Luận án Tiến sĩ: Hấp thụ Khí trong MOFs bằng Khái niệm Hiệu suất Bám dính (Iriowen)

Adsorption of Hydrogen, Methane and Carbon Dioxide Gases in Metal-Organic Frameworks using the Sticking Efficiency Concept; (A New Approach) BY ESOSA MARK IRIOWEN A DISSERTATION Submitted as a partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Applied Chemistry Graduate Program of Delaware State University DOVER, DELAWARE December 2015 DEDICATION This doctoral research work is specially dedicated; To: God Almighty. To: My wife (Dr. And my lovely son, Osawerene Iriowen (my big little me). To: my father; (Pastor) Samuel Imuetinyan Iriowen (April 7, 1933 – April 21, 2011).

and my mother, (Deaconess) Mary Iriowen. To: brother (Mr.) Peter Iriowen (Deceased) and sister (Ms.) Itohan Iriowen (Deceased) ii ACKNOWLEDGEMENTS The writing of this dissertation has been one of the most significant academic challenges I have ever had to face. Without the support, patience and guidance of the following people, this study would not have been completed. It is to them that I owe my deepest gratitude.

Andrew Goudy, (Director and Supervisor-Center for Hydrogen Storage Research (CHSR) at DESU) who undertook to act as my advisor despite his many other academic and professional commitments. His wisdom, knowledge and commitment to the highest standards inspired and motivated me. Department of Energy (DOE) and the U. Department of Transportation (DOT) for financially supporting this research.

Cherese Winstead, (Chairperson of Chemistry Department of Delaware State University) for making my learning and knowledge acquisition in the Department of Chemistry-DESU a success.  A big thank you to my Committee Members for their reviews of this masterpiece.  All faculty, staff and students of the Chemistry Department at DESU-USA. Michael Casson Jr., Director of the University Center for Economic Development and International Trade for love and peace you provided during my academic goal pursuit.

 My friends and colleagues,; (Drs.) Olanrewaju Sanusi, Orefuwa Samuel, Temitope Sabitu, Tolulope Durojaiye, Adeola Ibikunle, Kimberly Mellingan, Jalaal Hayes and iii Pushpika Katukampola, who inspired my final effort despite the enormous work pressures we were facing together.) Leida Sanchez, and others too many to list here due to space factor.  Rosemary Iriowen (MD), my wife, without whom this effort would have been worth nothing. Your love, support and constant patience have taught me so much about sacrifice and discipline. You are my number one fan.

 (Pastor) Samuel and (Deaconess) Mary Iriowen, my parents, who have always supported, encouraged, prayed and believed in me through all my endeavors and who so lovingly and unselfishly cared for me.  Osawerene Iriowen, my son, who was born before this dissertation was completed and who spent many days with his mother and grandmother at home to allow me to focus. I am deeply sorry for the time we spent apart and I deeply cherish and love every moment we are together playing and speaking gibberish over the phone.  My siblings, (Elder) Victor Iriowen, (Mrs) Irene Obadiaru, (Engr.) Osaro Iriowen, (Ms.) Osatohanmwen Iriowen and my mother-in-law, (Mrs.) Bridget Oviasojie for all your encouragement and profound understanding.

 To the Almighty Father (GOD) in the Upper House (Heaven), thank you for “Ephesians 3:20” over me and my household. iv Adsorption of Hydrogen, Methane and Carbon Dioxide Gases in Metal-Organic Frameworks using the Sticking Efficiency Concept; (A New Approach) Esosa Iriowen Advisor: Dr. Andrew Goudy ABSTRACT In this research, the adsorptions of three different gases namely Hydrogen (H2); Carbon Dioxide (CO2) and Methane (CH4) on a variety of Metal-Organic Frameworks (MOFs) such as zinc Benzene-1,4-dicarboxylate (Zn-BDC), Zinc 2,6- Napthalenedicarboxylate (Zn-NDC), Copper 1,3,5-Benzenetricarboxylate (Cu-BTC), Zinc Methyl-lmidazolate (Zn-Mim) and Iron and 1,3,5-Benzenetricarboxylate (Fe-BTC) were studied and compared at low and high pressures under different temperatures. It was expected that MOFs with large surface areas would adsorb more gas(es) than those with smaller surface areas.

However this is not always true because there are other factors such as the nature of the surface sites of these materials that also affect gas adsorption. Therefore, a new parameter denoted sticking efficiency (θ) was devised and tested to determine how well it would correlate with gas adsorption capacity. It was found that at low pressures, sticking efficiency correlated better with gas sorption capacity than did surface area. Since the sticking efficiency also correlated well with adsorption enthalpy, results show that the strength of interactions between the MOF surface and the adsorbed gas may be a v more important factor when it comes to adsorption capacity.

