Mesoporous Materials and Green Chemistry: Rosa María Martín Aranda Taipei, July 2018

Mesoporous Materials
and Green Chemistry
Rosa María Martín Aranda

Taipei, July 2018
Bilateral Worshop
COMMON ISSUES ON ENVIRONMENT FOR TAIWAN AND SPAIN
NATIONAL TAIWAN UNIVERSITY
Departamento de Química Inorgánica y Química Técnica
Parallel Histories: early 90s
Green Chemistry 1991: Anastas and Wagner
Mesoporous Materials 1992: Roth et al

Brief History of Green Chemistry
1991 "Green Chemistry" proposed the concept by the chemist

Paul Anastas of US Environmental Protection Agency (EPA)
1992 United Nations Conference on Environment and

Development (UNCED) in Rio de Janeiro. Agenda 21 was
adopted.
1995 President Bill Clinton’s initiative, EPA started to give a
yearly “the U.S. Presidential “Green Chemistry Challenge
Award”

Brief History of Green Chemistry
1997 “The Green Chemistry Institute” is formed by Joe

Breen in the United States (became part of ACS
operations since 2001)
1998 Paul Anastas and John C. Warner published the
book “Green Chemistry: Theory and Practice” (the
book includes “The Twelve Principles”
1999 The Royal Society of Chemistry formed “The Green
Chemistry Network” and started the journal “Green
Chemistry”

Definition of Green Chemistry
The design of products and

processes that reduce or eliminate
the use and generation of
hazardous substances
Paul Anastas and John C. Warner

Spirit of Green Chemistry
 Prevention
 Reduction
 Holistic thinking
 Smart Chemistry
looking for new materials

2020 Sustainability Goal
 Zero Waste
 Zero Toxic Substances
 100% Closed Loop Processes
 Sustainable Growth and Profitability

12 principles of Green Chemistry
1. Prevent waste
2. Atom economy
3. Less hazardous synthesis
4. Design beign chemicals
5. Benign solvents
6. Design for energy efficiency
7. Use renewable feedstocks
8. Reduce derivatives
9. Catalysis
10.Design for degradation
11.Real Time Analysis
12.Benign Chemistry for accident prevention
Green Chemistry
• It is more
effectiveefficientelegant
• It is Simply
Better Chemistry

Fine Chemistry and Green Chemistry
Clean process
Efficiency of a reaction
Atomic economy
E Factor = Kgwaste/Kgproduct
E Factor (Kgwaste/Kgproduct)
Sectors of industry
25 - <100 Pharmaceuticals
5 - <50 Fine Chemistry

Develop catalytic strategies for reaction
CATALYST Homogeneous
Chemical
Chemical Industry
Industry Heterogeneous
Biocatalysis
Higher productivity Better Yields and Selectivity
Milder conditions, reuseable

In 1992: new materials

History of mesoporous materials
Mesoporous Materials: pores 2-50 nm

• 1992 MCM-41, MCM-48, FSM-16
• Boom of new materials
• Interesting properties achieved and
undertood
MCM-41 FSM-16
Types of mesoporous materials
-Original: Si y Si-Al
-Further activities: aluminas,
Carbons, MOF

Current effort
- Optimizing synthesis
- Application in adsorption and

catalysis
- Catalysis interesting area

In catalysis : reusable
• Well described model material
• High surface area
• Narrow pore distribution
• Well defined chem properties of surface

Number of reactions
• Conversion of synthesis gas

• ODH of light alkanes
• Biomass transformation
• Knoevenagel reaction
• Claisen Schmidt condensation
• Acylation reactions
• Friedländer reactions
• Imidazole alkylation

Attention is payed to:
• Novel synthetic approaches

• Understanding their properties in
different reactions
• Catalytic behaviour

Synthesis of bioactive heterocycles catalyzed by
porous materials
Biologically active heterocyclic scaffolds
O, N, S,
•Six-membered rings
•Five-membered rings
•Four membered rings
“Porous catalytic systems in the synthesis of bioactive heterocycles and related

compounds. Biologically relevant heterocycles”
G. Brahmachari (Ed), Elsevier, 2015, 378-403.

