Raman Spectroscopic Characteristics of Zeolite Group Minerals
Abstract
:1. Introduction
2. Method
3. Results and Discussion
3.1. The Raman Spectroscopy of Zeolites
- The numbers (1–3) before each zeolite mineral indicate the number of specimens of the same species, since each species may have had more than one specimen available for analysis.
- We compared our results with the RRUFF database and chose the data that matched best with our data in the tabulated lists.
- The stoichiometric composition and sample locality of each sample are listed.
3.1.1. Natrolite Group
3.1.2. Analcime Group
3.1.3. Gismondine Group
3.1.4. Chabazite Group
3.1.5. Mordenite Group
3.1.6. Heulandite Group
3.1.7. Unknown Structure
3.2. Comparison between Different Zeolite Groups
- (1)
- The fibrous natrolite group can be identified by the characteristic peaks at 528–538 cm−1.
- (2)
- The singly-connected four-cycle chain analcime group can be identified by the characteristic peaks at 379–392 cm−1.
- (3)
- The doubly-connected four-cycle chain gismondine group has a pattern almost overlapping the zeolites of other groups, and only the characteristic peaks at 391–432 cm−1 can be used for the recognition of this group. The Al-O-Al modes of gismondine, amicite and gobbinsite fall in the spectral range of 391–432 cm−1, which overlaps with the Al-O-Al modes in the mordenite and heulandite groups. This group has a very wide composition.
- (4)
- The six-cycle ring chabazite group can be recognized by the unique presence of a characteristic peak at 320–340 cm−1.
- (5)
- The spectra of the mordenite group overlap with other zeolites, and the peaks at 800–965 cm−1 are suitable for its identification.
- (6)
- The spectra of the heulandite group also overlap with other zeolites in prominent characteristic peaks, and only the peak at 612–620 cm−1 can be used for its identification.
- (7)
- Most mordenite and heulandite groups have higher intense peaks in the range of Al-O-Al modes, which are different from the gismondine group.
3.3. The Meaning of Characteristic Vibration Modes
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
- Cronstedt, A.F. Observation and description of an unknown kind of rock to be named zeolites: Kongl. Vetenskaps. Acad. Handl. Stockh. 1756, 17, 120–123. [Google Scholar]
- Flenigen, E.M. Chapter 2 Zeolites and molecular sieves: An historical perspective. Stud. Surf. Sci. Catal. 2001, 137, 11–35. [Google Scholar]
- Nguyen, M.L.; Tanner, C.C. Ammonium removal from wastewaters using natural New Zealand zeolites. N. Zeal. J. Agric. Res. 1998, 41, 427–446. [Google Scholar] [CrossRef] [Green Version]
- Wiesmann, U. Biological nitrogen removal from wastewater. Adv. Biochem. Eng. Biotechnol. 1994, 51, 114–153. [Google Scholar]
- Chen, H.F.; Lin, Y.J.; Chen, B.H.; Yoshiyuki, I.; Liou, S.Y.H.; Huang, R.T. A further investigation of NH4+ removal mechanisms by using natural and synthetic zeolites in different concentrations and temperatures. Minerals 2018, 8, 499. [Google Scholar] [CrossRef] [Green Version]
- Gottardi, G.; Galli, E. Natural Zeolites; Springer: Berlin/Heidelberg, Germany, 1985; pp. 1–422. [Google Scholar]
- Hey, M. Studies on zeolites: Part Ι. General review. Miner. Mag. 1930, 22, 422–437. [Google Scholar] [CrossRef]
