Abstract
Carbon capture can mitigate point-source carbon dioxide (CO2) emissions, but hurdles remain that impede the widespread adoption of amine-based technologies. Capturing CO2 at temperatures closer to those of many industrial exhaust streams (>200°C) is of interest, although metal oxide absorbents that operate at these temperatures typically exhibit sluggish CO2 absorption kinetics and instability to cycling. Here, we report a porous metal–organic framework featuring terminal zinc hydride sites that reversibly bind CO2 at temperatures above 200°C—conditions that are unprecedented for intrinsically porous materials. Gas adsorption, structural, spectroscopic, and computational analyses elucidate the rapid, reversible nature of this transformation. Extended cycling and breakthrough analyses reveal that the material is capable of deep carbon capture at low CO2 concentrations and high temperatures relevant to postcombustion capture.
| Original language | English |
|---|---|
| Pages (from-to) | 814-819 |
| Number of pages | 6 |
| Journal | Science |
| Volume | 386 |
| Issue number | 6723 |
| DOIs | |
| State | Published - Nov 15 2024 |
Funding
Certain commercial equipment, instruments, or materials are identified in this document. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology (NIST), nor does it imply that the products identified are necessarily the best available for the purpose. The views expressed in the article do not necessarily represent the views of the US Department of Energy (DOE) or the US Government. The US Government retains and the publisher, by accepting the article for publication, acknowledges, that the US Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for US Government purposes. We thank A. Yakovenko (Argonne National Laboratory) for technical assistance with powder x-ray diffraction data refinement, and J. L. Peltier, B. E. R. Snyder, and J. Börgel (University of California, Berkeley) for helpful discussions. Funding: Gas adsorption analyses and the spectroscopic characterization of materials were supported by the US DOE, Office of Basic Energy Sciences, Separation Science in the Chemical Sciences, Geosciences, and Biosciences Division, under award DESC0019992. The synthesis of materials and computational efforts were supported by the Hydrogen Materials–Advanced Research Consortium (HyMARC), established as part of the Energy Materials Network under the US DOE, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, under contract DE-AC02-05CH11231. We further acknowledge fellowship support from the NASA Space Technology Graduate Research Opportunity program (R.C.R.), the Arnold and Mabel Beckman Foundation (K.M.C.), and the National Science Foundation Graduate Research Fellowship program (M.N.D.). J.R.L. acknowledges support from the Miller Institute for Basic Research in Science at the University of California, Berkeley. This research used resources of the Advanced Photon Source, a DOE Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH11357. R.A.K. gratefully acknowledges support from the US DOE Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office contract DE-AC36-8GO28308 to the National Renewable Energy Laboratory. Part of this work was supported by NIST. This research also used resources of the National Energy Research Scientific Computing Center (NERSC), a US DOE Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under contract DE-AC02-05-CH11231 using NERSC award BES-ERCAP-0023680. Electron microscopy was supported by the US DOE, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division under contract DE-AC02-05-CH11231 within the Electron Microscopy of Soft Matter Program (KC11BN). Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US DOE under contract DE-AC02-05CH1123. Computational modeling was supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US DOE through the Gas Phase Chemical Physics Program, under contract DE-AC02-05CH11231. A portion of this research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Author contributions: R.C.R., K.M.C., and J.R.L. formulated and directed the research. R.C.R. and K.M.C. synthesized materials, conducted isotherm and isobar measurements, and analyzed the data. R.C.R., K.M.C., and M.N.D. conducted and interpreted kinetics measurements. H.K., A.J.H., K.M.C., and J.W.T. assisted in the collection and refinement of single-crystal x-ray diffraction data. H.Z.H.J., R.A.K., S.L.K., Y.W., Y.Y., K.C.B., K.E.E., A.M.M., J.A.R., and C.M.B. conducted spectroscopic characterization. R.A.K. and C.M.B. collected and analyzed powder x-ray diffraction data. D.R.Y., R.A.K., and C.M.B. collected and analyzed powder neutron diffraction data. M.N.D. collected and interpreted breakthrough data. H.F. collected and interpreted pycnometer density measurements. A.R.M., N.V.T., and M.H.-G. performed computational analyses. R.C.R., K.M.C., and K.R.M. drafted the manuscript. All authors contributed to revision of the manuscript. Competing interests: The University of California, Berkeley, has applied for a patent on some of the technology discussed herein regarding high-temperature gas capture with porous materials, on which R.C.R., K.M.C., and J.R.L. are listed as co-inventors. Data and materials availability: The supplementary materials contain complete experimental and spectral details for all new compounds reported herein. Crystallographic data for solid-state structures obtained from single-crystal x-ray diffraction have been made available free of charge from the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers 2250026 (ZnEt-MFU-4l), 2250025 (Zn(O2CH)-MFU-4l), 2250027 (ZnH-MFU-4l), and 2166411 [CO2-derived Zn(O2CH)-MFU-4l]. Data for solid-state structures obtained from powder synchrotron x-ray and neutron diffraction data have been additionally deposited to the CCDC with deposition numbers 2263702–2263708 and 2352001. License information: Copyright © 2024 the authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original US government works. https://www. science.org/about/science-licenses-journal-article-reuse Certain commercial equipment, instruments, or materials are identified in this document. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology (NIST), nor does it imply that the products identified are necessarily the best available for the purpose. The views expressed in the article do not necessarily represent the views of the US Department of Energy (DOE) or the US Government. The US Government retains and the publisher, by accepting the article for publication, acknowledges, that the US Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for US Government purposes. We thank A. Yakovenko (Argonne National Laboratory) for technical assistance with powder x-ray diffraction data refinement, and J. L. Peltier, B. E. R. Snyder, and J. Börgel (University of California, Berkeley) for helpful discussions. Gas adsorption analyses and the spectroscopic characterization of materials were supported by the US DOE, Office of Basic Energy Sciences, Separation Science in the Chemical Sciences, Geosciences, and Biosciences Division, under award DE- SC0019992. The synthesis of materials and computational efforts were supported by the Hydrogen Materials–Advanced Research Consortium (HyMARC), established as part of the Energy Materials Network under the US DOE, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, under contract DE-AC02-05CH11231. We further acknowledge fellowship support from the NASA Space Technology Graduate Research Opportunity program (R.C.R.), the Arnold and Mabel Beckman Foundation (K.M.C.), and the National Science Foundation Graduate Research Fellowship program (M.N.D.). J.R.L. acknowledges support from the Miller Institute for Basic Research in Science at the University of California, Berkeley. This research used resources of the Advanced Photon Source, a DOE Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH11357. R.A.K. gratefully acknowledges support from the US DOE Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office contract DE-AC36-8GO28308 to the National Renewable Energy Laboratory. Part of this work was supported by NIST. This research also used resources of the National Energy Research Scientific Computing Center (NERSC), a US DOE Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under contract DE-AC02-05-CH11231 using NERSC award BES-ERCAP-0023680. Electron microscopy was supported by the US DOE, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division under contract DE-AC02-05-CH11231 within the Electron Microscopy of Soft Matter Program (KC11BN). Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US DOE under contract DE-AC02-05CH1123. Computational modeling was supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US DOE through the Gas Phase Chemical Physics Program, under contract DE-AC02-05CH11231. A portion of this research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.