Incorporation of Active Sites: Acids and Basic
1. One-step synthesis: active phase is added

to th reaction mixture
2. Post-synthesis: siliceous or aluminous

support is prepared followed by the
modification with active moieties or
precursors

Basic mesoporous materials MCM-41
Amino-grafted MCM-41 materials as basic

catalysts for eco-friendly processes

Preparation of the catalysts
Supports: MCM-41; NbMCM-41; AlMCM-41
Inorganic calcination
Surfactant +
precursors
823 K
Cetyltrimethylammonium Na-silicate,
chloride (CTACl)
Nb(V) oxalate Si/Nb=64
Al sulphate Si/Al=64
Basic medium – pH=~11

Modification of the supports
APMS
(3-Aminopropyl)trimethoxysilane
2APMS
[3-(2-Aminoethylamino)propyl]
trimethoxysilane
3APMS
3-[2-(2-Aminoethylamino)
ethylamino]propyl-trimethoxysilane

Modification of the supports
Grafting
 Cation exchange with aqueous solution of NH 4Cl.
 Calcination at 673 K towards H-forms.
 Grafting with APMS, 2APMS and 3APMS in dry toluene at 373 K;

filtration; washing in dry toluene, water and acetonitrile.
APMS/MCM-41; APMS/NbMCM-41; APMS/AlMCM-41

Basicity Probe Reaction:
Knoevenagel condensation
EWG Base
Knoevenagel
+
product
EWG
R R
393 K, 4h
Batch reactors, no solvent, equimolar amount

Knoevenagel Condensation
Basicity:
APMS/AlMCM-41>APMS/NbMCM-41>>APMS/MCM-
41
Grafted amines/ Basicity:

APMS/AlMCM-41>2APMS/AlMCM-41>3APMS/
AlMCM-41

Model of functionalization and grafting

 Imidazole alkylation
 Isomerization of olefins
Antiviral, antifungical Aromes, fragances
N-ALKYL
ISOSAFROL
IMIDAZOLES
VARICELAHERPES LABIAL
Batch reactor Ultrasounds
Solvent Free

ANTIVIRAL COMPOUNDS:
Synthesis of de N-alkyl imidazole
Key step for viral diseases
 Antimicotic properties :
 Antivirals
 Fungicides
 Bactericides

NITROGEN HETEROCYCLIC RINGS
 Nitrogen heterocycles are an important class of compounds
Vitamins
Natural Products
Hormones
Pharmacological Activities
Antibiotics
Alkaloids

FRIEDLÄNDER REACTION AND MESOPOROUS MATERIALS
AIMS
AIMS
 Design, synthesis and characterization of environmentally friendly and potentially

reusable heterogeneous catalysts based on molecular sieves with different acid/base
properties
AP/MCM-41, MAP/MCM-41 and DEAP/MCM-41 AP: aminopropyl

MAP: methylaminopropyl
Al-SBA-15 and (Cs)Al-SBA-15 DEAP: diethylaminopropyl
 Evaluation of their catalytic activity in the Friedländer reaction from 2-aminoaryl ketones
and ethyl acetocetate

FRIEDLÄNDER REACTION AND MESOPOROUS MATERIALS
MS = Molecular Sieves
R O O O R
Base-MS R CO2Et
Acid-MS
+
N O NH2 O OEt N
H
R = Me, Ph
DRAMATIC SELECTIVITY CHANGES

Acidic-MS Basic-MS
quinoline quinolone
Different reaction pathways

N-Alkylation of pyrazole
Br
N
N
N
NH
Catalyst
catalyst Solvent T t Conversion

[ºC] [h] [%]
KF/Al2O3 CH3CN 80 2 65
(Cs)Al-SBA 15 CH3CN 80 0.5 96
(Cs)Al-SBA 15 CH3CN 25 2 68
[1] P. J. N-Alkylation of pyrazole catalyzed by mesoporous silica.

Synthesis of chromene derivatives
Niobium Mesoporous Cellular Foams

(NbMCF), modified with alkaline metal
elements. Synthesis of chromene
derivatives
Ziolek, Martín-Aranda et al. Catal. Today, 277, 133-142 (2016)

Antibacteria
l
Synthesis of chromenes 1 from 2-hydroxybenzaldehydes 2 and

nitriles substituted at a position 3.

