presentation eldas infrared zeolit dan clay

Regions of the electromagnetic spectrum

Representation of an electromagnetic wave

Pentaammine isothiocyanatocobalt(III) ion

Pb2+ EDTA complex[Co(en)3]3+

complex ion

Zeolite-AZeolite-Y

Zeolite-MFI

Pokok Bahasan

1.Review Infrared Spectroscopy2.Infrared Spectroscopy of Inorganic Molekul3.Infrared Spectroscopy of Zeolite

Identification of dealumination process Identification of isomorphous reaction

process4.Infrared Spectroscopy of Clay

Identification of pillarization process5.Infrared Adsorbed Molecule on zeolite

structureand metal oxide

6. Conclusion

Regions of the electromagnetic spectrum

Representation of an electromagnetic wave

Change in the dipole moment of a heteronuclear diatomic molecule

A molecule that has infrared absorptions it must possess a specific feature, i.e an electric dipole moment of the molecule must change during the vibrations

Normal modes of vibration of linear and bent XY2 molecules

+ and – denote vibrations moving upwards and downwards, respectively,in direction perpendicular to the palne of the paper

Normal modes vibration in CO2

Normal modes vibration in H2O

1 is Raman-active2 and 3 are Infrared-active

Frequency vibrations of Various Inorganic Molecules (1/cm)

Infrared spectra of (a) dihydrate, (b) hemihydrate, and (c) anhydrous CaSO4

Jenis isotop unsur-unsur logam menentukan frekwensi vibrasi inframerah molekul anorganik

Spektra inframerah molekul NiF2

CompoundCompound StructureStructure 1 (cm-1) 2 (cm-1) 3 (cm-1)

BeFBeF22 linearlinear (680)(680) 345345 15551555

BeClBeCl22 linearlinear (390)(390) 250250 11351135

BeBrBeBr22 linearlinear (230)(230) 220220 10101010

BeIBeI22 linearlinear (160)(160) (175)(175) 873873

MgFMgF22 linearlinear 550550 249249 842842

MgClMgCl22 linearlinear 327327 9393 601601

MgBrMgBr22 linearlinear 198198 8282 497497

MgIMgI22 linearlinear 148148 5656 445445

(680) frequencies Raman-active or Infrared-inactive

Vibrational Frequencies of XY2 – Type Metal Halides

Normal modes of vibration of planar (a) and pyramidal (b)of XY3 molecules

Frequency vibrations of Various Molecules of planar and pyramidal of XY3 (1/cm)

Raman Spectra of the SnX3- ions in diethyl ether extracts from SnX2 in HX solution

Daerah near infra red

Normal modes of vibration of tetrahedral (a) and square planar (b) of XY4 molecules

Frequency vibrations of Various Molecules of tetrahedral and square planar of XY4 (1/cm)

Vibrational Modes of NH4Cl

55 and and 66 are lattice vibrational modes

ClK

KClO3

K I

KClO3 KIO3

Infrared spectra of KClO3 (solid line) and KIO3 (dash line)

Primary and Secondary Building Unit Zeolites Structure

PBU

SBU

(1)Garis tebal : Tetrahedral internal(tidak sensitif struktur, sensitif

komposisi kimia, rasiio Si/Al)

(2) Garis putus-putus : Jalinan Eksternal(sensitif struktur, tidak sensitifkomposisi kimia)

Tetrahedral InternalTetrahedral Internal Jalinan EksternalJalinan Eksternal

Jenis vibrasiJenis vibrasi (cm(cm-1-1)) Jenis vibrasiJenis vibrasi (cm(cm-1-1))

Regangan asimetrisRegangan asimetris 1250-9501250-950 Regangan asimetrisRegangan asimetris 750-820750-820

Regangan simetrisRegangan simetris 720-650720-650 Regangan simetrisRegangan simetris 1050-11501050-1150

Bend T-OBend T-O 420-500420-500 Cincin gandaCincin ganda 650-500650-500

Pori terbukaPori terbuka 300-420300-420

Assignment infra merah Zeolite

IR spectra of OH groups in Mazzites Zeolite of Si/Al = 4,4 ; 10 ; 30

(a)activated mazzite, (b) ammonia adsorption, (c) pyridine adsorption, (d) reacting with pyridine (a minus c)

IR spectra of OH groups MAZ 4,4 (a), 10 (b), 30 (c) after benzene adsorption

IR spectra of OH groups MAZ 4,4 (a), (b) after benzene adsorption, (c) a-b

(1)Garis tebal : Tetrahedral internal(tidak sensitif struktur, sensitif

komposisi kimia, rasiio Si/Al)

(2) Garis putus-putus : Jalinan Eksternal(sensitif struktur, tidak sensitifkomposisi kimia)

