Heterogeneous Catalysts for Clean Technology: Spectroscopy, Design, and Monitoring

Reactive, but not a reactant. Heterogeneous catalysts play an unseen role in many of today‘s processes and products. With the increasing emphasis on sustainability in both products and processes, this handbook is the first to combine the hot topics of heterogeneous catalysis and clean technology and in–situ monitoring. It focuses on the development of heterogeneous catalysts for use in clean chemical synthesis, dealing with how modern spectroscopic techniques can aid the design of catalysts for use in liquid and vapour phase reactions, their application in industrially important chemistries – including selective oxidation, hydrogenation, solid acid– and base–catalyzed processes – as well as the role of process intensification and use of renewable resources in improving the sustainability of chemical processes. With its emphasis on applications, this book is of high interest to those working in the industry.

Preface XVII List of Contributors XIX 1 Introduction to Clean Technology and Catalysis 1 James H. Clark 1.1 Green Chemistry and Clean Technology 1 1.2 Green Chemistry Metrics 3 1.3 Alternative Solvents 5 1.4 Heterogeneous or Homogeneous 6 1.5 Alternative Energy Reactors for Green Chemistry 7 1.6 Concluding Remarks 9 References 9 2 Mechanistic Studies of Alcohol Selective Oxidation 11 Adam F. Lee 2.1 Introduction 11 2.2 Metal–Catalyzed Alcohol Selox 13 2.3 Oxide, Sulfide, and Vanadate Catalysts 22 2.4 Solvent Selection 22 2.5 In Situ and Operando X–Ray Studies of Selox Catalysts 24 2.6 Conclusions 32 References 33 3 Reaction Monitoring in Multiphase Systems: Application of Coupled In Situ Spectroscopic Techniques in Organic Synthesis 39 Leif R. Kn¨opke and Ursula Bentrup 3.1 Introduction 39 3.2 Method Coupling 41 3.3 Spectroscopic Reactors and Practical Aspects 45 3.4 Selected Examples of Use 50 3.5 Conclusion and Outlook 60 References 61 4 In Situ Studies on Photocatalytic Materials, Surface Intermediates, and Reaction Mechanisms 65 Hendrik Kosslick, Vu A. Tuan, and Detlef W. Bahnemann 4.1 Introduction 65 4.2 In Situ Investigations 66 4.3 Concluding Remarks 98 References 99 5 Enantioselective Heterogeneous Catalysis 103 Christopher J. Baddeley 5.1 Introduction 103 5.2 Strategies for the Creation of Enantioselective Heterogeneous Catalysts 105 5.3 Concluding Remarks–A Comparison of the Various Approaches to Heterogeneous Enantioselective Catalysts 120 References 121 6 Mechanistic Studies of Solid Acids and Base–Catalyzed Clean Technologies 125 Atsushi Takagaki, Shun Nishimura, and Kohki Ebitani 6.1 Introduction 125 6.2 New Catalytic Systems 126 6.3 Biomass Conversions 144 6.4 Summary 163 References 163 7 Site–Isolated Heterogeneous Catalysts 173 Mizuki Tada and Satoshi Muratsugu 7.1 Introduction 173 7.2 Assembled Monolayers of Metal Complexes on Single–Crystal Surfaces 174 7.3 Reaction–Induced and Photoinduced Formation of Unsaturated Ru Complexes Supported on SiO2 Surfaces 177 7.4 Manganese Triazacyclononane Catalysts Grafted under Reaction Conditions 181 7.5 Well–Defined Silica–Supported Mo–Imido Alkylidene Complexes for Metathesis 184 7.6 Double Catalytic Activation Using a Bifunctional Catalyst with Both Acid and Base on Solid Surfaces 186 7.7 Summary 189 References 189 8 Designing Porous Inorganic Architectures 193 Juan A. Melero, Jos´e Iglesias, and Gabriel Morales 8.1 Introduction 193 8.2 Templated Methods for the Preparation of Ordered Porous Materials 194 8.3 Hierarchical Porous Materials 218 8.4 Concluding Remarks 233 References 234 9 Tailored Nanoparticles for Clean Technology – Achieving Size and Shape Control 