Introduction and synthesis of zeolites Reporters： Yu, Peiyao; Liu, Xin; Kuang, Tingrui;Li, Tianyu; Lu, Haoran 1

CONTENT Introduction Crystal Growth Instruments Methods New prepare method 2

PART 01 Introduction 3

Introduction Fig. 1. Zeolites Schematic diagram of molecular sieve structure 4

Introduction Semiconductor Pharmaceuticals Gas-storage materials Radio-active waste Storage materials 5

Introduction Fig. 2. TEM Patterns of four kinds of zeolites (a): NiY; (b): CoY; (c): NiTiY; (d): CoTiY 6

PART 02 Crystal Growth 7

Crystal Growth Take the zeolite SAPO-18 as an example. SAPO-18 has the framework code AEI and the structure is given in Fig. 3. Fig. 3. SAPO-18 Cage structure and unit cell of SAPO-18 showing the double 6-rings (grey) and both orientations of the AEI-cage (red and green): (a) viewed along the a direction; (b) viewed along the b direction. The 'nose' of the AEI-cage is on the right in the A layer and the left in the B layer in (a). 8

Crystal Growth The growth model of SAPO-18. Fig. 4. Schematic showing the basic structure of the screw dislocation and relative grow rates. 9

Crystal Growth Fig. 5. (a) Top-down view of the cage structure of the screw dislocation with terraces edges indicated by white lines; (b) alternative structure where the order of A and B layers are reversed; (c) oblique view of the structure shown in (a) 10

Crystal Growth The discovery of screw dislocations. Fig. 6. (a) In situ dissolution of SAPO-18 after 102 minutes in solution; (b) schematic showing a trace of the terraces edges and the spiral dissolution pit on the dissolved crystal; (c) 3D representation of a simple round spiral growth hillock with a spiral dissolution pit at its core. Red arrows show two terraces winding down from the same layer. Scale bar shown in (a) is 500 nm. 11

Crystal Growth Fig. 7. a) Schematic of the centre of the spiral for the crystal given in Fig. 2a showing the small spiral dissolution pits at the core of the spiral growth hillock; (b) enlarged AFM image of the centre of the screw dislocation. The terrace pattern is a result of a composite of four screw dislocations. The spiral dissolution pits can be seen as dark defects on the crystal surface. Scale bar shown on (b) is 500 nm. 12

PART 03 Instruments 13

Instruments X-ray diffraction (XRD) 14

Instruments Scanning electron microscopy (SEM) 15

Atomic force microscopy Instruments Atomic force microscopy (AFM) 16

Instruments Solid-state nuclear magnetic resonance (NMR) 17

Instruments 18

PART 04 Methods 19

Methods Hydrothermal solution Solvothermal Synthesis of crystalline solid materials Ionothermal solid 20

Methods Hydrothermal autoclave crystallon culture A device for growing crystals by hydrothermal method 21 https://image.baidu.com/search/detail

Methods Solvothermal https://image.baidu.com/search/detail 22

Methods Ionothermal 23

PART 04 New prepare method 24

What is 2D zeolite? Fig. 8. Regard UTL crystalline zeolite as infinite layer putting together, forming a 3D structure. What if we just pull out one or several layers? 25

ADOR process Fig. 9. Assemble Disassemble Organization Reassemble 26

Example Fig. 12. XRD pattern from 1-408 2q for UTL, lamellar IPC-1P, swollen IPC-1SW, pillared IPC-1PI, IPC-2 and IPC-4. Fig. 11. ADOR processes to novel materials from hydrolysis of zeolite UTL. 28

What happened in disassemble process? Fig. 10. Scanning electron microscopy images of a) UTL; b) IPC-1P; c) IPC-2; d) IPC-4; e,f) IPC-1SW; g,h) IPC-1PI. The characteristic square and rectangular terrace patterns, low angle defects and intergrowths are all still present. It is believed that the zeolite is just divided into 2D layers in the disassembly process, and simply reassemble in different ways depending on the conditions. 27

Reference [1]Smith, Rachel L. , et al. "Anatomy of screw dislocations in nanoporous SAPO-18 as revealed by atomic force microscopy." Chem. Commun. 51.28(2015):6218-6221. [2]Smith, Rachel L. , et al. "Nanoporous Intergrowths: How Crystal Growth Dictates Phase Composition and Hierarchical Structure in the CHA/AEI System." Chemistry of Materials 27.12(2015):4205-4215. [3]Holland, Brian T. ,  L. Abrams , and  A. Stein . "Dual Templating of Macroporous Silicates with Zeolitic Microporous Frameworks." Journal of the American Chemical Society 121.17(1999):4308-4309. [4]Panda, Tamas , et al. "Amino functionalized zeolitic tetrazolate framework (ZTF) with high capacity for storage of carbon dioxide." Chemical Communications 47.7(2011):2011-2013. [5]Yu, Jihong , and  R. Xu . "Rational Approaches toward the Design and Synthesis of Zeolitic Inorganic Open-Framework Materials." Accounts of Chemical Research 43.9(2010):1195-1204. [6]Lewis, Dewi W. , et al. "Zeolitic imidazole frameworks: structural and energetics trends compared with their zeolite analogues." CrystEngComm 11.11(2009):2272. [7]Smith, Rachel L. , et al. "Atomic Force Microscopy of Novel Zeolitic Materials Prepared by Top-Down Synthesis and ADOR Mechanism." Chemistry - A European Journal 20.33(2014):10446-10450. 29

THANK YOU FOR LISTENING Reporters：Yu, Peiyao; Liu, Xin; Kuang, Tingrui;Li, Tianyu;Lu, Haoran 30