H-Zeolite-Y

H-Zeolite-ZSM20

DealuminatedZeolite-US

DealuminatedZeolite-Y

DealuminatedZeolite-ZSM20

IR Spectra in the region lattice vibrations of hydrated Faujasite type Zeolitesbefore and after dealumination

Dealumination process

Infrared spectra padatan hasil reaksi isomorphous abu layang dan (NH4)2HPO4

Diambil dari IR Spectroscopy in catalysis, Catalysis today 68 (2001) 263-281EBOOK-IR Review, halaman 312

In faujasite zeolites, the cations in the beta-cages and the double six-ring(SD6R, the hexagonal prism) (i.e., at sites SI, SI, and SII) are sterically inaccessible to nitrogen, and so only the supercage cations (i.e., those at SII andDiambil dari Adsorbent Fundamental and Application, EBook, Chapter X, hal 287

Unit cell of faujasite-type (X and Y) zeolites, including cation sites.

(Top) Site II cation on six-membered oxygen ring as the basic unit on A and X zeolites. T denotes Si or Al. (Bottom) Geometry-optimized cluster model to represent the chemistry of Ag-zeolite.

Diambil dari Adsorbent Fundamental and Application, EBook, Chapter VII, hal 174

(a) Extra-framework cation sites in X- and Y-type zeolites. (b) Far- infrared spectrumof Na-Y with band assignments to cation sites according to [232]. (c) Experimental IR spectrum in comparison to simulated spectra calculated according to the shell model and occupancy of different cation sites. (d) Experimental spectrum in comparison to power spectra simulated by MD at occupancy of different cation sites (parts c and d from [79] with permission) halaman 67

Far-infrared (FIR) spectra of alkali-metal cation-exchanged faujasites and H-Y zeolite

IR Spektra Montmorillonit yg di treatment dgn asam 6 M HCl pada variasiWaktu (a) 0, (b) 2, (c) 4, (d) 6, (e) 8, (f) 10, (g) 12, (h) 18, (i) 24 dan (j) 30 jam

Pita yg paling intensif didekat 1048 cm-1 diindikasikan sbg vibrasi stretching Si-O dari lapisan tetrahedral. Pita 524 cm-1 adalah vibrasi Si-O-Al ( dimana Al adalah kation oktahedral) Pita 466 cm-1 adalah vibrasi bending Si-O-Si. Pita serapan pada 621 cm-1 ini sesuai dgn vibrasi tegak lurus dari kation oktahedral (M-O-Si) dimana M adalah Al, Mg dan Li Tiga puncak pada daerah bending OH adalah :

(a) 917 cm-1 (Al2OH)(b) 886 cm-1 (AlFeOH)(c) 850 cm-1 (AlMgOH)

Al oktahedral disubstitusi oleh Fe dan Mg. Intenditas yg rendah dari puncak pita MgAlOH mengindikasikan kandungan Mg yang rendah. Puncak doublet pada 799 dan 779 mengindikasikan adanya campuran mineral lain dalam hal ini adalah mineral kuarsa.

Pita 524 cm-1 adalah vibrasi Si-O-Al ( Al adalah kation oktahedral) Intensitas puncak 524 berkurang dgn kenaikan waktu Pita doublet 799 dan 779 indikasi adanya mineral kuarsa, Intensitas puncak 799 bertambah dgn kenaikan waktu (dealuminasi kuarsa) Tiga puncak pada daerah bending OH adalah :


Ketiga puncak berkurang dgn kenaikan waktu (dealuminasi, penukaran kation) Pita 1048 cm-1 diindikasikan sbg vibrasi stretching Si-O (tetrahedral) Puncak makin membesar indikasi terbentuknya amorphous silika

IR Spektra Hectorite yg di treatment dgn asam 0,25 M HCl pada variasiWaktu (a) 1, (b) 3, (c) 5 dan (d) 8 jam

Hectorite adalah trioktahedral smectite yg berisi Mg dan Li sebagai kation oktahedral Puncak 654 cm-1 bending OH

Puncak 1012 cm-1 stretching Si-O Puncak 701 cm-1 bending Si-O tegak lurus bidang Puncak 467 cm-1 bending Si-O dlm bidang Pita 524 cm-1 adalah vibrasi Si-O-Al ( Al adalah kation oktahedral) Intensitas puncak 524 berkurang dgn kenaikan waktu Tiga puncak pada daerah bending OH adalah :


Ketiga puncak berkurang dgn kenaikan waktu (dealuminasi, penukaran kation) Pita 1048 cm-1 diindikasikan sbg vibrasi stretching Si-O (tetrahedral) Puncak makin membesar indikasi terbentuknya amorphous silika

IR Spektra Smectite yg di treatment dgn asam 6 M HCl pada variasi suhu(a) asli, (b) 60oC dan (c) 95oC