- Zoltai, T. Classification of Silicates and other minerals with tetrahedral structures. Am. Mineral. 1960, 45, 960–973. [Google Scholar]
- Meier, W.M. Zeolite structures. In Molecular Sieves; Society of Chemical Industry: London, UK, 1968; pp. 10–27. [Google Scholar]
- Ghobarkar, H.; Schaf, O.; Massiani, Y.; Knauth, P. The Reconstruction of Natural Zeolites; Springer: Dordrecht, The Netherlands, 2003; pp. 1–154. [Google Scholar]
- Hong, S.T. Raman Spectroscopic Study of Zeolite Group Minerals. Master’s Thesis, National Taiwan Normal University, Taipei, Taiwan, 2005; 103p. (In Chinese). [Google Scholar]
- Chiang, Z.H. A Study on Raman Spectroscopy and Thermogravimetric Analysis of Natural and Synthetic Zeolites. Master’s Thesis, National Taiwan Ocean University, Keelung, Taiwan, 2008; 159p. (In Chinese). [Google Scholar]
- Chen, H.F.; Fang, J.N.; Lo, H.J.; Song, S.R.; Chung, S.H.; Chen, Y.L.; Lin, I.C.; Li, L.J. Syntheses of zeolites of the gismondine group: West. Pac. Earth Sci. 2002, 2, 331–346. [Google Scholar]
- Chen, H.F.; Fang, J.N.; Lo, H.J.; Song, S.R.; Chen, Y.L.; Chung, S.H.; Lee, C.Y.; Li, L.J.; Lin, I.C. The synthesis of merlinoite. West. Pac. Earth Sci. 2002, 2, 371–386. [Google Scholar]
- Goryainov, S.V.; Smirnov, M.B. Raman spectra and lattice-dynamical calculations of natrolite. Eur. J. Mineral. 2001, 13, 507–519. [Google Scholar] [CrossRef]
- Wopenka, B.; Freeman, J.J.; Nikischer, T. Raman Spectroscopic Identification of Fibrous Natural Zeolites. Appl. Spectrosc. 1998, 52, 54–63. [Google Scholar] [CrossRef]
- Mozgawa, W. The relation between structure and vibrational spectra of natural zeolites. J. Mol. Struct. 2001, 596, 129–137. [Google Scholar] [CrossRef]
- Knops-Gerrits, P.P.; Vos, D.E.D.; Feijen, E.J.P.; Jacobs, P.A. Raman spectroscopy on zeolites. Microporous Mater. 1997, 8, 3–17. [Google Scholar] [CrossRef]
- Gujar, A.C.; Moye, A.A.; Coghill, P.A.; Teeters, D.C.; Roberts, K.P.; Price, G.L. Raman investigation of the SUZ-4 zeolite. Microporous Mesoporous Mater. 2005, 78, 131–137. [Google Scholar] [CrossRef]
- Chen, H.F.; Lo, H.J.; Song, S.R.; Fang, J.N.; Chen, Y.L.; Li, L.J.; Lin, I.C.; Chung, S.H.; Lee, Y.T. The synthesis of phillipsite. West. Pac. Earth Sci. 2002, 2, 409–420. [Google Scholar]
- Dutta, P.K.; Barco, B.D. Raman Spectroscopy of Zeolite A: Influence of Si/Al Ratio. J. Phys. Chem. 1988, 92, 354–357. [Google Scholar] [CrossRef]
- Dutta, P.K.; Twu, J. Influence of Framework Silicon-Aluminum Ratio on the Raman Spectra of Faujasitic Zeolites. J. Phys. Chem. 1991, 95, 2498–2501. [Google Scholar] [CrossRef]
- Yu, Y.; Xiong, G.; Li, C.; Xiao, F.S. Characterization of aluminosilicate zeolites by UV Raman spectroscopy. Microporous Mesoporous Mater. 2001, 46, 23–34. [Google Scholar] [CrossRef]
Zeolite Group | Minerals | Zeolite Group | Minerals |
---|---|---|---|
Natrolite group (fibrous) | Natrolite * | Chabazite group (six-cyclic ring) | Gmelinite * |
Pranatrolite | Chabazite * | ||
Tetranatrolite | Willhendersonite | ||
Mesolite | Levyne * | ||
Scolecite * | Erionite * | ||
Gonnardite | Offretite | ||
Edingtonite | Faujasite | ||
Thomsonite * | Goosecreekite | ||
Analcime group (singly connected 4-ring chains) | Analcime * | Gismondine group (doubly connected four-ring) | Gismondine * |
