Scholars' Mine Doctoral Dissertations Student Theses and Dissertations Spring 2018 Atomic layer deposition prepared nanostructured materials for various catalytic reactions Xiaofeng Wang Follow this and additional works at: https://scholarsmine.mst.edu/doctoral_dissertations Part of the Chemical Engineering Commons, Environmental Engineering Commons, and the Nanotechnology Commons Department: Chemical and Biochemical Engineering Recommended Citation Wang, Xiaofeng, "Atomic layer deposition prepared nanostructured materials for various catalytic reactions" (2018). Doctoral Dissertations. 2901. https://scholarsmine.mst.edu/doctoral_dissertations/2901 This thesis is brought to you by Scholars' Mine, a service of the Missouri S&T Library and Learning Resources. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact [email protected]. ATOMIC LAYER DEPOSITION PREPARED NANOSTRUCTURED MATERIALS FOR VARIOUS CATALYTIC REACTIONS by XIAOFENG WANG A DISSERTATION Presented to the Faculty of the Graduate School of the MISSOURI UNIVERSITY OF SCIENCE AND TECHNOLOGY In Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY in CHEMICAL ENGINEERING 2018 Approved by: Dr. Xinhua Liang, Advisor Dr. Douglas K. Ludlow Dr. Fateme Rezaei Dr. Jee-Ching Wang Dr. Honglan Shi 2018 Xiaofeng Wang All Rights Reserved iii PUBLICATION DISSERTATION OPTION This dissertation consists of the following eight articles that have been published or pending submission for publication as follows: Paper I: Pages 13-39 have been published in Journal of Nanoparticle Research. Paper II: Pages 40-86 have been submitted to ACS Catalysis. Paper III: Pages 87-116 have been submitted to Green Chemistry. Paper IV: Pages 117-142 have been published in Catalysis Letters. Paper V: Pages 143-169 have been published in Nanotechnology. Paper VI: Pages 170-189 have been submitted in ChemCatChem. Paper VII: Pages 190-209 are intended for submission to ACS Catalysis. Paper VIII: Pages 210-237 are intended for submission to Nano Letters. iv ABSTRACT Atomic layer deposition (ALD) has been widely used for thin film coating and metal nanoparticles (NPs) preparation. In this report, the applications of ALD prepared nanostructured materials in catalysis were examined. Highly dispersed Pt monometallic catalysts with different substrates and multi- walled carbon nanotubes (MWCNTs) supported Pt-Co bimetallic catalysts were synthesized by ALD for selective hydrogenation of α, β‐unsaturated aldehydes to unsaturated alcohols (UA). Pt/MWCNTs showed the highest selectivity of UA in selective hydrogenation of citral, as compared to Pt/SiO2, Pt/ALD-Al2O3, and Pt/γ-Al2O3. After adding Co, the highest selectivity was achieved with high conversion in hydrogenation of both cinnamaldehyde and citral over an optimized Pt-Co/MWCNTs catalyst. Highly dispersed Pt-Co/MWCNTs bimetallic catalysts were also used for hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) reaction. High yield of DMF (> 90%) was achieved in hydrogenolysis of HMF over an optimized Pt-Co/MWCNTs catalyst after 8 hr of reaction time under mild conditions. Fe NPs and single atoms were deposited on various substrates via ALD. Fe/SiO2 NPs showed a high activity in CO oxidation reaction with a long-term stability at high temperature. The TiO2 NPs deposited with Fe single atoms showed the highest activity and had an up to six-fold photocatalytic activity enhancement over pure TiO2. CeO2 ALD and ZrO2 ALD were also applied on TiO2 to boost the photocatalytic activity of TiO2, and both two methods improved the photocatalytic efficiency of TiO2 significantly. v ACKNOWLEDGMENTS This study was conceived and completed from August 2014 to May 2018 in the Department of Chemical and Biochemical Engineering (ChBE) at Missouri S&T. I would like to express my appreciation to the people who helped me during my graduate studies. In particular, I would like to express my deep gratitude to my advisor, Dr. Xinhua Liang, for his willingness to share his experience, precious and tireless advice, encouragement, and endless patience all throughout my graduate studies. I also want to express my thanks to Dr. Douglas K. Ludlow, Dr. Fateme Rezaei and Dr. Jee-Ching Wang in the ChBE Department, and Dr. Honglan Shi in the Chemistry Department for being my graduation thesis committee. Their constructive suggestions for my research were vital. In addition, I would like to thank technicians in the Materials Research Center (Dr. Eric Bohannan for XRD analysis, Dr. Jessica Terbush and Dr. Jingjing Qing for TEM analysis, and Dr. Clarissa Weisner for SEM analysis), and technician (Dean Lenz) and staff (Marlene Albrecht, Emily Kost, and Dawn Schacht) in the ChBE Department. I am