IR Spektra Hectorite yg di treatment dgn asam HCl pada variasi konsentrasi(a) 0, (b) 0,1, (c) 0,25 dan (d) 0,5 M

Surfactan~ 3 % b/b

Acid Leaching

Hydrotermal

HEKSAGONAL MESOPORE CLAY( H M C )

Natural Bentonite

Calcination

Infrared Spectra Natural Bentonite and Leached bentonite resulted from nonswelling leaching in various concentrasion of Hydrochloride Acid,

(a) Natural Bentonit

(b) 7M (c) 8 M,(d) 9 M

and (e) 10 M

Difractogram Spectra Natural Bentonite and Leached bentonite resulted from nonswelling leaching in various concentrasion of Hydrochloride Acid,


(b) 7M (c) 8 M,(d) 9 M

and (e) 10 M

Infrared Spectra Natural Bentonite and Leached bentonite resulted from swelling leaching in various concentrasion of Hydrochloride Acid,


(b) 4M (c) 5 M, and (d) 6M

Difractogram Spectra Natural Bentonite and Leached bentonite resulted from swelling leaching in various concentrasion of Hydrochloride Acid,


(b) 4M (c) 5 M, and (d) 6M

Difractogram Spectra of Composed Bentonite prepared from Leached bentonite resulted by swelling method in various concentrasion of Hydrochloride Acid and C14TMA

(a) 4M

(b) 5M and (c) 6M

Spectra Infrared of Heksagonal Mesopore Clay

a) before calcination

b) after calcination

Difraktogram Spectra of Heksagonal Mesopore Clay

(a)before calsination

(b) after calcinations

d001 2,10o, 42,03 Å

a

b

d110 3,88o, 22,73 Å

d200 4,42o, 19,94 Å

d110 3,93o, 21,83 Å

d200 4,46o, 19,04 Å

d001 2,14o, 41,13 Å

t = 6-12 A

da

Å

d = basal spacing ~ 41,31 Å

a = distance between center pore

t = pore wall thickness, for MCM-41

~ 6-12 Å

AAd

a 49,473

21

13,41

30cos Å

Å

Pore diameter = a – t = 47,49 Å – 12 Å = 35,49 Å

Two dimension Ilustration of HMC pore

Isoterm Adsorpsi-desorpsi HMC

0

50

100

150

200

250

300

350

0 0.2 0.4 0.6 0.8 1

P/Po

V (c

c/g)

adsorpsi

desorpsi

Isoterm Adsorption-Desorption

SBET = 614,647 m2/g

dpore = 36,49 Å

Pore Size Distribution

-0.05

0

0.05

0.1

0.15

0.2

0.25

0 5 10 15 20 25 30 35 40

rP rata-rata

Vp

/de

lta

rP

13,2 Å

The XRD patterns of Cp sample (Fig. 1) showed that the main crystalline phases correspond to clinoptilolite. The FTIR spectrum of Cp is shown in Fig. 2. The peaks at 3600, 3440 cm-1 are related to stretching mode of H-O-H, the peaks at1080 and 1150 cm-1 belong to antisymmetrical stretching and peaks at 680 and 740 cm-1 are symmetricall stretchings of SiO4 and AlO4, respectively

The FTIR spectrum of Clinoptilolite

(Top) Site II cation on six-membered oxygen ring as the basic unit on A and X zeolites. T denotes Si or Al. (Bottom) Geometry-optimized cluster model to represent the chemistry of Ag-zeolite.

Diambil dari Adsorbent Fundamental and Application, EBook, Chapter VII, hal 174

Diambil dari IR Spectroscopy in catalysis, Catalysis today 68 (2001) 263-281EBOOK-IR Review, halaman 312

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, VibrationalSpectroscopy, EBOOK halaman 51

Zeolite framework vibrations according to the interpretation of Flanigen et al. (adopted from[112]); 1, solid lines: intra-tetrahedral vibrations; 2, broken lines: inter-tetrahedral vibrations

Wavenumbers of various framework vibrations as a function of the mole fraction of aluminum in tetrahedral (T) sites of the zeolite framework; s indicates the slope, i.e., the decrease of the wavenumber (cm–1) per 0.1 atom fraction of Al ion substitution (adopted from [112]). D6R means double six-membered ring, ns and nas stand for symmetric and asymmetric stretching modes, respectively (cf. text and list of abbreviations)

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 52

Approximate assignments of observed lattice vibrational frequencies of Na-X zeolite [246] based on calculations [113]



Raman spectra of zeolites (a) Na-Y (nSi/nAl = 2.6) and (b) Na-X (nSi/nAl = 1.18)

Raman spectra of ion-exchanged Y-type zeolites (nSi/nAl = 2.6), viz. (a) Na-Y, (b) K-Y, (c) Rb-Y, (d) Cs-Y


