Aluminum and Copper-Chromium layered double hydroxides hosts

0,3. 0,4. 0,5. 0,6. 0,7. 0,8. 0,9. 1,0. A b sorbance (arb. u.) Wave Number (cm-1). 3090. -O---HO- bonds. 3447. Free OH. Electronic Supplementary Material (ESI) ...
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Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics This journal is © The Owner Societies 2011

Electronic Supplementary Information

Intercalation and grafting of benzene derivatives into ZincAluminum and Copper-Chromium layered double hydroxides hosts: an XPS monitoring.

Solenne Fleutot1, Jean-Charles Dupin*1, G. Renaudin2, Hervé Martinez1

1

IPREM - UMR CNRS 5254, Université de Pau et des Pays de l'Adour, Pau, FRANCE.

2

LMI - UMR CNRS 6002, Université Blaise Pascal, Aubière, FRANCE.

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics This journal is © The Owner Societies 2011

Cu2p

80000

O1s

CuL3M23M45 CuL3M23M45

60000

N(E)/a.u.

CuL3M45M45

40000

Cr2p

CuL2M45M45

20000

C1s Cu3p S2p

0

0

200

400

600

800

1000

Binding Energy (eV)

Figure ESI1- Auger lines evidence in Cu2Cr-HBS XPS survey (RoomT)

1200

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics This journal is © The Owner Societies 2011

a) N1s peak

b) Cl2p peak

Cu2Cr-HBS

Zn2Al-HBS

Cu2Cr-NO3

Zn2Al-Cl

2p3/2 NO3

2p1/2

*

*

* : peaks coming from XRay beam reduction of nitrates 398

400

402

404

406

Binding Energy (eV)

408

410

412

192

194

196

198

200

202

204

Binding Energy (eV)

Figure ESI2- a) N1s XPS peak of Cu2Cr-NO3 and Cu2Cr-HBS, and b) Cl2p XPS peak of Zn2AlCl and Zn2Al-HBS

206

208

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics This journal is © The Owner Societies 2011

1,0

3447 Free OH

Absorbance (arb. u.)

0,9 0,8 0,7

3090 -O---HObonds

0,6 0,5 0,4 0,3 4000

3500

3000

2500

2000

-1

Wave Number (cm )

Figure ESI3 – Snapshot of Zn2Al-HBS FTIR spectrum in the 4000-2000cm-1 region

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics This journal is © The Owner Societies 2011

a)

b) 933.9 578.5 576.3

Sat.

928

932

936

940

Binding Energy (eV)

Sat.

944

948

570

572

574

576

578

580

Binding Energy (eV)

Figure ESI4- XPS peak of Cu2Cr-HBS at 300°C: a) Cu2p3/2 and b) Cr2p3/2

582

584

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics This journal is © The Owner Societies 2011

HBSqS (e-)

HBC-

Al(OH)3

1.10

Hybrid system HBS/ Al(OH)3 1.16

1.07

qAl (e-)

1.10

0.49

qC (e-) qO (e-)

-0.86

Over pop S-O (e-) Over pop Al-O (e-)

0.313

Hybrid system HBC-/ Al(OH)3

-0.74

1.08

Grafted system HBS-- Al(OH)3

1.25

1.25

1.16

0.54

-0.57

-0.53

0.182

0.265

0.144

0.206

Single link

Double link

0.52 -0.6

0.260

-0.58

-0.59

Table ESI1- Theoretical calculations of atoms net charges (q) and Mulliken electronic overlapping population (Over pop) for the HBS, HBC organic molecules, a model mineral fragment and the hybrid systems considering the intercalation or the grafting mode.

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics This journal is © The Owner Societies 2011

compound

2CuO,Cr2O3

BE region O1s C1s

Cu 2p3/2

Cr2p3/2

529.5

(1.4)

35.0%

531.1

(1.8)

16.4%

284.6

(1.3)

28.0%

287.9

(2.3)

4.7%

933.9

(3.6)

2.4%

941.4

(3.1)

1.3%

944.8

(2.2)

0.7%

576.2 578.5

(2.3) (2.6)

8.4% 3.1%

Table ESI2: XPS data of the manufactured (CAS#209317, Aldrich) 2CuO,Cr2O3: Binding Energies and FWHM of peaks (in parentheses) are reported in eV and atomic percentage (%).