Zeolite-Y
Zeolite-A
Pokok Bahasan
1. Review Infrared Spectroscopy 2. Infrared Spectroscopy of Inorganic Molekul 3. Infrared Spectroscopy of Zeolite Identification of dealumination process Identification of isomorphous reaction process 1. Infrared Spectroscopy of Clay Identification of pillarization process 1. Infrared Adsorbed Molecule on zeolite structure and metal oxide 6. Conclusion
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
Infrared spectra of (a) dihydrate, (b) hemihydrate, and (c) anhydrous CaSO4
Structure
linear linear linear linear linear linear linear linear
1 (cm -1 )
(680) (390) (230) (160) 550 327 198 148
2 (cm -1 )
345 250 220 (175) 249 93 82 56
3 (cm -1 )
1555 1135 1010 873 842 601 497 445
Raman Spectra of the SnX 3 - ions in diethyl ether extracts from SnX in HX solution
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 NH 4 Cl
Cl KClO3
I KIO3
KClO3 Infrared spectra of KClO 3 (solid line) and KIO 3 (dash line)
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 sensitif komposisi kimia)
Jalinan Eksternal
Jenis vibrasi (cm -1 )
750-820 1050-1150 650-500 300-420
(cm -1 )
1250-950 Regangan asimetris 720-650 420-500 Regangan simetris Cincin ganda Pori terbuka
(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), (b) after benzene adsorption, (c) a-b
IR spectra of OH groups MAZ 4,4 (a), 10 (b), 30 (c) after benzene adsorption
1) Garis tebal : Tetrahedral internal (tidak sensitif struktur, sensitif komposisi kimia, rasiio Si/Al)
2) Garis putus-putus : Jalinan Eksternal (sensitif struktur, tidak sensitif komposisi kimia)
H-Zeolite-Y H-Zeolite-ZSM20
Dealumination process
Infrared spectra padatan hasil reaksi isomorphous abu layang dan (NH4)2HPO4
Diambil dari IR Spectroscopy in catalysis, Catalysis today 68 (2001) 263-281 EBOOK-IR Review, halaman 312
Unit cell of faujasite-type (X and Y) zeolites, including cation sites. 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 and Diambil dari Adsorbent Fundamental and Application, EBook, Chapter X, hal 287
(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 spectrum of 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
IR Spektra Montmorillonit yg di treatment dgn asam 6 M HCl pada variasi Waktu (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 : (a) 917 cm-1 (Al2OH) (b) 886 cm-1 (AlFeOH) (c) 850 cm-1 (AlMgOH) 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 variasi Waktu (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 : (a) 917 cm-1 (Al2OH) (b) 886 cm-1 (AlFeOH) (c) 850 cm-1 (AlMgOH) 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 konsentras (a) 0, (b) 0,1, (c) 0,25 dan (d) 0,5 M
Natural Bentonite
Surfactan ~ 3 % b/b Acid Leaching Hydrotermal 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, (a) Natural Bentonit (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, (a) Natural Bentonit (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, (a) Natural Bentonit (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
Difraktogram Spectra of Heksagonal Mesopore Clay (a) before calsination (b) after calcinations
a=
t = 6-12 A
Isoterm Adsorption-Desorption
Iso term Ad so rp si-d eso rp si H M C
350 300 250 V (cc/g) 200 150 100 50 0
0 0 .2 0 .4 0 .6 0 .8 1
P/Po
The FTIR spectrum of Clinoptilolite 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 at 1080 and 1150 cm-1 belong to antisymmetrical stretching and peaks at 680 and 740 cm-1 are symmetricall stretchings of SiO4 and AlO4, respectively
(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) 263-281 EBOOK-IR Review, halaman 312
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 Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 51
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 (cm1) 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]
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 53
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) KY, (c) Rb-Y, (d) Cs-Y Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 59
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 65
(a) Extra-framework cation sites in X- and Y-type zeolites. (b) Far- infrared spectrum of 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
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 69
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 73
Infrared spectra in the OH stretching region of Y-type zeolite after dealumination via steam treatment. C alcined 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 ]
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 79 dan 83
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] Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 85
Gmelinite cage, hexagonal prism and cancrinite cage of the offretite structure and indication of crystallographically different oxygen atoms and corresponding OH groups therein [487]
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 89
Infrared bands of OH groups in hydrogen offretite (a: with 2.3 K+ cations per unit cell left 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]
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 98
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 framework region in comparison with the experimental INS spectrum of H-Y (from [577])
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 100 dan 104
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])
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 105
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]
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 107 dan 108
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 113
IR spectra of CO adsorbed at 0.13 mbar on autoreduced Ru, Na-Y in the temperature range 75298 K [624]
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 113
Schematic representation of the fundamental vibrations of carbon dioxide, CO2; the mode n 2 is twofold degenerated ( n 2a, n 2b)
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 119 dan 121
Top : Sorption geometries of (a) CO2 and (b) N2O in zeolite Na4Ca4-A. Bottom :Observed fundamental vibrations n 3 (a) of CO2 and n 3(b) and n 1 (c) of N2O in zeolite Na4Ca4-A (adopted from [596])
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 120
Infrared spectra of methane,CH4, adsorbed on NaA; the spectra obtained at 104 and 105 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
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 123 dan 124
Infrared spectra of water vapor adsorbed on H-ZSM-5 at low pressures (1051 mbar); the spectra obtained at 104 and 105 mbar were expanded by the factors 5 and 10, respectively (adopted from [127])
Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 113
Calculated potential energy surface for the adsorption of a single water molecule on a zeolitic Brnsted site (bridging OH group); AD: adsorption energy,PT: proton transfer energy (in kJ mol1), 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, Vibrational Spectroscopy, EBOOK halaman 128 dan 129
Scheme for the quantitative evaluation of zeolite spectra using integrated or maximum absorbance [128] Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 36