Wairakite | Garronite * | ||
Hsianghualite | Amicite * | ||
Viseite | Gobbinsite * | ||
Laumontite * | Phillipsite * | ||
Leonhardite | Harmotome | ||
Roggianite | Merlinoite * | ||
Yugawaralite | Mazzite | ||
Partheite | Paulingite | ||
Pollucite | |||
Mordenite group | Mordenite * | Heulandite group | Heulandite * |
Dachiardite | Clinoptilolite * | ||
Epistilbite | Stilbite * | ||
Ferrierite | Stellerite | ||
Bikitaite | Barrerite | ||
Unknown group | Cowlesite | Brewsterite |
Zeolite | RRUFF No. | Composition | Locality |
---|---|---|---|
Thomsonite (3) | R050103 | NaCa2(Si5Al5)O20·6H2O Na0.76Ca2.19(Si4.96Al5)O20·nH2O | Folknare, North Bohemia, Czech Republic |
Natrolite (2) | R040112 | Na2(Si3Al2)O10·2H2O Na2.02Ca0.01(Si3Al1.99)O10·nH2O | Partridge Island, NS, Canada |
Edingtonite | R040110 | Ba(Si3Al2)O10·4H2O | Ice River, BC, Canada |
Scolecite | R040111 | Ca(Si3Al2)O10·3H2O Ca0.98Si3.04Al1.96O10·nH2O | Nashik, Maharashtra, India |
Mesolite (2) | R050013 | Na2Ca2(Si9Al6)O30·8H2O | Aurangabad, Maharashtra, India |
Gonnardite | (Na,Ca0.5)8−10(Al8+xSi12−x)O40·12H2Ox = 0–2 | Schellkopf, Brenk, Niederzissen, Eifel, Rhineland-Palatinate, Germany |
No. | RRUFF No. | Composition | Locality | |
---|---|---|---|---|
Analcime (2) | R040128 | NaSi2AlO6·H2O Na0.95Si2.04Al0.96·nH2O | Wasson’s bluff, Bay of Fundy, NS, Canada | |
Laumontite | R040020 | Ca(Si4Al2)O12·4H2O Na0.02Ca1(Si4.01Al1.98)O12·nH2O | Ozar, Nashik, India | |
Pollucite | R050344 | Cs(Si2Al)O6·nH2O | Chamachho, Skardu, Pakistan |
No. | RRUFF No. | Composition | Locality |
---|---|---|---|
Harmotome | R070015 | Ba2(Si12Al4)O32·12H2O | Strontian, Argylshire, Scotland, UK |
Paulingite | R070604 | (K,Ca,Na,Ba)10(Si,Al)42O84·34H2O | Vinařice, Kladno, Central Bohemia, Czech Republic |
R060457 | (Na2,K2,Ca,Ba)5Al10Si35O90·45H2O | ||
Gismondine | R060809 | Ca2(Si4Al4)O16·8H2O (Na0.05K0.01Ca2.17)(Si3.9Al4)O16·nH2O | Arensberg, Zilsdorf, Walsdorf, Gerolstein, Vulkaneifel District, Rhineland-Palatinate, Germany |
Garronite | R050281 | Ca3(Si10Al6)O32·14H2O (Na0.08K0.02Ca2.53)(S10.65A5.42)O32·nH2O | Synthetic zeolite from Chen et al. (2002) [13] |
Amicite | R080066 | Na2K2(Si4Al4)O16·5H2O Na1.52K1.52Ca0.07Si4.29Al3.89O16·nH2O | Synthetic zeolite from Chen et al. (2002) [13] |
Merlinoite | R130095 | K5Ca2(Si23Al9)O64·24H2O (Na2.14K7.06Ca0.19)(Si22.06Al10.05)·nH2O | Synthetic zeolite from Chen et al. (2002) [14] |
Gobbinsite | n/a | Na5(Si11Al5)O32·11H2O (Na5.08K0.01Ca0.02)(Si10.73Al5.32)O32·nH2O | Synthetic zeolite from Chen et al. (2002) [13] |
Phillipsite 1, 2 | R050078 | Ca3(Si10Al6)O32·12H2O (K1.34Na0.08Ca1.2)(Si12.19Al3.81)·nH2O | Rydec, Usti nad Labem, North Bohemia, Czech Republic |
R070271 | Na6(Si10Al6)O32·12H2O |
No. | RRUFF No. | Composition | Locality |
---|---|---|---|
Chabazite | R050014 | Ca2Si8Al4O24·13H2O | Wasson’s bluff, bay of Fundy, Novascotia, Canada |
R120032 | (K2NaCa0.5)Si8Al4O24·11H2O K2.70Na0.02Ca0.99Si8.68Al2.86O24·nH2O | ||
R061095 | (Na3K)Si8Al4O24·11H2O | ||
Levyne | R070270 | Ca3(Si12Al6)O36·18H2O (Na1.29K0.26Ca1.8)(Si12.19Al6.04)·nH2O | Moonen Bay, Isle of Skye, Scotland, UK |
R060021 | Na6(Si12Al6)O36·18H2O | ||
