Inorganic Material Lab. SKKU

Selective Intercalation of Various Muconates into

[LiAl2(OH)6]ClH2O Layered Double Hydroxide (LDH)

jisanrhee@hanmail.netdyjung@chem.skku.ac.kr031-290-5974 (tel)031-290-7075 (fax)

이석우 , 정덕영 *

성균관대학교 화학과 -BK21

Inorganic Material Lab. SKKU

The LDHs intercalated with (Z,Z)- and (E,E)-muconates, [LiAl2(OH)6]2[C6H4O4]nH2O

were synthesized by the reaction of [LiAl2(OH)6]ClH2O with aqueous muconates solution. T

he properties of LDHs were investigated by the XRPD, FT-IR, SEM, TGA and 1H NMR.

The XRPD analyses show that [LiAl2(OH)6]2[(Z,Z)-C6H4O4]nH2O and [LiAl2(OH)6]2[(E,

E)-C6H4O4]nH2O gave different basal spacings after intercalation and the metastable phases

exist in the case of [LiAl2(OH)6]2 [(Z,Z)-C6H4O4]nH2O. Furthermore, it was found that (E,

E)-muconate presents high selectivity in the intercalation reaction into the [LiAl2(OH)6]Cl

H2O from the mixture of (Z,Z)- and (E,E)-muconate isomers.

Abstract

Inorganic Material Lab. SKKU

Muconic Acids

(Z,Z)-form:

Polyester

Precursor of adipic acid: polyamides

Crystal engineering of polymuconic acid

(E,E)-form:

Urinary metabolite of benzene metabolism

Biological marker of occupational and

environmental exposure of benzene

Muconic acid: 2,4-hexadienedioic acid

O

O

OH

HO

O OH

HO O

OHO

HO

O

(Z,Z)-form

(E,Z)-form (E,E)-form

H 2O

, ref

lux

I2 , hv

I2, hv

MeOH

MeO

H

Inorganic Material Lab. SKKU

Experimental Sections

 2[LiAl2(OH)6]Cl + (Z,Z)-C6H4O42-

1. Synthesis of [LiAl2(OH)6]ClyH2O

2Al(OH)3(s) + LiCl(aq)H2O, reflux

[LiAl2(OH)6]ClyH2O

2. Synthesis of LDHs Intercalated with (Z,Z)- and (E,E)-muconates

[LiAl2(OH)6]2[(Z,Z)-C6H4O4] + (E,E)-C6H4O42-

[LiAl2(OH)6]2[(Z,Z)-C6H4O4] + 2Cl-

2[LiAl2(OH)6]Cl + (E,E)-C6H4O42- [LiAl2(OH)6]2[(E,E)-C6H4O4] + 2Cl-

3. Competitive Intercalation Reaction of (Z,Z)- and (E,E)-muconates

[LiAl2(OH)6]2[(E,E)-C6H4O4] + (Z,Z)-C6H4O42-

ref) Chem. Mater. 1997, 9, 241 & 1998, 10, 351

K

Inorganic Material Lab. SKKU

Chemical Analyses and Physical Techniques

1. Elemental Analyses: - C, N, H: EA 1110 elemental analyzer of CE Instrument - metals: ICPS-1000IV analyzer of Shimadzu - chloride: chloride ion-selective electrode of Istek combined electrode.

2. X-ray Powder Diffraction: - a MAC Science 18XMF diffractometer - using Cu K radiation (1.54056 Å)

- with a graphite monochromater - at a rate 2 = 15 o min-1 - with a range 2 = 3.5 - 80 o

3. FT-IR Spectra: - Nicolet 205 FT-IR spectrometer - on KBr pellets - in the range of 4000 - 400 cm-1

- resolution was 2 cm-1, 16 scans

4. Thermogravimetric Analyses: - under air flow of 10 cm3 min-1 - on a TGA 2960 of TA instrument - with the heating rate of 10.0 oC min-1

- in the range rt - 1000 oC

5. 1H NMR Spectra: - Varian 500 spectrometer - at 20 oC - chemical shifts () against TMS - D2O

Inorganic Material Lab. SKKU

X-ray Powder Diffraction Patterns of LDHs

0 10 20 30 40 50 60 70 80

LiA

l2-E

E-M

U, a

s m

ade

2 (CuK)

Rel

ativ

e in

tens

itie

s (a)

(b)

(c)

(d)

(e)

7.68

13.07

9.97 7.77

14.06

12.80

(a) [LiAl2(OH)6]ClyH2O

(b) wet and (c) dried [LiAl2(OH)6]2[(Z,Z)-C6H4O4]zH2O

(d) wet and (e) dried [LiAl2(OH)6]2[(E,E)-C6H4O4]zH2O

Inorganic Material Lab. SKKU

OO

OO

OO

OO

OO

OO

OO

OO

OO

OO

dLT

dHB

dIL

dHB

13.0

7 Å

OO

OO

OO

OO

OO

OO

OO

OO

OO

OO

OO

OO

dLT

dHB

dIL

dHB

14.0

6 Å

Schematic Diagrams for LDHs Intercalated with Muconates

[LiAl2(OH)6]2[(Z,Z)-C6H4O4]zH2O [LiAl2(OH)6]2[(E,E)-C6H4O4]zH2O

OO

OO

Inorganic Material Lab. SKKU

FT-IR and Thermal Analysis of LDHs

0 200 400 600 800 1000

Res

idua

l wei

ght (

%)

