Record High Hydrogen Storage Capacity in the Metal–Organic Framework Ni₂(m-dobdc) at Near-Ambient Temperatures

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Summary:
The authors from UC Berkeley, LBNL, NREL, NIST and partners developed Ni₂(m-dobdc) MOF with record open-metal-site density, achieving 23 g L⁻¹ usable H₂ capacity (−75 → 25 °C, 100 → 5 bar) for near-ambient automotive storage.

Background:
1. To address the DOE 30 g L⁻¹ system target, prior cryo-adsorbents and high-pressure tanks showed insufficient volumetric density or required extreme conditions.
2. The team now proposes isomeric m-dobdc frameworks whose higher charge density at Ni²⁺ sites boosts H₂ binding enthalpy to −13.7 kJ mol⁻¹.

Research Content:
1. Synthesis: one-pot solvothermal reaction of resorcinol-derived H₄(m-dobdc) with NiCl₂ in MeOH/DMF at 120 °C, followed by 180 °C vacuum activation.
2. Characterizations:
   1) BET 0.56 cm³ g⁻¹ micropore volume; narrow 10–14 Å channels.
   2) SEM ~200 nm rod-like crystals; TEM confirms high crystallinity.
   3) VT-IR shows H₂ ν-HH red-shift to 4035 cm⁻¹ (Ni²⁺ site) and 4125 cm⁻¹ (secondary site); neutron diffraction locates 7 D₂ sites with 2.86 Å D₂···D₂ separation—denser than solid H₂.
3. Application: volumetric isotherms measured 198–373 K, 0–100 bar; 11.0 g L⁻¹ delivered at 25 °C, 18.2 g L⁻¹ with −40 → 25 °C swing, 23.0 g L⁻¹ with −75 → 25 °C swing.
4. Mechanism: open Ni²⁺ centers polarize H₂, creating primary chemisorption; cooperative polarization propagates to secondary physisorbed layers, enabling dense packing without spillover.

Outlook:
Ni₂(m-dobdc) sets a new benchmark for physisorptive H₂ storage under near-ambient conditions and guides future MOF designs targeting −15 to −20 kJ mol⁻¹ binding for full DOE compliance.

Record High Hydrogen Storage Capacity in the Metal–Organic Framework Ni₂(m-dobdc) at Near-Ambient Temperatures
Authors: Matthew T. Kapelewski, Tomče Runčevski, Jacob D. Tarver, Henry Z. H. Jiang, Katherine E. Hurst, Philip A. Parilla, Anthony Ayala, Thomas Gennett, Stephen A. FitzGerald, Craig M. Brown, Jeffrey R. Long
DOI: 10.1021/acs.chemmater.8b03276
Link: https://pubs.acs.org/doi/10.1021/acs.chemmater.8b03276

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