Applications of X-ray and Electron Crystallography in Structural Investigations of Zeolites

doi:10.7503/cjcu20200406

Abstract

Abstract:

Zeolites， a class of crystalline microporous materials with unique channels or cavities， have excellent performance in adsorption， separation， and catalysis. In order to correlate the structure-property relationship， it is essential to determine the crystallographic structures of zeolite at the atomic level. In this review， a series of conventional and emerging techniques regarding X-ray crystallography and electron crystallography for characterizing the crystallographic structures of zeolites through real space and reciprocal space are introduced. Furthermore， 85 recently discovered novel zeolites are systemically summarized based on the structure determination approaches and their chemical compositions. Nine zeolites with different framework type codes（FTCs） are further highlighted due to their unique synthetic methodologies or structural features.

Key words: Zeolite, Structural characterization, X-ray crystallography, Electron crystallography, Framework type code

CLC Number:

O611.2

TrendMD:

MA Chao, LIU Xiaona, NIE Chenyang, CHEN Lu, TIAN Peng, XU Hongyi, GUO Peng, LIU Zhongmin. Applications of X-ray and Electron Crystallography in Structural Investigations of Zeolites[J]. Chem. J. Chinese Universities, 2021, 42(1): 188.

Figures/Tables 10

Fig.1 STOE SXRD(left) and its schematic illustration(right)(A) and Ge and F atoms located in NUD?2(B)(A) By courtesy of Dr. Yangchun Rong from STOE.

Fig.2 An RSS approach facilitating the targeted synthesis of DNL?6 and SAPO?42(A); in the as?made FER zeolite(blue: Al or Si atom, red: O atom), unprotonated pyridine located in the fer cage(B) and 10?ring channel(C), respectively; Na+ ion is in the 10?ring channel only(D); in the pyridine? adsorbed sample, the protonated pyridine is occluded in the 10?ring channel and forms hydrogen bonding with framework oxygen O2(E)[16]Copyright 2017, Royal Society of Chemistry.

Fig.3 Schematic illustration of RED method(A)[36]; HRTEM images of a thin edge(B) and broken crystal piece(C) of Beta?TEAOH[23]; low magnification TEM image of ZSM?57?Na(D); HRTEM images of the highlighted orange area(E) and isolated fragment from the same sample(F)[27](A) First, 2D electron diffraction pattern was collected at each combined tilt angle. Then, 3D electron diffraction data was reconstructed and processed. Finally, the structure model can be solved. Copyright 2013, Wiley?Blackwell; (B, C) The stacking sequences of 12?ring channels are marked in the images.The inserts are FFT patterns of the thin area of the images. Copyright 2015, Springer Nature; (D, E, F) Copyright 2019, Wiley?VCH.

Fig.4 Schematic illustration of STEM system(A)[42]; HAADF image of site?isolated Pt atoms in KLTL zeolite in the oxidized sample(B)[6]; iDPC images of the surface terminations from the [010] direction in the ZSM?5(C—F); iDPC image of the (010) interfaces between ZSM?5 particles(G); iDPC image of the PX?adsorbed ZSM?5 from the [010] direction(H)[12] and iDPC image of Mo/ZSM?5(I)[14](A) The inner is the segmented detector for iDPC imaging, while the outer is the HAADF detector.Copyright 2020, American Association for the Advancement of Science; (B) White features in dashed blue circles indicate Pt atoms.Copyright 2014, Wiley?VCH; (C―H) Copyright 2019, Wiley?VCH; (I) Copyright 2020, Wiley?VCH.

