Materiales sólidos básicos

En las siguientes figuras se presentan diversas diaposi7vas

(en inglés) correspondientes a un trabajo desarrollado en
este Departamento.
Se han seleccionado las que más pueden aportar a un
alumno de este máster.
Se trata del estudio del carácter básico de la superficie de
un sólido. ¿Qué es eso? Pues un sólido que en su superficie
posee centros funcionales capaces de ceder electrones,
como lo hacen las bases de Lewis. Éstos se pueden valorar,
como las disoluciones ácidas.
Correspondientemente, un sólido ácido es aquel cuya
superficie posee funciones químicas capaces de aceptar
electrones.
Basic materials for catalytic
fine chemical processes
A. Mickiewicz University
Rosa M. Martin Aranda Faculty of Chemistry
Dpt. of Inorganic Chemistry Poznan; POLAND
UNED, Madrid, Spain
April,2005

Rosa M. Martin Aranda

Dept. de Quimica Inorganica
UNED, Madrid, SPAIN
 Solid catalysts
Redox

Acids Solid catalysts Bases

Bifunc'onal catalysts

Rosa M. Martin Aranda

Dept. de Quimica Inorganica
UNED, Madrid, SPAIN
Basic solids in fine chemistry
PERFUMES FRAGANCES

FINE CHEMICALS

PHARMACEUTIC PESTICIDES
PRODUCTS

Rosa M. Martin Aranda

Dept. de Quimica Inorganica
UNED, Madrid, SPAIN
 Basicity
• Recently, basic solids receive a great deal of aHen'on in FINE
CHEMISTRY
• However, alkaline carbons have been much less studies

Metallic oxides Anionic resins

Zeolites Base Superbases

catalysts
Hydrotalcites Sepiolites

Alkaline carbons

Rosa M. Martin Aranda

Dept. de Quimica Inorganica
UNED, Madrid, SPAIN
 Concepts of base catalysts
• Surface basicity
– Surface site capable of dona7ng an electron pair to an
adsorbed molecule (Lewis base site)
• Basic strength
– Ability to done and electron pair to an adsorbed acid
• Related to the total number of surface Lewis sites per unit
weight or unit surface area of solid

NUMBER AND STRENGTH

Rosa M. Martin Aranda
Dept. de Quimica Inorganica
UNED, Madrid, SPAIN
 Characteriza7on
Titra7on with Acid
• Catalysts can be prepared Indicators adsorp7on
with different basic
strength
Characteriza7on
Probe methods Test
• No characteriza7on Molecules reac7ons
method gives a complete
Spectroscopy methods
informa7on about the
base proper7es of solids.

•K. Tanabe “Catalysis: Science and Technology”, vol.2, Eds.

J.Anderson et al., Springer, Berlin (1981), page 231
•H. Noller et al., Mater Chem. Phys. 18 (1988) 577

Rosa M. Martin Aranda

Dept. de Quimica Inorganica
UNED, Madrid, SPAIN
 Titra7on using indicators
• Indicators with variable pKa
• Weak acid indicators, HA, react with surface basic sites:
– HA + B ‐‐> A‐ + HB+
• Hammet basicity func7on H‐, indicates the site strength:
– H‐ = pKa + log ([A‐]/[HA])
• Technique
– Equilibra7ng a slurry of solid base in an inert solvent, with
increasing amount of 7trants (benzoic acid)
• Limita7ons
– Basic site accesibility
– Difficult in achieve equilibrium

Rosa M. Martin Aranda

Dept. de Quimica Inorganica
UNED, Madrid, SPAIN
 Base‐catalyzed reac7ons

1. Double bond migra7on

2. Dehydrogena7on
3. Hydrogena7on
4. Amina7on
5. Alkyla7on
6. Aldol addi7on and condensa7on
7. Michael addi7on
8. Knoveangel condena7on
9. Ring tranforma7on

H. Hattori, Chem. Rev. 95 (1995) 537

Rosa M. Martin Aranda

Dept. de Quimica Inorganica
UNED, Madrid, SPAIN
 Effect of alkaline ca7on size
• Benzaldehyde and ethyl
cyanoacetate (413 K)
• Introduc7on of alkaline
ca7on increases the
basicity of the carbon
• Ac7vity increases with the
radius of the ca7on:

Li < Na < K < Cs

A. Corma, V. Fornés, R. M. Martín-Aranda, H. García, J. Primo.

Appl. Catal., 59 (1990) 237-248
Rosa M. Martin Aranda
Dept. de Quimica Inorganica
UNED, Madrid, SPAIN