Temperature (oC)

(a)

(b)

(c)

100

50

100

50

100

50

FT-IR Spectra TGA Profiles

1000200030004000

Tra

nsm

ittan

ce (

%)

Wavenumber (cm -1)

(a)

(b)

(c)

(a) [LiAl2(OH)6]ClyH2O, (b) [LiAl2(OH)6]2[(Z,Z)-C6H4O4]zH2O, (c) [LiAl2(OH)6]2[(E,E)-C6H4O4]zH2O

Inorganic Material Lab. SKKU

SEM Image of LDHs

Inorganic Material Lab. SKKU

Schematic Diagrams for Selective Intercalation of Muconates

ClClCl

ClCl

Cl

ClClCl

ClCl

Cl

OO

OO

OO

OO

OO

OO

OO

OO

OO

OO

OO

OO

OO

OOOO

OO

12 Cl-

6 + 6

OO

OO

6

Inorganic Material Lab. SKKU

Spectroscopic Analysis of LDHs Intercalated with Mixed Muconates

XRPD Patterns 1H NMR Spectra

starting solution: 35 mL, [LiAl2(OH)6]ClyH2O: 2.52 mmol, total muconates: 3.02 mmol

4 8 12 16

Rel

ativ

e in

tens

itie

s

2 (CuK)

(a)

(b)

(c)

(d)

(e)

(E,E) (Z,Z)

(E,E) (Z,Z)

5.56.06.57.07.5

Chemical shifts, ppm

(a)

(b)

(c)

(d)

(e)

(E,E) (Z,Z)(E,E) (Z,Z)

(E,E)0/(Z,Z)0

0/100

25/75

50/50

75/25

100/0

Inorganic Material Lab. SKKU

Shape-selective Intercalation of Muconates into [LiAl2(OH)6]+ Lattice

0.0

0.2

0.4

0.6

0.8

1.0

0.0 0.2 0.4 0.6 0.8 1.0

(E,E

)

x(E,E),0

3

1

2

Extreme Models for the Intercalation Reaction from

Aqueous Isomeric Mixture of Muconates

1) exclusive intercalation of (Z,Z)-muconate

2) intercalation of two isomer with same affinity

3) exclusive intercalation of (E,E)-muconate.

(E,E) vs. x(E,E),0 Plot

- (E,E), mole fraction of (E,E) in the interlayer

- x(E,E),0, mole fraction of initial (E,E) in the sol’n.

- experimental data( )◆

- [LiAl2(OH)6]ClyH2O: 2.52 mmol

- total muconates: 3.02 mmol

- aqueous sol’n: 35 mL

Inorganic Material Lab. SKKU

Thermodynamic Approach to Shape-selective Intercalation

-1

0

1

2

0.0 0.2 0.4 0.6 0.8 1.0

log

K'

(E,E)

log K' vs. (E,E) Plot Apparent Partition Constant K'

[LiAl2(OH)6]2[(Z,Z)-C6H4O4] + (E,E)-C6H4O42-

[LiAl2(OH)6]2[(E,E)-C6H4O4] + (Z,Z)-C6H4O42-

K

[[LiAl2(OH)6]2[(E,E)-C6H4O4]]eq[(Z,Z)-C6H4O42-]eq

[[LiAl2(OH)6]2[(Z,Z)-C6H4O4]]eq[(E,E)-C6H4O42-]eq

K' =

Thermodynamic Equilibrium Constant K

),(1

0dK'logK log EE

K = 3.73

Inorganic Material Lab. SKKU

Schematic Diagrams for Selective Intercalation of Muconates

[LiAl2(OH)6]ClyH2O

[LiAl2(OH)6]2[(E,E)-C6H4O4]zH2O

(E,E)-muconate (Z,Z)-muconate

+N2

rt, 2 h

separation

Inorganic Material Lab. SKKU

Conclusion

Layer-structured Materials Intercalated with Muconates were Synthesied

[LiAl2(OH)6]2[(Z,Z)-C6H4O4]zH2O

[LiAl2(OH)6]2[(E,E)-C6H4O4]zH2O.

Shape-selective Intercalation with Isomeric Mixtures of Muconates

is thermodynamically controlled competitive reaction. depends on the mole fractions of muconates in both solid and sol’n. could explained with apparent partition constant K’. has its thermodynamic equilibrium constant K of 3.73.

, it is clear that the shape of dicarboxylate anion plays a key role in the determining the selectivity for the host lattice because it induces different interaction between anions and positive layers.

Inorganic Material Lab. SKKU

Future Work

Future Works

, effects of concentration of [LiAl2(OH)6]ClyH2O and muconates,

reaction temperature, solvent, and atmospheric conditions are under investigation.

Acknowledgements. This work was supported by Korea Foundation Grant (KRF-2000-031-000). Rhee, S. W. also acknowledge KRF for BK-21 fellowship.