However, at high pressures, surface area correlated better with the gas sorption capacity than did sticking capacity. The most likely reason for this is that saturation generally occurs at high pressures and, when the surfaces are fully covered, the MOF with the greatest surface area will adsorb the most. vi TABLE OF CONTENTS DEDICATION. v TABLE OF CONTENTS.

vii LIST OF TABLES. xii LIST OF FIGURES. xiv CHAPTER ONE INTRODUCTION .0 Literature Review and Motivation .1 Hydrogen Gas, Properties and Storage.2 Methods of Hydrogen Storage from Department of Energy Perspective .3 Different Ways of Hydrogen Storage .1 Cryogenic Storage for Hydrogen .2 Compressed Storage for Hydrogen .3 Solid State method for Storing Hydrogen .4 Hydrogen Atoms in Metal (Chemisorption) .5 Hydrogen in Porous Materials (Physisorption) .6 Compounds of Hydrogen with Ionic Character (Complex and Metallic Hydrides) .4 Carbon Dioxide Gas, Properties, and Storage .5 Carbon Dioxide Storage and Department of Energy (DOE) Goals .6 Methane Gas, Properties and Storage .7 Methane Storage and Department of Energy Target .1 Compressed Natural Gas (CNG) .2 Liquefied Natural Gas (LNG) .3 Solid State Storage for Adsorbed Natural Gas (ANG) .8 Adsorption History, Importance, Principles and Applications .1 Adsorption by Powders .2 Adsorptions by Porous Materials .3 Classifications and Types of Adsorption Isotherms .4 Physisorption and Chemisorption Principles .9 Metal Organic Frameworks (MOFs); and IUPAC Understanding .1 Types, Applications and Limitations of Metal-Organic Frameworks.2 Overviews of All Selected MOFs-Materials for This Research.3 Zinc Benzene-1,4-dicarboxylate (Zn-BDC) or Isorecticular Metal-Organic Frameworks – 1 (IRMOF-1/MOF-5) .6 Zinc Methyl-lmidazolate (Zn-Mim) or Zeolitic Imidazolate Framework (ZIF-8) .7 Iron and 1,3,5-Benzenetricarboxylate (Fe-BTC) Framework (Basolite F300) .11 Objectives, Goals of This Research. 31 CHAPTER TWO EXPERIMENTAL PROTOCOL .4 Sample Handling and MOF Synthesis .5 Zn-NDC Synthesis .6 Zn-BDC Synthesis.7 Cu-BTC Synthesis .8 Zn-Mim and Fe-BTC Synthesis .9 Material Characterizations, Measurements and Sample Handling .11 Using the X-RAY Diffraction (XRD) for Analysis .13 Laser Diffraction Particle Size Analyzer (LDPSA) .14 Fourier Infrared Spectroscopy Analyzer .15 Surface Area and Porosity Analyzer .16 High Pressure Volumetric Analyzer (HPVA) .17 Scanning Electron Microscope (SEM).

57 CHAPTER THREE MATERIAL CHARACTERIZATIONS .0 Characterizing the Selected Metal-Organic Frameworks (MOFs).1 Obtaining the Optimum Surface Area for Zn-BDC .2 Obtaining the Thermal Stabilities (TGA) of Synthesized MOFs .3 XRD Spectra of Synthesized MOFs.4 Laser Diffraction Particle Size Analysis (LDPSA) of Studied MOFs .5 Scanning Electron Microscope (SEM) .6 Fourier Transformed Infrared Spectroscopy (FTIR) for Studied MOFs .7 Surface Areas and Pore Volume for Studied MOFs .8 Surface Area and Gas(es) Adsorption Isotherms. 74 CHAPTER FOUR HYDROGEN GAS ADSORPTIONS .0 Sticking Efficiency (Ɵ) the Concept .1 Relationship Between Surface Area (SSA) and Sticking Efficiency (S(θ)) .2 Hydrogen Adsorptions and Isotherms .3 Enthalpy of Adsorptions. 100 CHAPTER FIVE METHANE GAS ADSORPTIONS .0 Methane Gas Adsorption Isotherms .1 Methane Adsorption and Sticking Efficiency (Ɵ).2 Enthalpy of Adsorptions. 117 CHAPTER SIX CARBON DIOXIDE GAS ADSORPTIONS .0 Carbon Dioxide Gas Adsorption Isotherms .1 Carbon Dioxide Gas Adsorption .2 Enthalpy of Adsorptions.