Na and K/NbMCF
Na and K/NbMCF (Ox serie) resulted in the best catalytic

conversion to 1 decrease when the cation size is increased (Et serie)
Synthesis of 2-amino-4H-chromenes catalyzed by alkaline NbMCF

after 60 min of reaction time.
New concept towards creation of basicity
Imidazole immobilization in nanopores

of silicas and niobiosilicates SBA-15
and MCF – a new concept towards
creation of basicity
Modification with imidazole via functionalization by

(3-chloropropyl)trimethoxysilane (ClPTMS)
D. Kryszak , K. Stawicka, V. Calvino-Casilda, R. Martin-Aranda, M.

Ziolek
Appl. Catal. A. Gen. 531, 139-150 (2017)
Highlights
A novelty is growth of activity in Knoevenagel reaction by Nb

inclusion to supports and estimation of imidazole stability.
MCF structure increases effectivity of imidazole anchoring and

activity in Knoevenagel reaction in comparison to SBA-15.
The new niobiosilicates can be used in acid-base catalyzed

reactions and the temperature treatment controls activity.

niobium containing mesoporous silicas as the supports for imidazole
The functionalization and immobilization reactions pathway.
H
N
H3C H3C
O N H3C
and niobiosilicate
Mesoporous silica
O I O O
and niobiosilicate
and niobiosilicate
Mesoporous silica
Mesoporous silica
Et3N O
+ H3C Si Cl Si Cl
I O
H3C O Refluxing 24 h Refluxing 48 h Si N N
in toluene I O in toluene
I O
Modification with imidazole via functionalization by

(3-chloropropyl)trimethoxysilane (ClPTMS)

Nb influence
CN
H3C O
Conversion of benzaldehyde [%]

COOEt
NC
100 +
COOEt
80
60 SBA-15
SBA-15-Im
NbSBA-15-Im
40 MCF
MCF-Im
20 NbMCF-Im
0 30 60 90 120 150 180 210 240

Time [min]
Knoevenagel condensation with ethyl cyanoacetate over modified

SBA-15 and MCF materials. 1 wt.% of catalyst, 90 oC.
Bifunctional materials
they are able to coexist and work in the same reaction mixture

Michael Additions
N
N
N
+ CO2Et
N
H
A CO2Et
100
Batch reactor
95
Conversion (%)
90
85
80
NbMCM-41 APMS/NbMCM AlMCM-41 APMS/AlMCM
60 minutes 333 K 0,02g

Bifunctional materials
Michael addition:
Condensation of imidazole and ethyl acrylate.

Nb effect
Michael addition: imidazole and ethyl

acrylate. 333 K. Thermal vs Ultrasound
Alkylation: Imidazole
N N
+ Br + BrH
N N
H
Batch reactor
Catalyst Conv(%)
APMS / AlMCM-41 88
APMS / NbMCM-41 74
APMS / MCM-41 43
60min 333 K 0,02 g cat
ISOSAFROLE: fragances
Isosafrole

Safrole isomerization
Salfrole Isosafrole
Isomerization of safrole over amino-grafted MCM-41

materials.
Isosafrole synthesis
T= Al, Nb
Conversión, %
Tiempo, h
Isomerization of safrole on T-MCM-41.

Safrole (0.4 g), cat (0.25 g).15 mL DMF. 433 K.
Hybrid materials
Azide and propargyl groups to form triazole, in the presence of copper salt
The generation of acidic and basic centers on mesoporous

molecular sieves by click chemistry
Organic species anchoring by click chemistry reaction. R: -NH 2, -SO3H.

Ta vs Nb MCF
Nb and Ta show shared properties but

different interaction with alkaline metals in
Me/TMCF.
Me/TaMCF samples showed higher Brönsted

basicity than the Me/Nb analogues.
Ziolek and Martín-Aranda, In Press, Catal. Today

Basic HYBRID materials from natural sources
involved in the green synthesis of 2-amino-4h-chromenes
Synthesis of 2-amino-4H-chromenes over TMCF silicas modified with alkaline

metals.

chromenes

chromenes
Conversion values for the reaction between salicylaldehyde 2 and malononitrile 4 catalyzed
by Me/TMCF mesoporous silicas (Me = Li, K, Cs), at 303 K, under solvent-free conditions.

