Thermal Activation of a Copper-Loaded Covalent Organic Framework for Near-Ambient Temperature Hydrogen Storage and Delivery

Braunecker, Wade A.; Shulda, Sarah; Martinez, Madison B.; Hurst, Katherine E.; Koubek, Joshua T.; Zaccarine, Sarah; Mow, Rachel; Pylypenko, Svitlana; Sellinger, Alan; Gennett, Thomas; Johnson, Justin C

doi:10.1021/acsmaterialslett.9b00413

Title: Thermal Activation of a Copper-Loaded Covalent Organic Framework for Near-Ambient Temperature Hydrogen Storage and Delivery

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Abstract

Copper(II) formate is efficiently incorporated into the pores of a 2D imine-based covalent organic framework (COF) via coordination with the phenol and imine groups. The coordinated metal ion is then reduced to Cu(I) with a thermal treatment that evolves CO₂. After loading with hydrogen gas, the majority of H₂ desorbs from the coordinatively saturated Cu(II) COF at temperatures < -100 degrees C. However, the activated Cu(I) COF retains adsorbed H₂ above room temperature. Adsorption/desorption of H₂ was highly reversible. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) strongly supports a molecular hydrogen interaction with Cu(I). A Kissinger analysis of variable ramp rate desorption experiments estimates the enthalpy of H₂ desorption from Cu(I) at 15 kJ mol^-1. The results represent an advance toward practical H₂ storage and delivery in a lightweight, stable, and highly versatile material.

Authors:

^[1]; Shulda, Sarah ^[2]; Martinez, Madison B. ^[1];

^[2]; Koubek, Joshua T. ^[3]; Zaccarine, Sarah ^[3];

^[1]; Pylypenko, Svitlana ^[1]; Sellinger, Alan ^[1]; Gennett, Thomas ^[1];

^[4]

National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Colorado School of Mines, Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Publication Date:: Fri Jan 31 00:00:00 EST 2020

Research Org.:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office

OSTI Identifier:: 1600127

Report Number(s):: NREL/JA-5900-74789
Journal ID: ISSN 2639-4979

Grant/Contract Number:: AC36-08GO28308

Resource Type:: Accepted Manuscript

Journal Name:: ACS Materials Letters

Additional Journal Information:: Journal Volume: 2; Journal Issue: 3; Journal ID: ISSN 2639-4979

Publisher:: ACS Publications

Country of Publication:: United States

Language:: English

Subject:: 08 HYDROGEN; covalent organic frameworks; desorption; metals; materials; enthalpy

Citation Formats


                    Braunecker, Wade A., Shulda, Sarah, Martinez, Madison B., Hurst, Katherine E., Koubek, Joshua T., Zaccarine, Sarah, Mow, Rachel, Pylypenko, Svitlana, Sellinger, Alan, Gennett, Thomas, and Johnson, Justin C. Thermal Activation of a Copper-Loaded Covalent Organic Framework for Near-Ambient Temperature Hydrogen Storage and Delivery.  United States: N. p., 2020. 
Web.  doi:10.1021/acsmaterialslett.9b00413.

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                    Braunecker, Wade A., Shulda, Sarah, Martinez, Madison B., Hurst, Katherine E., Koubek, Joshua T., Zaccarine, Sarah, Mow, Rachel, Pylypenko, Svitlana, Sellinger, Alan, Gennett, Thomas, & Johnson, Justin C. Thermal Activation of a Copper-Loaded Covalent Organic Framework for Near-Ambient Temperature Hydrogen Storage and Delivery.  United States.  https://doi.org/10.1021/acsmaterialslett.9b00413

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                    Braunecker, Wade A., Shulda, Sarah, Martinez, Madison B., Hurst, Katherine E., Koubek, Joshua T., Zaccarine, Sarah, Mow, Rachel, Pylypenko, Svitlana, Sellinger, Alan, Gennett, Thomas, and Johnson, Justin C. Fri .  
"Thermal Activation of a Copper-Loaded Covalent Organic Framework for Near-Ambient Temperature Hydrogen Storage and Delivery".  United States.  https://doi.org/10.1021/acsmaterialslett.9b00413.  https://www.osti.gov/servlets/purl/1600127.

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@article{osti_1600127,

  title        = {Thermal Activation of a Copper-Loaded Covalent Organic Framework for Near-Ambient Temperature Hydrogen Storage and Delivery},

  author       = {Braunecker, Wade A. and Shulda, Sarah and Martinez, Madison B. and Hurst, Katherine E. and Koubek, Joshua T. and Zaccarine, Sarah and Mow, Rachel and Pylypenko, Svitlana and Sellinger, Alan and Gennett, Thomas and Johnson, Justin C},

  abstractNote = {Copper(II) formate is efficiently incorporated into the pores of a 2D imine-based covalent organic framework (COF) via coordination with the phenol and imine groups. The coordinated metal ion is then reduced to Cu(I) with a thermal treatment that evolves CO2. After loading with hydrogen gas, the majority of H2 desorbs from the coordinatively saturated Cu(II) COF at temperatures < -100 degrees C. However, the activated Cu(I) COF retains adsorbed H2 above room temperature. Adsorption/desorption of H2 was highly reversible. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) strongly supports a molecular hydrogen interaction with Cu(I). A Kissinger analysis of variable ramp rate desorption experiments estimates the enthalpy of H2 desorption from Cu(I) at 15 kJ mol-1. The results represent an advance toward practical H2 storage and delivery in a lightweight, stable, and highly versatile material.},

  doi          = {10.1021/acsmaterialslett.9b00413},

  journal      = {ACS Materials Letters},

  number       = 3,

  volume       = 2,

  place        = {United States},

  year         = {Fri Jan 31 00:00:00 EST 2020},

  month        = {Fri Jan 31 00:00:00 EST 2020}

}

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