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This is an open access article published under a Creative Commons Attribution (CC-BY)

License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

pubs.acs.org/CR

Review

Heterogeneously Catalyzed Hydrothermal Processing of C5−C6 Sugars

Xingguang Zhang, Karen Wilson, and Adam F. Lee*

European Bioenergy Research Institute, Aston University, Birmingham B4 7ET, United Kingdom

ABSTRACT: Biomass has been long exploited as an anthropogenic energy source; however, the 21st century challenges of energy security and climate change are driving resurgence in its utilization both as a renewable alternative to fossil fuels and as a sustainable carbon feedstock for chemicals production. Deconstruction of cellulose and hemicellulose carbohydrate polymers into their constituent C5 and C6 sugars, and subsequent heterogeneously catalyzed transformations, offer the promise of unlocking diverse oxygenates such as furfural, 5-hydroxymethylfurfural, xylitol, sorbitol, mannitol, and gluconic acid as biorefinery platform chemicals. Here, we review recent advances in the design and development of catalysts and processes for C5−C6 sugar reforming into chemical intermediates and products, and highlight the challenges of aqueous phase operation and catalyst evaluation, in addition to process considerations such as solvent and reactor selection.

CONTENTS

1. Introduction

1.1. Biomass Conversion and Hydrothermal

Processing of Sugars

1.2. Scope of the Current Review

2. C5−C6 Sugar Transformations

2.1. Isomerization

2.2. Dehydration

2.3. Hydrogenation/Hydrogenolysis 2.4. Selective Oxidation

3. Heterogeneous Catalysts for Sugar Transforma- tions

3.1. Solid Acids/Bases for Isomerization

3.1.1. Zeolitic Solid Lewis Acids

3.1.2. Hydrotalcite Solid Bases

3.1.3. Other Solid Base Catalysts

3.1.4. Process Considerations

3.1.5. Summary of Solid Base Isomerization Catalysts

3.2. Solid Acids for Dehydration

3.2.1. Zeolitic Materials

3.2.2. Sulfonic Acid and Sulfated Metal Oxides

3.2.3. Metal Phosphates

3.2.4. Composite Metal and Nonmetal Oxides

3.2.5. Other Solid Acid Catalysts

3.2.6. Process Considerations

3.2.7. Summary of Solid Acid Dehydration

Catalysts

3.3. Metal Catalysts for Hydrogenation

3.3.1. Amorphous Alloys 3.3.2. Ni

3.3.3. Ru

3.3.4. Pt

3.3.5. Other Hydrogenation Catalysts

© 2016 American Chemical Society

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3.3.6. Process Considerations

3.3.7. Summary of Hydrogenation Catalysts 3.4. Selective Oxidation

3.4.1. Pd

3.4.2. Nanoporous/Colloidal Au

3.4.3. Au

3.4.4. Supported Alloys

3.4.5. Process Considerations

3.4.6. Summary of Glucose Oxidation Cata-

lysts

3.4.7. Nonglucose Monosaccharide Oxida-

tions

4. Future Perspectives

4.1. Process and Economic Considerations

4.2. Future Catalyst Development 5. Conclusions

Author Information

Corresponding Author Notes

Biographies

Acknowledgments References

1. INTRODUCTION

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1.1. Biomass Conversion and Hydrothermal Processing of Sugars

The quest for sustainable resources to meet the energy, food, and materials nexus of needs for a rising global population, set against the backdrop of climate change and dwindling ecodiversity, necessitates new chemical technologies. Global

Received: May 16, 2016 Published: September 28, 2016

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DOI: 10.1021/acs.chemrev.6b00311 Chem. Rev. 2016, 116, 12328−12368

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