Far-infrared (FIR) spectra of alkali-metal cation-exchanged faujasites and H-Y zeolite

(a) Extra-framework cation sites in X- and Y-type zeolites. (b) Far- infrared spectrumof Na-Y with band assignments to cation sites according to [232]. (c) Experimental IR spectrum in comparison to simulated spectra calculated according to the shell model and occupancy of different cation sites. (d) Experimental spectrum in comparison to power spectra simulated by MD at occupancy of different cation sites (parts c and d from [79] with permission) halaman 67


Calculated and experimental FIR spectrum of Ba-ZSM-5 (nSi/nAl = 13), adopted from [363] with permission


Comparison of far-infrared spectra of zeolites Na-Y and K-Y before and after adsorption of pyrrole [371] and pyrrolidine (from [372] with permission)

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 79 dan 83

Infrared spectra in the OH stretching region of Y-type zeolite after dealumination via steam treatment. Calcined in A: moist air at 813 K; B: self-steam at 813 K; C: moist air at 1033 K; D: self-steam at 1033 K [411]

Wavenumbers and intensities of the OH stretching bands of a homologous series of zeolites, viz. mordenites ion-exchanged with alkaline earth

cations [443]


Correlation between the absorbance of the OH stretching band produced on sorption of H2S into faujasite-type zeolites and the population of the SIII sites (cf. Fig. 16a) by Na+ cations [454]


Gmelinite cage, hexagonal prism and cancrinite cage of the offretite structure and indication of crystallographically different oxygen atoms and corresponding OH groups therein [487]

Infrared bands of OH groups in hydrogen offretite (a: with 2.3 K+ cations per unit cellleft after exchange; b: with 0.6 K+ cations per unit cell left after exchange): Left: before (full line) and after (dotted line) adsorption of pyridine. Right: before (full line) and after (dotted line) adsorption of ammonia [487]


Diffuse reflectance IR spectra of H-ZSM-5 (adopted from [546])


Near-infrared spectra of H-ZSM-5 with combination bands, n˜(OH)+d(OH) on increasing activation temperatures (adopted from [557])

Calculated power spectra of zeolites H-Y and D-Y in the mid-infrared frameworkregion in comparison with the experimental INS spectrum of H-Y (from [577])

INS spectra of bulk pyrrole obtained with the spectrometers (a) TFXA and (b) IN1BeF and of pyrrole adsorbed in (c) Na-Y and (d) Rb-Y; the asterisks indicate the most intense peaks, cf. text (from [585])



Infrared fundamentals of molecular deuterium, nitrogen and oxygen adsorbed on A-type zeolites [587]

Supercage of zeolite A with the main cation positions and symmetry axes [588]


IR spectra of CO adsorbed at 0.13 mbar on autoreduced Ru, Na-Y in the temperaturerange 75–298 K [624]

Schematic representation of the fundamental vibrations of carbon dioxide, CO2; the mode n2 is twofold degenerated (n2a, n2b)

Schematic representation of the fundamental vibrations of nitrous oxide,N2O



Top : Sorption geometries of (a) CO2 and (b) N2O in zeolite Na4Ca4-A. Bottom :Observed fundamental vibrations n3 (a) of CO2 and n3(b) and n1 (c) of N2O in zeolite Na4Ca4-A (adopted from [596])


Infrared spectra of methane,CH4, adsorbed on Na-A; the spectra obtained at 10–4 and 10–5 mbar (adopted from [599])

Schematic representation of the fundamental vibrations of the bent triatomic molecules of sulfur dioxide, SO2, hydrogen sulfide,H2S, and water, H2O


Infrared spectra of water vapor adsorbed on H-ZSM-5 at low pressures (10–5–1 mbar); the spectra obtained at 10–4 and 10–5 mbar were expanded by the factors 5 and 10, respectively (adopted from [127])


Calculated potential energy surface for the adsorption of a single water molecule on azeolitic Brønsted site (bridging OH group); AD: adsorption energy,PT: proton transfer energy (in kJ mol–1), showing the hydroxonium ion as a transition structure and not in an energy minimum [655, 656]

Hydroxonium ion on a zeolite surface stabilized by a second water molecule where both surface species, (H2O)2 and (H3O+◊◊H2O) become stable [655, 656]. For the meaning of AD and PT see caption of Fig. 43 or list of abbreviations

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, VibrationalSpectroscopy, EBOOK halaman 36

Scheme for the quantitative evaluation of zeolite spectra using integrated or maximum absorbance [128]

presentation eldas infrared zeolit dan clay

Documents

leached bentonite

heksagonal

sensitif komposisi

optimized

site ii cation

tidak sensitif

power spectra

simulated