241 Vladimir Golovko 9.1 Introduction 241 9.2 Size effects–setting the scene 242 9.3 Size effects illustrated by way of examples of selected industrially important reactions 262 9.4 Shape effects 272 9.5 Conclusions 282 References 283 10 Application of Metal–Organic Frameworks in Fine Chemical Synthesis 293 Jerome Canivet and David Farrusseng 10.1 Metal–Organic Frameworks as Heterogeneous Catalysts 293 10.2 Applications in Carbon–Carbon Bond Formation 303 10.3 Applications in Oxidation, Carbon–Oxygen, and Carbon–Nitrogen Bond Formation 310 10.4 Applications in Asymmetric Synthesis 316 10.5 Concluding Remarks 321 Acknowledgments 325 List of Abbreviations 325 References 326 11 Process Intensification for Clean Catalytic Technology 333 Albert Renken 11.1 Introduction 333 11.2 Effect of Transport Phenomena on Heterogeneous Catalysis 334 11.3 Intensification of Transport Phenomena 340 11.4 Conclusion 360 List of Symbols 361 References 362 12 Recent Trends in Operando and In Situ Characterization: Techniques for Rational Design of Catalysts 365 Andrew M. Beale, Jan Philipp Hofmann, Meenakshisundaram Sankar, Evelien M. van Schrojenstein Lantman, and Bert M. Weckhuysen 12.1 Introduction 365 12.2 Catalyst Nascence 366 12.3 Synthesis of Silicalite–1 Molecular Sieves 367 12.4 Preparation of Supported Metal Catalysts 373 12.5 Catalyst Life 380 12.6 Elucidating the Reaction Mechanism of Aerobic Oxidation of Benzyl Alcohol 381 12.7 Determination of the Active Sites in Aerobic Oxidation of Benzyl Alcohol 385 12.8 Catalyst Death 392 12.9 Methanol to Hydrocarbons 392 12.10 Propane Dehydrogenation 400 12.11 Summary and Conclusions 406 References 407 13 Application of NMR in Online Monitoring of Catalyst Performance 413 Michael Neugebauer and Michael Maiwald 13.1 Online Monitoring with NMR Spectroscopy 413 13.2 Quantitative NMR Spectroscopy in Technical Samples 417 13.3 Flow and High–Pressure NMR Spectroscopy for Reaction Monitoring 422 13.4 Selected Applications of NMR in Online Monitoring of Catalyst Performance 426 13.5 Conclusions 433 Acknowledgments 434 References 434 14 Ambient–Pressure X–Ray Photoelectron Spectroscopy 437 Andrey Shavorskiy and Hendrik Bluhm 14.1 Introduction 437 14.2 Technical Aspects 438 14.3 Applications of APXPS 445 14.4 Outlook 464 Acknowledgments 465 References 465 Index 469

Dr Wilson was educated at the Universities of Cambridge (PhD supervisor: Prof. Richard Lambert) and Liverpool. She moved to York in 1998, undertaking post–doctoral research on new mesoporous solid acids with Prof. James Clark, and was subsequently appointed to a lectureship at York in 1999. Karen was promoted to Senior Lecturer in 2007, prior to her appointment as Reader in Physical Chemistry at Cardiff University. Her research interests lie in the design of hierarchical porous solid catalysts for clean chemical synthesis, particularly the development of tuneable solid acids and bases for sustainable bio–diesel synthesis. She has recently been awarded a Royal Society Industry fellowship to work on new catalysts for biofuel production. Prof Lee carried out undergraduate and postgraduate studies at the University of Cambridge (PhD supervisor: Prof. Richard Lambert). He was appointed to a lectureship at the University of Hull in 1996, before moving to the University of York where he was promoted to Senior Lecturer (2006). In 2009, Adam was awarded an EPSRC Leadership Fellowship and appointed Professor of Physical Chemistry at Cardiff University. His research interests lie in the design of tailored nanocatalysts for green chemistry, and the development of in situ methodologies to provide mechanistic insight into surface processes.