14/4/8

Two pathways for doping

Lesson 5

Direct synthesis and post-synthesis

Atoms of the third main group (such as B, Al, Ga, etc) and some
transi<on metals serve as the most important doping components
for the silicate-based mesoporous molecular sieves
Aluminum Doping aluminum incorpora<on is one of the most
important topics in modica<on of mesoporous silicas
Boron Doping Boron, generally presents a +3 valence in
compounds and therefore can also generate Bronsted acids aCer
replacing tetrahedral Si4+
Gallium and Indium Doping they are other candidates with
availability of doping in the mesoporous silica, because they oCen
exist as 3+ ca<ons in compounds

Doping in Mesoporous Molecular Sieves

The Bronsted-Lowry concept

In this idea, the ionization of an acid by water
is just one example of an acid-base reaction.
Cl H
acid

H
base

+
H
HO
+

H
conjugate acid conjugate base

Lewis acid vs. Bronsted acid

Conclusion

the ability of the surface to convert an adsorbed

neutral base into its conjugate acid

donor : -COOH, -OH,-HSO3,etc.

from the Si-OH or other functional groups

on the material
OH

can be determined by Ka

Bronsted

OH

OH
OH
Si O Si O Si

O
OO

Si
Si O Si O Si
Si
O

the e- acceptor

Ammonia adsorption calorimetry

Strength of solid acidic sites

Bronsted acidic site

Lewis acidic site

Solid-state NMR

The acidity of material can be determined by its

There are two types of acidic sites on our material

the

IR
Titration

Cl

conjugate acid-base pairs

Acids and bases are identified based on
whether they donate or accept H+.
Conjugate acids and bases are found on
the products side of the equation. A conjugate
base is the same as the starting acid minus H
+.

H+

How to determine acidity?

Amount of acidic sites

how many H+ can be released
how many vacant orbitals to accept the e-

Lewis

from the framework of the material

(ex: SiO2,TiO2,etc)

14/4/8

FTIR

FTIR

furnace

Pyridine on different types of acid site

different characteristic peaks in IR spectrum

vacuumed
10torr

2h

organics are burned

under O2
RT

filtration

Cleavage of other
impurity w/o O2

OH
OH
OH
OH Si O Si O
Si
O
OO
Si
Si O Si O Si
Si

150,200,300,400oC

evacuated
10torr

60min

relative acid strength

pre-LPMSN

400oC

pyridine

Heating and comparing the tendency of pyridine desorption

100oC
10min

cooled to
RT

IR analysis

pyridine
desorption

This method is suitable for:

(1) inorganic material
(2) strength of acidic sites
(3) Bronsted & Lewis acid

400oC
overnight

LPMSN

Measurement of the pyridine adsorption on acid sites.

FTIR

Titration

For example

Hammett and Deyrup's H0 acidity function

Surf. Interface Anal. 2010, 42,959962

mordenite

ZSM-5

NH4-Y

Step1: Choose the suitable indicator

ColorcolorsColor
Each
indicator has different
in acid form
indicator
pKa and base form.
base form acid form

acid
strength
H0 yellow
Methyl
red
red
+4.8
Lewis

p-Dimethylaminoazobenzene yellow

Bronsted

T absorbance of pyridine

The tendency of decrease

The acidic strength

Titration

catalyst
color acid form
Benzeneazodiphylamine
yellow
+
Crystal violet color baseblue
form
indicator

red

+3.3

H0,cat < pKaind

purple

+1.5

yellow
H,

+0.8
pKa
ind

0 cat >

Dicinnamalacetone

yellow

red

4-Nitrotoluene

colorless

yellow

-3.0

-11.35

We
can find 2 indicatorscolorless
let pKayellow
pKaind2
2,4-Dinitrofluorobenzene
ind1< H0cat<-14.25

