Washington University in St. Louis Washington University Open Scholarship Arts & Sciences Electronic Theses and Dissertations Arts & Sciences Summer 8-15-2019 Solid-State NMR of CO2 Mineralization and NMR Crystallography Jinlei Cui Washington University in St. Louis Follow this and additional works at: https://openscholarship.wustl.edu/art_sci_etds Part of the Physical Chemistry Commons Recommended Citation Cui, Jinlei, "Solid-State NMR of CO2 Mineralization and NMR Crystallography" (2019). Arts & Sciences Electronic Theses and Dissertations. 1894. https://openscholarship.wustl.edu/art_sci_etds/1894 This Dissertation is brought to you for free and open access by the Arts & Sciences at Washington University Open Scholarship. It has been accepted for inclusion in Arts & Sciences Electronic Theses and Dissertations by an authorized administrator of Washington University Open Scholarship. For more information, please contact [email protected]. WASHINGTON UNIVERSITY IN ST. LOUIS Division of Chemistry Dissertation Examination Committee: Sophia E. Hayes, Chair Alexander Barnes Julio M. D’Arcy Joseph A. Fournier Jill D. Pasteris Solid-State NMR of CO2 Mineralization and NMR Crystallography by Jinlei Cui A dissertation presented to The Graduate School of Washington University in partial fulfillment of the requirements for the degree of Doctor of Philosophy August 2019 St. Louis, Missouri © 2019, Jinlei Cui Table of Contents List of Figures ................................................................................................................................. v List of Tables ................................................................................................................................ xii List of Abbreviations ................................................................................................................... xiii Acknowledgments........................................................................................................................ xiv Abstract of the Dissertation ....................................................................................................... xviii Chapter 1: ........................................................................................................................................ 1 Introduction ..................................................................................................................................... 1 1.1 CO2 Capture and Storage ................................................................................................. 1 1.2 Nuclear Magnetic Resonance ........................................................................................... 4 1.2.1 Spin Quantum Number ......................................................................................................... 4 1.2.2 NMR Hamiltonian................................................................................................................. 6 1.2.3 Magic Angle Spinning ........................................................................................................ 10 1.2.4 Spin Process and Detection ................................................................................................. 12 1.3 NMR Pulse Sequence ..................................................................................................... 14 1.3.1 Bloch Decay ........................................................................................................................ 14 1.3.2 Hahn Echo ........................................................................................................................... 15 1.3.3 Rotational Echo Double Resonance .................................................................................... 16 1.4 NMR Crystallography .................................................................................................... 18 1.5 Conclusions .................................................................................................................... 20 Chapter 2: NMR Study of Magnesium Carbonate Formation Through In-Situ Solid-State NMR ....................................................................................................................................................... 22 2.1 Introduction .................................................................................................................... 22 2.2 Experimental methods .................................................................................................... 24 2.2.1 Probe Design for In-Situ Solid-State NMR in Batch Reactions ......................................... 24 2.2.2 Probe Design for Flow-Through NMR Apparatus .............................................................. 26 2.2.3 Synthesis of Starting Materials ........................................................................................... 30 2.2.4 In-Situ Solid-State 13C NMR Experiment ........................................................................... 31 2.2.5 Ex-Situ Solid-State 13C NMR Experiment .......................................................................... 32 2.2.6 Microscopy of Reacted Sample .......................................................................................... 33 2.3 Results and Discussion ................................................................................................... 34 ii 2.3.1 Fractured Cylinder Experiment ........................................................................................... 34 2.3.2 Fracture Cylinder Sample in Flow-through Experiments ................................................... 39 2.4 Conclusions .................................................................................................................... 41 2.5 Acknowledgements ........................................................................................................ 42 Chapter 3: Evidence from 29Si Solid-State NMR of Dissolution-Precipitation Reactions of Forsterite ....................................................................................................................................... 44 3.1 Introduction .................................................................................................................... 44 3.2 Experimental methods .................................................................................................... 45 13 3.2.1 Reactions of Forsterite with CO2 under Elevated Temperature and Pressure .................. 45 29 1 3.2.2 Si { H} MAS NMR .......................................................................................................... 47 13 1 3.2.3 C{ H} MAS Solid-State NMR ......................................................................................... 48 3.3 Results and Discussion ................................................................................................... 49 3.3.1 The Silica-Rich Layer ......................................................................................................... 49 3.3.2 T1 Measurement of Forsterite and Amorphous Silica ......................................................... 50 3.3.3 29Si{1H} MAS NMR as a Function of Depth ...................................................................... 53 3.3.4 Analysis of Qn Sites in Amorphous Silica ........................................................................... 55 3.3.5 13C{1H} MAS NMR ............................................................................................................ 58 3.4 Conclusions .................................................................................................................... 60 3.5 Acknowledgements ........................................................................................................ 61 Chapter 4: NMR Crystallography: Evaluation of Hydrogen Positions in Hydromagnesite ......... 62 4.1 Introduction .................................................................................................................... 62 4.2 Experimental methods .................................................................................................... 63 4.2.1 Preparation of 10% 13C Enriched Hydromagnesite ............................................................. 63 4.2.2 Powder XRD ....................................................................................................................... 64 4.2.3 Solid-State NMR ................................................................................................................. 64 4.2.4 DFT Calculations ................................................................................................................ 66 4.3 Results and Discussion ................................................................................................... 68 4.3.1 XRD of Synthesized Hydromagnesite ................................................................................ 68 4.3.2 13C MAS NMR and 1H MAS NMR .................................................................................... 69 4.3.3 Static 13C NMR and Slow Spinning 13C CPMAS NMR ..................................................... 70 4.3.4 Chemical Shift Computation by DFT and Simulation of Static Lineshape ........................ 73 4.3.5 13C{1H} REDOR and SIMPSON Simulation ..................................................................... 77 iii 4.3.6 Comparison between Experimental XRD curve and Prediction ......................................... 82 4.3.7 Comparison of vdW-DF2, GGA-PBE