also grateful to Dr. Rajankumar Patel, Dr. Zeyu Shang, and all of my colleagues in Dr. Liang’s group for their willingness to share ideas and their help with experiments. This work was supported in part by the National Science Foundation (NSF-CBET 1402122) and American Chemical Society Petroleum Research Fund. Last but not least, I would like to convey a special thanks to my parents for their understanding, caring, and endless love. Without their encouragement and support, I would not be able to accomplish my study. vi TABLE OF CONTENTS Page PUBLICATION DISSERTATION OPTION .................................................................... iii ABSTRACT ....................................................................................................................... iv ACKNOWLEDGMENTS .................................................................................................. v LIST OF ILLUSTRATIONS ............................................................................................ xii LIST OF TABLES ........................................................................................................... xvi SECTION 1. INTRODUCTION ...................................................................................................... 1 1.1. ATOMIC LAYER DEPOSITION ...................................................................... 1 1.2. SELECTIVE HYDROGENATION OF A, B-UNSATURATED ALDEHYDES TO UNSATURATED ALCOHOLS ......................................... 3 1.3. HYDROGENOLYSIS OF 5-HYDROXYMETHYLFURFURAL TO 2,5- DIMETHYLFURAN .......................................................................................... 4 1.4. PHOTOCATALYTIC DEGRADATION OF ORGANIC POLLUTANTS BY TIO2-BASED PHOTOCATALYSTS ................................................................ 7 1.5. SUPPORTED FE SINGLE ATOMS .................................................................. 8 1.6. DISSERTATION SUMMARY .......................................................................... 9 PAPER I. SELECTIVE HYDROGENATION OF CITRAL OVER SUPPORTED PT CATALYSTS: INSIGHT INTO SUPPORT EFFECTS ......................................... 13 ABSTRACT ............................................................................................................. 13 1. INTRODUCTION ............................................................................................... 14 2. EXPERIMENTAL ............................................................................................... 16 vii 2.1. MATERIALS ............................................................................................ 16 2.2. CATALYST PREPARATION .................................................................. 17 2.3. CATALYST CHARACTERIZATION ..................................................... 17 2.4. CATALYTIC PERFORMANCE .............................................................. 18 3. RESULTS AND DISCUSSION .......................................................................... 19 3.1. CHARACTERIZATION OF SUPPORTS AND CATALYSTS .............. 19 3.2. CATALYTIC PERFORMANCE .............................................................. 22 4. CONCLUSIONS.................................................................................................. 35 CONFLICT OF INTEREST .................................................................................... 36 ACKNOWLEDGEMENTS ..................................................................................... 36 REFERENCES ........................................................................................................ 36 II. ATOMIC LAYER DEPOSITED PT-CO BIMETALLIC CATALYSTS FOR SELECTIVE HYDROGENATION OF A, B-UNSATURATED ALDEHYDES TO UNSATURATED ALCOHOLS ....................................................................... 40 ABSTRACT ............................................................................................................. 40 1. INTRODUCTION ............................................................................................... 41 2. EXPERIMENTAL SECTION ............................................................................. 43 2.1. CATALYST PREPARATION .................................................................... 43 2.2. CATALYST CHARACTERIZATION ...................................................... 44 2.3. HYDROGENATION OF UNSATURATED ALDEHYDES .................... 45 3. RESULTS AND DISCUSSION .......................................................................... 46 3.1. CATALYST CHARACTERIZATION ...................................................... 46 3.2. CATALYTIC PERFORMANCE .............................................................