Titration

Take our HSO3-MSN for example

Step2: Titrated by base

indicator

Color
Color
base form acid form

pKa

Methyl red

yellow

red

+4.8

p-Dimethylaminoazobenzene yellow

red

+3.3

Benzeneazodiphylamine

yellow

purple

+1.5

Crystal violet

blue

yellow

+0.8

Dicinnamalacetone

yellow

red

-3.0

4-Nitrotoluene

colorless

yellow

-11.35

2,4-Dinitrofluorobenzene

colorless

yellow

-14.25

pKaDic< H0HSO3-LPMSN< pKaMet

-3.0< H0HSO3-LPMSN< +4.8

NaOH

Moles of OH- = Moles of H+

We can know the number of acid sites

Indicator/benzene
+
-
Na+ Cl Na Na+
-
Cl
Na+ Cl-
Cl-
H O O HO
H
H O

This method is suitable for:

(1) organic/inorganic material
(2) strength & amount of acidic sites
(3) Bronsted acid

MSN

14/4/8

Solid-State NMR
1H

Solid-State NMR
15N

spectrum

1H{27Al}

MAS spin-echo double-resonance

experiment

Bronsted

spectrum

Pyridine adsorption

Quantify the Bronsted acid

Bronsted

Distinguish Bronsted acid sites from

Lewis acid sites.
Lewis

13C

spectrum
Acetone adsorption
The chemical shift of acetone-2-13C changes upon
complexation with either Bronsted or Lewis acids.

Solid-State NMR
31P

Solid-State NMR

spectrum

For example

Chem. Mater. 2000, 12, 2448 2459

Measure the shift of 31P chemical shift.

acid strength
31P

too close
Adsorption of triethylphospineoxide (TEPO)

P
strong Bronsted acid site

P
O

OH

weak Lewis acid site

This method is suitable for:

(1) organic/inorganic material
(2) strength & amount of acidic sites
(3) Bronsted & Lewis acid

OH
OH Si O Si O
Si
O
OO
Si
Si O Si O Si
Si
O

O
P

OH

chemical shifts

Ammonia adsorption calorimetry

Ammonia adsorption calorimetry

Green Chem., 2010, 12, 13831391

Differential Scanning Calorimetry (DSC)

pre-activated

1ml of 1%NH3/He gas

injected @ regular interval

NH3 input

Measure the release of heat by NH3

adsorption on acid sites.

Range:

100oC

Mass
NH3 output
spectrometer
Monitor the
down-stream [NH3]

-120~725oC

Monitor the heat evolved

in each injection

# of NH3,ab.= # of NH3,input(known)- # of NH3,output(mass spectrometer)

H(per injection)=calculated from the DSC thermal curve.
Range: RT~625oC

H0Ads NH3

14/4/8

Ammonia adsorption calorimetry

For example

Ammonia adsorption calorimetry

Green Chem., 2010, 12, 13831391

TGA

XPS

Mass

DSC

Deduced from NH3,ad

H0Ads NH3 acid strength

# of acid sites = # of NH3,ad

(for H0Ads NH 3>80 kJ mol-1)

Comparison between the measurement mentioned above.

Method

Advantage

Disadvantage

IR

(1) Convenient& cheap to use

(1) Low resolution (2) Tedious procedure

(3) Unsuitable for organics

Titration

(1) Both strength & amount

measurable
(2) Suitable for organics

(1) Less precise

Solid-state
NMR

(1) Most precise

(2) Suitable for organics
(3) Both strength & amount
measurable

(1) Expensive
(2) take long time to wait for the data

Ammonia
adsorption
calorimetry

(1) Suitable for organics

(2) Both strength and amount
measurable
(3) Convenient
(4) Analyzable easily

(1) Not the most precise

The most suitable!

This method is suitable for:

(1) organic/inorganic material
(2) strength & amount of acidic sites
(3) Bronsted & Lewis acid

Summary
In summary, due to the amorphous framework feature of
mesoporous materials, most of the main group and transi<on -
metal elements can theore<cally be incorporated to change their
physicochemical proper<es.
The amorphous framework, however, causes the problem of poor
stability and surface acidity, which become another important
topic.
As for the dopant composi<ons in the silica framework, their
states and chemical environments play a crucial role on the
proper<es of the composite materials