Goosecreekite | n/a | CaSi6Al2O16·5H2O | Nashik, Maharashtra, India |
Gmelinite | R060168 | Na4(Si8Al4)O24·11H2O (Na2.19K1.21Ca0.25)(Si8.12Al3.87)O24·nH2O | Five Island, NS, Canada |
Erionite | R060836 | Ca5(Si26Al10)O72·30H2O (Ca1.76Mg0.71Na0.47K2.58) (Si28.19Al7.76)O72·nH2O | Little Ajo Mountains, AZ, USA |
No. | RRUFF No. | Composition | Locality |
---|---|---|---|
Epistilbite | R061105 | Ca3(Si18Al6)O48·16H2O | Ojhar mine, Nashik, Maharashtra, India |
Mordenite | R061118 | (Na2,Ca,K2)4(Si40Al8)O96·28H2O (Na1.24K1.45Mg0.03Ca2.05) (Si40.93Al7.14)O96·nH2O | Nashik, Maharashtra, India |
Dachiardite | R061097 | Ca2(Si20Al4)O48·13H2O | Pahlia river, Culverden, Canterbury, South Island, New Zealand |
Bikitaite | R050160 | Li(AlSi2O6)·H2O | Kings Mountain, NC, USA |
No. | RRUFF No. | Composition | Locality |
---|---|---|---|
Brewsterite | R070120 | Ba(Al2Si6)O16·5H2O | Yellow Lake, Osoyoos Mining Division, BC, Canada |
R070227 | Sr(Al2Si6)O16·5H2O | ||
Clinoptilolite (2) | R060662 | Ca3(Si30Al6)O72·20H2O (Ca1.7Mg0.03Na1.31K1.07)(Si29.69Al6.47)O72·nH2O | Malheur co., OR, USA |
R110201 | K6(Si30Al6)O72·20H2O | ||
R061099 | Na6(Si30Al6)O72·20H2O | ||
Stellerite (2) | R040174 | Ca4(Si28Al8)O72·28H2O | Tisgaon Mine, Aurangabad, Maharashtra, India |
Stilbite (2) | R050012 | NaCa4(Si27Al9)O72·28H2O (Na0.46K0.01Ca4.06)(Si27.79Al8.08)O72·nH2O | Nashik, Maharashtra, India |
Barrerite | R050135 | Na2(Al2Si7)O18·6H2O | Alaska garnet Mines, Kuiu Island, AK, USA |
Heulandite | R050017 | NaCa4(Si27Al9)O72·24H2O (Na1.89K0.15Ca3.26)(Si27.69Al8.23)O72·nH2O | Nashik, Maharashtra, India |
R061137 | KCa4(Si27Al9)O72·24H2O | ||
R070281 | (Na,Ca)6(Si,Al)36O72·24H2O | ||
R070272 | NaSr4(Si27Al9)O72·24H2O |
No. | RRUFF No. | Composition | Locality |
---|---|---|---|
Cowlesite | R060627 | Ca(Al2Si3)O10·5−6H2O | County Antrim, Northern Ireland, UK |
Al-O-Al Modes | Si-O-Si Modes | Others | |
---|---|---|---|
Natrolite group | 433–447 | 528–538 | |
Analcime group | 379–392 | 475–497 | |
Gismondine group | 391–432 | 463–497 | |
Chabazite group | 477–509 | 320–340 | |
Mordenite group | 397–410 | 470–529 | 800–965 |
Heulandite group | 402–416 | 480–500 | 612–620 |
Wavenumber Range (cm−1) | Vibration Mode |
---|---|
250–360 | M-O (M stands for cations) |
379–447 | O vibration in T-O-T (T stands for Al) |
459–538 | O vibration in T-O-T (T stands for Si) |
530–575 | T-O bending |
780–980 | Si in tetrahedron |
1100–1450 | T-O bending |
3224, 3474 | OH stretching |
3550 | OH stretching (bridging) |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
Share and Cite
Tsai, Y.-L.; Huang, E.; Li, Y.-H.; Hung, H.-T.; Jiang, J.-H.; Liu, T.-C.; Fang, J.-N.; Chen, H.-F. Raman Spectroscopic Characteristics of Zeolite Group Minerals. Minerals 2021, 11, 167. https://doi.org/10.3390/min11020167
Tsai Y-L, Huang E, Li Y-H, Hung H-T, Jiang J-H, Liu T-C, Fang J-N, Chen H-F. Raman Spectroscopic Characteristics of Zeolite Group Minerals. Minerals. 2021; 11(2):167. https://doi.org/10.3390/min11020167
Chicago/Turabian StyleTsai, Ying-Lai, Eugene Huang, Yu-Ho Li, Hsiao-Tien Hung, Jhih-Hao Jiang, Teh-Ching Liu, Jianng-Neng Fang, and Huei-Fen Chen. 2021. "Raman Spectroscopic Characteristics of Zeolite Group Minerals" Minerals 11, no. 2: 167. https://doi.org/10.3390/min11020167