Published: December 28, 2011 r2011 American Chemical Society 724 dx.doi.org/10.1021/cr2003272 | Chem. Rev. 2012, 112, 724–781 REVIEW pubs.acs.org/CR Carbon Dioxide Capture in MetalOrganic Frameworks Kenji Sumida, † David L. Rogow, † Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm, Tae-Hyun Bae, and Jeffrey R. Long* Department of Chemistry, University of California, Berkeley, California 94720-1460, United States CONTENTS 1. Introduction 724 1.1. Carbon Dioxide Emission from Anthropogenic Sources 725 1.2. CO 2 Capture at Stationary Point Sources 726 1.3. Options for CO 2 Sequestration 727 1.4. Current CO 2 Capture Materials 727 1.4.1. Aqueous Alkanolamine Absorbents 728 1.4.2. Solid Porous Adsorbent Materials 729 1.5. MetalOrganic Frameworks 731 1.5.1. Synthesis and Structural Features 731 1.5.2. Physical Properties 732 2. CO 2 Adsorption in MetalOrganic Frameworks 733 2.1. Capacity for CO 2 733 2.2. Enthalpy of Adsorption 733 2.3. Selectivity for CO 2 739 2.3.1. Estimation from Single-Component Isotherms 741 2.3.2. Ideal Adsorbed Solution Theory (IAST) 742 2.3.3. Gas Mixtures and Breakthrough Experiments 742 2.4. In Situ Characterization of Adsorbed CO 2 742 2.4.1. Structural Observations 743 2.4.2. Infrared Spectroscopy 744 2.5. Computational Modeling of CO 2 Capture 745 3. Post-combustion Capture 746 3.1. MetalOrganic Frameworks for CO 2 /N 2 Separation 746 3.2. Enhancing CO 2 /N 2 Selectivity via Surface Functionalization 746 3.2.1. Pores Functionalized by Nitrogen Bases 746 3.2.2. Other Strongly Polarizing Organic Functional Groups 749 3.2.3. Exposed Metal Cation Sites 750 3.3. Considerations for Application 752 3.3.1. Stability to Water Vapor 752 3.3.2. Other Minor Components of Flue Gas 754 4. Pre-combustion Capture 754 4.1. Considerations for Pre-combustion CO 2 Capture 755 4.1.1. Advantages of Pre-combustion Capture 755 4.1.2. Hydrogen Purification 755 4.1.3. Metrics for Evaluating Adsorbents 755 4.1.4. Non-CO 2 Impurities in CO 2 /H 2 Streams 756 4.1.5. MetalOrganic Framework-Containing Membranes for Pre-combustion CO 2 Capture 756 4.2. MetalOrganic Frameworks as Adsorbents 756 4.2.1. Investigations Based on Single- Component Isotherms 757 4.2.2. Computational Studies 757 5. Oxy-fuel Combustion 760 5.1. MetalOrganic Frameworks for O 2 /N 2 Separation 761 6. MetalOrganic Framework-Containing Membranes 762 6.1. Continuous Films of MetalOrganic Frameworks 763 6.2. Mixed-Matrix Membranes 767 7. Concluding Remarks and Outlook 770 Author Information 771 Biographies 771 Acknowledgment 772 List of Abbreviations 772 References 774 1. INTRODUCTION The sharply rising level of atmospheric carbon dioxide result- ing from anthropogenic emissions is one of the greatest environ- mental concerns facing our civilization today. These emissions, which stem predominantly from the combustion of coal, oil, and natural gas (ca. 80% of CO 2 emissions worldwide), 1 are pro- jected to continue to increase in the future due to economic growth and industrial development, particularly in developing nations. 2 Although the transition of the existing infrastructure from carbon-based sources to cleaner alternatives would be ideal in this regard, such a change requires considerable modifications to the current energy framework, and many of the proposed technologies are not yet sufficiently developed to facilitate large- scale industrial implementation. Thus, carbon capture and sequestration (CCS) technologies that efficiently capture CO 2 from existing emission sources will play a vital role until more significant modifications to the energy infrastructure can be realized. Special Issue: 2012 Metal-Organic Frameworks Received: August 19, 2011