Table 1 Eighty-five novel zeolites discovered since 2007

Code	Material	Structure determination	Code	Material	Structure determination
*?SVY	SSZ?70^a	Modelling+HRTEM+PXRD	*PCS	IPC?6^a	Modelling+PXRD
CSV	CIT?7^a	RED+PXRD	*SFV	SSZ?57^a	PXRD
IFY	ITQ?50^a	PXRD	*MRE	ZSM?48^a	Modelling+HRTEM+PXRD
OKO	IPC?2^a	Modelling+PXRD	?SVR	SSZ?74^a	PXRD+HRTEM
PCR	IPC?4^a	Modelling+PXRD	*STO	SSZ?31^a	Modelling+HRTEM+PXRD
―	IDM?1^a	cRED+PXRD^[44]	―	ECNU?36^a	3DEDT+HRTEM+PXRD^[45]
―	NUD?5^a	SXRD^[46]	―	NUD?6^a	SXRD^[47]
ETV	EMM?37^b	cRED	MWF	ZSM?25^b	RED+PXRD
―	PST?20^b	RED+PXRD^[9]	―	PST?25^b	RED+PXRD^[9]
―	PST?26^b	SAED+PXRD^[25]	―	PST?28^b	SAED+PXRD^[25]
PWN	PST?29^b	SXRD+PXRD	*?EWT	EMM?23^b	RED+PXRD
MRT	ZSM?43^b	RED+PXRD	*?ITN	ITQ?39^b	HRTEM
PTY	PST?30^b	PXRD	*?SSO	SSZ?61^b	Modelling+HRTEM+PXRD
PWO	PST?21^b	PXRD	EEI	SSZ?45^b	RED+PXRD
PWW	PST?22^b	PXRD	SFW	SSZ?52^b	PXRD+HRTEM
YFI	YNU?5^b	PXRD	LTJ	Linde type J^b	PXRD
ETL	EU?12^b	PXRD	LTF	LZ?135^b	PXRD
EWO	ECNU?21^c	cRED	ITG	ITQ?38^c	Modelling+HRTEM+PXRD
?SYT	SYSU?3^c	cRED	ITT	ITQ?33^c	PXRD
SOV	SCM?15^c	RED+PXRD	SVV	SSZ?77^c	PXRD
*UOE	IM?18^c	RED+PXRD	?ITV	ITQ?37^c	PXRD
*CTH	CIT?13^c	RED+PXRD	IRR	ITQ?44^c	PXRD
SOR	SCM?14^c	RED+PXRD	UWY	IM?20^c	PXRD
?IFT	ITQ?53^c	RED+PXRD	ITR	ITQ?34^c	PXRD
?IFU	ITQ?54^c	RED+PXRD	UOS	IM?16^c	PXRD
IRN	ITQ?49^c	PXRD	IWS	ITQ?26^c	SAED+PXRD
POS	PKU?16^c	RED+PXRD	SOF	SU?15^c	SXRD
UOV	IM?17^c	RED+PXRD	STW	SU?32^c	SXRD
?IRY	ITQ?40^c	SXRD+PXRD	―	NUD?1^c	SXRD^[48]
EWS	EMM?26^d	RED+PXRD	MVY	MCM?70^d	PXRD
IFW	ITQ?52^d	PXRD	SFS	SSZ?56^d	PXRD
SEW	SSZ?82^d	PXRD	SSF	SSZ?65^d	PXRD
JSR	GaGeO?JU64^e	SXRD	BOF	UCSB?15^e	SXRD
BOZ	Be?10^e	SXRD	BSV	UCSB?7^e	SXRD
JST	GaGeO?CJ63^e	SXRD	SBN	UCSB?9^e	SXRD
PUN	PKU?9^e	SXRD	JOZ	LSJ?10^e	SXRD
AVE	AlPO?78^f	PXRD	IFO	ITQ?51^f	RED+PXRD
POR	PST?14^f	cRED+PXRD	JSN	CoAPO?CJ69^f	SXRD
SWY	STA?20^f	SAED+PXRD	JSW	CoAPO?CJ62^f	SXRD
PSI	PST?6^f	RED+PXRD	NPT	Oxonitridophosphate?2^f	PXRD
JNT	JU?92?300^f	SXRD	SAF	STA?15^f	PXRD
AFV	ZnAlPO?57^f	PXRD	JRY	CoAPO?CJ40^f	SXRD
AVL	ZnAlPO?59^f	PXRD

Fig.5 CBUs of ITQ?29(d4r, sod, and lta) and ITQ?50(d4r, sti, sod, and ify)(A) and different 8?ring channels of ITQ?50 viewed along [110] and [001] directions(B)Bridging O atoms have been omitted for clarity(blue: Si atom).

Fig.6 Building layer(pst?21 layer) nonjointly comprising bre CBUs(A); PST?21 and PST?22 structures viewed along the c?axis(B); the building layer(bre_L1 layer) nonjointly comprising bre CBUs are stacked PST?30 structure with 8?ring and 10?ring channels viewed along the c? and a?axis(C)Bridging O atoms have been omitted for clarity(blue: Al or Si atom). (B) The building layers in PST?21 and PST?22 are stacked in sequences AAAA… and AAtAAt… along the a?axis, respectively.

Fig.7 Framework representations of cross?sections of RHO?G1 to RHO?G8 in the RHO familyBridging O atoms have been omitted for clarity(blue: Al or Si atom).

Fig.8 Condense layer of EMM?26(A); 3D framework generated by connecting the adjacent layers, which are related by a mirror perpendicular to the a?axis(B) and location of the OSDA in the cavity of EMM?26(C)Oxygen atoms have been omitted for clarity.(A) fer and mor CUBs are highlighted in red and yellow, respectively.

Fig.9 ac?plane of SCM?14(A), 3D framework of SOR(B), ac?plane of SCM?15(C) and 3D framework of SOV(D)Oxygen, germanium and non?framework atoms have been omitted for clarity.

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