This book describes a detailed multi-scale approach integrating nano- (active site), meso- (porous catalyst architecture) and macroscale (reactor) efforts, to address the challenges of producing a better epoxidation catalyst.
It contains an in-depth study of the design and synthesis of gold nanoparticles and their application as a catalyst for direct gas phase propylene epoxidation. “Direct” means using only hydrogen and oxygen in one step, which is key for sustainable manufacturing, as opposed to commercialised, more complex production routes requiring multiple steps, or integration with another chemical plant. The insights gained can be used for rational design for stable and selective catalysts for other reactions. It also details the step-by-step process to build an epoxidation reactor system with a focus on safety aspects, which can be used as a guidebook for undergraduate and graduate students in chemical engineering. Beyond heterogeneous catalysis, the new, easily accomplished methodology for synthesising atomically precise nanoparticles is shown to be relevant to electrocatalysis and to healthcare applications, such as anti-microbial surfaces.
This book will be of interest to researchers, engineers and experts in the related areas of chemical engineering, chemistry, material science and electrochemistry.

lgrsnf/1121.pdf

Springer Nature Switzerland AG

Springer theses, Cham, 2022

Switzerland, Switzerland

S.l, 2023

Supervisor’s Foreword
Abstract
Publications Related to This Thesis
Acknowledgements
Declaration
Contents
Abbreviations
1 Introduction
1.1 Importance of Propylene Oxide and Its Production
1.2 Chlorohydrin Process (CHPO)
1.3 The Hydroperoxide Process
1.4 The Hydrogen Peroxide to Propylene Oxide (HPPO) Process
1.5 Gold Nanoparticle-Based Catalysis and Direct Gas Phase Epoxidation
1.5.1 Introduction to Gold Nanoparticles and Their Properties
1.5.2 Gold Nanoclusters
1.5.3 Catalytic Properties of Gold NCs/NPs
1.5.4 Interaction of Gold NCs/NPs with Different Oxide Supports
1.5.5 Synthesis of Supported NCs/NPs
1.5.6 Synthetic Methods for Gold Nanoparticles/Nanoclusters
1.5.7 Characterisation Techniques and Methods
1.5.8 Direct Gas Phase Epoxidation Reaction
1.5.9 Reaction Mechanism
1.5.10 Recent Catalyst Development for Direct Gas Phase Epoxidation
1.6 Direct Oxidation Using Molecular Oxygen
1.7 Epoxidation by Nitrous Oxide
1.8 Conclusion and Challenges
1.9 Aims and Objective of This Thesis
References
2 Propylene Epoxidation Reactor Design
2.1 Introduction
2.2 Materials and Methods
2.3 Safety
2.3.1 Hazard 1. Fire
2.3.2 Hazard 2. Gases in Cylinders
2.4 Designing and Calibration
2.4.1 Reactor Assembly
2.4.2 Reactor
2.4.3 Gas Chromatography
2.5 Analysis
2.6 Conclusion
References
3 Synthesis of Gold Cluster-Based Catalyst and the Effect of Pre-Treatments on Its Catalytic Performance
3.1 Introduction
3.2 Experimental
3.2.1 Chemicals
3.2.2 Synthesis of Phosphine-Bound Gold Clusters
3.2.3 Synthesis of Titanium Silicalite-1 (TS-1) Support
3.2.4 Synthesis of Gold Clusters in a Continuous Flow
3.2.5 Catalyst Preparation: Colloidal Immobilisation
3.2.6 Catalyst Characterisation
3.2.7 Catalytic Testing
3.3 Results and Discussions
3.3.1 Synthesis of Gold Clusters and Characterisation
3.3.2 Immobilisation of Gold Clusters onto TS-1
3.4 Catalytic Performance of Au/TS-1 Catalyst
3.5 Conclusion
References
4 Supported Gold Clusters as a Stable Catalyst for Propylene Epoxidation
4.1 Introduction
4.2 Experimental
4.2.1 Catalyst Preparation
4.2.2 Catalyst Characterisation
4.3 Results and Discussion
4.3.1 Catalyst Synthesis and Characterisation
4.3.2 Catalytic Performance of Au/TS-1
4.3.3 Performance of Au/TS-1PT Catalyst Over Longer Times on Stream
4.3.4 Investigation of Factors Underpinning the Enhanced Stability
4.4 Conclusion
References
5 Tailoring Gold Nanoparticles with Tunable Core Size and Their Catalytic Applications
5.1 Introduction
5.2 Experimental
5.2.1 Materials
5.2.2 Synthesis of Gold Nanoparticles—P1
5.2.3 Synthesis of Gold Nanoparticles—P2
5.2.4 Synthesis of Gold Nanoparticles—P3
5.2.5 Synthesis of Supported Gold Catalyst
5.3 Results and Discussion
5.3.1 Synthesis and Characterisation of Gold Nanoparticles
5.3.2 Immobilisation of AuNPs onto TS-1
5.3.3 The Catalytic Activity of Supported AuNPs
5.4 Conclusion
References
6 Propylene Epoxidation on Au/Ti-Containing Supports: The Effect of the Support
6.1 Introduction
6.2 Experimental
6.2.1 Materials
6.2.2 Synthesis of TS-1
6.2.3 Synthesis of m-TS-1
6.2.4 Synthesis of MCM-41
6.2.5 Synthesis of SBA-15
6.2.6 Grafting of Ti on SBA-15 and MCM-41
6.2.7 Synthesis of Phosphine Bound Gold Clusters
6.2.8 Purification of Synthesised Au Clusters
6.2.9 Immobilisation of Au onto Various Supports
6.2.10 Characterisation
6.3 Results and Discussion
6.3.1 Synthesis and Characterisation of Supports
6.3.2 Immobilisation of Au Clusters on the Supports
6.3.3 Catalytic Performance of Supported Au Catalyst
6.3.4 Analysis of the Spent Catalyst
6.4 Conclusion
References
7 Controlled Engineering of Supported Metal Nanoparticles Using Electrospraying: Robust Removal of Stabilising Ligands
7.1 Introduction
7.2 Experimental
7.2.1 Materials
7.2.2 Synthesis of Metal Nanoparticles
7.2.3 Immobilisation of Metal NPs onto Various Supports
7.2.4 Electrochemical Measurements
7.3 Results and Discussion
7.3.1 Synthesis and Characterisation of Au and Ag Nanoparticles
7.3.2 Synthesis and Characterisation of AuPd Bimetallic Nanoparticles
7.3.3 Synthesis and Characterisation of Supported Metal Nanoparticles
7.3.4 Preparation of Au/TS-1 Catalyst
7.3.5 Immobilisation of AuPd Bimetallic Nanoparticles
7.4 Conclusion
References
8 Conclusions and Future Work
8.1 Conclusions
8.2 Future Work and the Bigger Picture
8.2.1 Investigation of Au Loading and Ti/Si Ratio
8.2.2 Bimetallic Nanoparticles for Enhanced Propylene Epoxidation
8.2.3 Nanoconfinement Effects in Catalysis
8.2.4 Electrospraying Technique for the Synthesis of Bimetallic Nanoparticles
8.2.5 Antimicrobial Properties of the Au Clusters
References
Appendix
About the Author

2024-04-11