Inorganic Material Lab. SKKU Selective Intercalation of Various Muconates into [LiAl 2 (OH) 6 ]Cl  H 2 O Layered Double Hydroxide (LDH) (tel) (fax) 이석우, 정덕영 * 성균관대학교 화학과 - BK21

Inorganic Material Lab. SKKU The LDHs intercalated with (Z,Z)- and (E,E)-muconates, [LiAl 2 (OH) 6 ] 2 [C 6 H 4 O 4 ]  nH 2 O were synthesized by the reaction of [LiAl 2 (OH) 6 ]Cl  H 2 O with aqueous muconates solution. The properties of LDHs were investigated by the XRPD, FT-IR, SEM, TGA and 1 H NMR. The XRPD analyses show that [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ]  nH 2 O and [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ]  nH 2 O gave different basal spacings after intercalation and the metastable phases exist in the case of [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ]  nH 2 O. Furthermore, it was found that (E,E)-muconate presents high selectivity in the intercalation reaction into the [LiAl 2 (OH) 6 ]Cl  H 2 O 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

Inorganic Material Lab. SKKU Experimental Sections 2[LiAl 2 (OH) 6 ]Cl + (Z,Z)-C 6 H 4 O Synthesis of [LiAl 2 (OH) 6 ]Cl  yH 2 O 2Al(OH) 3 (s) + LiCl(aq) H 2 O, reflux [LiAl 2 (OH) 6 ]Cl  yH 2 O 2. Synthesis of LDHs Intercalated with (Z,Z)- and (E,E)-muconates [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ] + (E,E)-C 6 H 4 O 4 2- [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ] + 2Cl - 2[LiAl 2 (OH) 6 ]Cl + (E,E)-C 6 H 4 O 4 2- [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ] + 2Cl - 3. Competitive Intercalation Reaction of (Z,Z)- and (E,E)-muconates [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ] + (Z,Z)-C 6 H 4 O 4 2- 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 ( Å) - with a graphite monochromater - at a rate 2  = 15 o min -1 - with a range 2  = o 3. FT-IR Spectra: - Nicolet 205 FT-IR spectrometer - on KBr pellets - in the range of cm -1 - resolution was 2 cm -1, 16 scans 4. Thermogravimetric Analyses: - under air flow of 10 cm 3 min -1 - on a TGA 2960 of TA instrument - with the heating rate of 10.0 o C min -1 - in the range rt o C 5. 1 H NMR Spectra: - Varian 500 spectrometer - at 20 o C - chemical shifts (  ) against TMS - D 2 O

Inorganic Material Lab. SKKU X-ray Powder Diffraction Patterns of LDHs (a) [LiAl 2 (OH) 6 ]Cl  yH 2 O (b) wet and (c) dried [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ]  zH 2 O (d) wet and (e) dried [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ]  zH 2 O

Inorganic Material Lab. SKKU d LT d HB d IL d HB Å d LT d HB d IL d HB Å Schematic Diagrams for LDHs Intercalated with Muconates [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ]  zH 2 O [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ]  zH 2 O

Inorganic Material Lab. SKKU FT-IR and Thermal Analysis of LDHs FT-IR SpectraTGA Profiles (a) [LiAl 2 (OH) 6 ]Cl  yH 2 O, (b) [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ]  zH 2 O, (c) [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ]  zH 2 O

Inorganic Material Lab. SKKU SEM Image of LDHs

Inorganic Material Lab. SKKU Schematic Diagrams for Selective Intercalation of Muconates Cl 12 Cl

Inorganic Material Lab. SKKU Spectroscopic Analysis of LDHs Intercalated with Mixed Muconates XRPD Patterns 1 H NMR Spectra starting solution: 35 mL, [LiAl 2 (OH) 6 ]Cl  yH 2 O: 2.52 mmol, total muconates: 3.02 mmol (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 [LiAl 2 (OH) 6 ] + Lattice 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( ◆ ) - [LiAl 2 (OH) 6 ]Cl  yH 2 O: 2.52 mmol - total muconates: 3.02 mmol - aqueous sol’n: 35 mL

Inorganic Material Lab. SKKU Thermodynamic Approach to Shape-selective Intercalation log K' vs.  (E,E) Plot Apparent Partition Constant K' [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ] + (E,E)-C 6 H 4 O 4 2- [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ] + (Z,Z)-C 6 H 4 O 4 2- K [[LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ]] eq [(Z,Z)-C 6 H 4 O 4 2- ] eq [[LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ]] eq [(E,E)-C 6 H 4 O 4 2- ] eq K' = Thermodynamic Equilibrium Constant K K = 3.73

Inorganic Material Lab. SKKU Schematic Diagrams for Selective Intercalation of Muconates [LiAl 2 (OH) 6 ]Cl  yH 2 O [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ]  zH 2 O (E,E)-muconate(Z,Z)-muconate + N2N2 rt, 2 h separation

Inorganic Material Lab. SKKU Conclusion Layer-structured Materials Intercalated with Muconates were Synthesied [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ]  zH 2 O [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ]  zH 2 O. 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 [LiAl 2 (OH) 6 ]Cl  yH 2 O and muconates, reaction temperature, solvent, and atmospheric conditions are under investigation. Acknowledgements. This work was supported by Korea Foundation Grant (KRF ). Rhee, S. W. also acknowledge KRF for BK-21 fellowship.