Surface modification with ionic Liquids
direct co-condensation and post-grafting methods
Mesoporous SBA-15 functionalized with ionic liquid with

imidazole core. Structure of [SBA-Im]HSO 4.
ILs functionalized materials remain still less abundant

one-pot pseudo four-component reaction of malononitrile,
salicylaldehydes, and secondary amines
Synthesis of benzopyranopyrimidines derivatives catalyzed by

SBA-Im-NH2.

Conclusions
1.- In the last decade, mesoporous silica catalytic

applications have increased exponentially
2.- Industrial processes need to implement new catalytic

technologies more efficient and selective for the production
of fine chemicals and, hence, for a better and sustainable
society

Conclusions
3.- Provide a general view of the catalytic applications of

mesoporous materials: Mesoporous Silicas, MOFs and
Carbons.
4.- Show the great potential of mesoporous materials as

catalysts for the synthesis of biologically active heterocycles

Acknowledgements
 Group “Catálisis no Convencional Aplicada a la

Química Verde” UNED, Spain
 University of Adam Mickiewicz, Poznan, Poland
 Heyrovsky Institute of Prague, Checz Republic
 University of Science and Technology of Hong Kong,
China
 University Nova of Lisbon, Portugal
Spanish Ministry Project: CTM-2014-56668-R
Thank you !!!


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Mesoporous Materials

and Green Chemistry

Rosa María Martín Aranda

Green Chemistry 1991: Anastas and Wagner

Mesoporous Materials 1992: Roth et al

Departamento de Química Inorgánica y Química Técnica

1991 "Green Chemistry" proposed the concept by the chemist

1992 United Nations Conference on Environment and

Departamento de Química Inorgánica y Química Técnica

1997 “The Green Chemistry Institute” is formed by Joe

Departamento de Química Inorgánica y Química Técnica

The design of products and

Paul Anastas and John C. Warner

Departamento de Química Inorgánica y Química Técnica

looking for new materials

Departamento de Química Inorgánica y Química Técnica

 Zero Toxic Substances

 100% Closed Loop Processes

 Sustainable Growth and Profitability

Departamento de Química Inorgánica y Química Técnica

Departamento de Química Inorgánica y Química Técnica

Departamento de Química Inorgánica y Química Técnica

Higher productivity Better Yields and Selectivity

Milder conditions, reuseable

Departamento de Química Inorgánica y Química Técnica

Mesoporous Materials: pores 2-50 nm

Departamento de Química Inorgánica y Química Técnica

- Application in adsorption and

Departamento de Química Inorgánica y Química Técnica

• Well described model material

• High surface area

• Narrow pore distribution

• Well defined chem properties of surface

Departamento de Química Inorgánica y Química Técnica

• Conversion of synthesis gas

Departamento de Química Inorgánica y Química Técnica

• Novel synthetic approaches

Departamento de Química Inorgánica y Química Técnica

Biologically active heterocyclic scaffolds

“Porous catalytic systems in the synthesis of bioactive heterocycles and related

Departamento de Química Inorgánica y Química Técnica

1. One-step synthesis: active phase is added

2. Post-synthesis: siliceous or aluminous

Departamento de Química Inorgánica y Química Técnica

Amino-grafted MCM-41 materials as basic

Departamento de Química Inorgánica y Química Técnica

Supports: MCM-41; NbMCM-41; AlMCM-41

Basic medium – pH=~11

Departamento de Química Inorgánica y Química Técnica

Departamento de Química Inorgánica y Química Técnica

 Calcination at 673 K towards H-forms.

 Grafting with APMS, 2APMS and 3APMS in dry toluene at 373 K;

APMS/MCM-41; APMS/NbMCM-41; APMS/AlMCM-41

Departamento de Química Inorgánica y Química Técnica

Departamento de Química Inorgánica y Química Técnica

Grafted amines/ Basicity:

Departamento de Química Inorgánica y Química Técnica

Departamento de Química Inorgánica y Química Técnica

Antiviral, antifungical Aromes, fragances

Departamento de Química Inorgánica y Química Técnica

Key step for viral diseases

Departamento de Química Inorgánica y Química Técnica

 Nitrogen heterocycles are an important class of compounds