin and the antibiotic tetracycline and could interfere with
the action of some chemotherapy and immunosuppressant drugs.

The supplements shouldn’t be used by transplant patients because zeolite could

potentially cause a reaction triggering rejection of the transplanted organ.

Bottom line: no published studies show that zeolite has an antitumor effect in humans
or offers any benefit to persons with cancer. Your sister has a very serious disease.
Make sure that she is in the care of a team of doctors experienced in treating her
condition and forget zeolite. Tecnologías de los Nanomateriales