138 CHAPTER SEVEN CONCLUSION.1 Future Works Recommendation. 151 Publications From This Research. 158 xi LIST OF TABLES Table 1.1 Quick Scan: Porous Solids.2 Quick Scan: Powders .3 Quick Scan: Adsorption .1 Getting the synthesis temperature for Zn-BDC, using the rapid solvothermal method.2 Particle sizes for the synthesized and purchased MOFs used for this work .3 Showing both synthesized and purchased MOFs surface area and pore volume at 50 cm3/g .1 Low Pressure (LP) and High Pressure (HP) values for hydrogen gas adsorptions on selected MOFs along with their BET surface area and corresponding sticking efficiencies .2 Hydrogen adsorption analysis data at 77 K under low pressure .3 High Pressure Hydrogen adsorption analysis data at 77 K .1 Methane low and high pressure weight percent data .2 High pressure data for CH4 adsorption @ 298 K .3 Low pressure data for CH4 adsorption @ 298 K .4 Low Pressure (LP) and High Pressure (HP) calculated values for methane gas adsorptions on selected MOFs .1 Low Pressure (LP) and High Pressure (HP) calculated values for carbon dioxide gas adsorptions on selected MOFs .2 Carbon Dioxide Adsorption Sticking Efficiency (Ɵ) at Low and High Pressures Studies. 124 xiii LIST OF FIGURES Fig.

Probe accessibility over surface of material .1 The figure indicates the classification of adsorption isotherms defined by IUPAC .Pictorial structure of MOFs members formation sharing same topology and length. The expansions of their links increases their internal void space and allows for catenation formations. Rational modification, otherwise known as MOFs functionalizaton. Some structures of organic linkers for MOFs synthesis .1 Ball-milling machine, courtesy of Center for Hydrogen Storage and Research (CHSR) laboratory at Delaware State University, Dover.

The Glove Box. Courtesy of Delaware State University, Dover. Center for Hydrogen Storage and Research (CHSR). A PANalytical X’pert X-Ray Diffractometer Instrument.

Courtsey of Delaware State University, Dover. Center for Hydrogen Storage and Research (CHSR). The Perkin-Elmer Diamond TG/DTA Analyzer. Courtsey of Delaware State University, Dover.

Center for Hydrogen Storage and Research (CHSR).5 Laser diffraction particle size analyzer (Model: SALD-2201) from Shimadzu. Courtesy of Delaware State University, Dover. Center for Hydrogen Storage and Research (CHSR). (a) IRPrestige-21 Spectrometer from Shimadzu.(b) Sample studs, potassium bromide (KBr) (from Sigma-Aldrich and sample holder.

Courtesy of Delaware State University, Dover. Center for Hydrogen Storage and Research (CHSR). (a) Front-view of the Micromeritics ASAP 2020 surface area and porosity analyzer.(b) Back-view of the instrument showing the filters, vacuum pumps, beads column and all the different gas tanks connected. Courtesy of Delaware State University, Dover.

Center for Hydrogen Storage and Research (CHSR). Sample glass-tube, filler rod and seal frit used for BET and gas adsorption analysis. Courtsey of Delaware State University, Dover. Center for Hydrogen Storage and Research (CHSR) .(b) Rare-view of the instrument showing all the different gas tanks connected.

The insert photo shows the sample holder (2cc) with the gasket supplied by Swagelok. Courtesy of Delaware State University, Dover. Center for Hydrogen Storage and Research (CHSR. (a) Coating instrument (Denton Vacuum Desk IV) (b) Sample studs with samples on top.

Courtesy of University of Delaware, U. Center for Material Sciences, Department of Chemistry. JOEL JSM 7400F scanning electron microscope instrument, with insert snapshot of its resting base. Courtesy of University of Delaware, U.

Center for Material Sciences, Department of Chemistry. Snapshots of Zn-BDC (MOF-5), Zn-NDC (MOF-8) and Cu-BTC (HKUST-1) after synthesis from CHSR-DSU Laboratory, U.1 Chart of MOF-5 synthesis for this work, showing various temperature range of synthesis and corresponding error bar .2 Thermogravimetric (TGA) plots for synthesized and purchased MOFs used in this work.3 XRD patterns for Cu-BTC, Fe-BTC, Zn-Mim, Zn-BDC and Zn-NDC for this work showing their peak intensities versus 2Ɵ-angle. Particle distributions for the three synthesized MOFs and the two commercial MOFs used in this study. SEM capture photo for Zn-Mim MOF for this work.

SEM capture photo for Zn-NDC MOF for this work. SEM capture photo for Zn-BDC MOF for this work .8 SEM capture photo for Fe-BTC MOF for this work. SEM capture photo for Cu-BTC MOF for this work. IR-band spectra for synthesized and purchased MOFs used in this work.

Graph of surface area for synthesized and purchased MOFs. Graph of surface area and pore volume for synthesized and purchased MOFs. BET- Isotherms for synthesized and purchased MOFs for this studies. Chart showing relationship between BET surface area and sticking efficiencies for hydrogen (H2) at liquid nitrogen temperature (77 K) under high pressure .2 Hydrogen adsorptions Isotherms at low pressure (77 K) for MOFs used in this work.

Hydrogen adsorptions Isotherms at low pressure (196 K) for MOFs used in this work .