Garrido et al. (2023): Implementing vanadium peroxides as direct air carbon capture materials

Eduard Garrido Ribó, Zhiwei Mao, Jacob S. Hirschi, Taylor Linsday, Karlie Bach, Eric D. Walter, Casey R. Simons, Tim J. Zuehlsdorff, May Nyman IN: Chemical Science, DOI: 10.1039/D3SC05381D

Here the authors explore metastable early d⁰ transition metal peroxide molecules that undergo stabilization via multiple routes, including DAC. Specifically here, they describe via experiment and computation the mechanistic conversion of A₃V(O₂)₄ (tetraperoxovanadate, A = K, Rb, Cs) to first a monocarbonate VO(O₂)₂(CO₃)³⁻, and ultimately HKCO₃ plus KVO₄. Single crystal X-ray structures of rubidium and cesium tetraperoxovanadate are reported here for the first time, likely prior-challenged by instability. Infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), ⁵¹V solid state NMR (nuclear magnetic resonance), tandem thermogravimetry-mass spectrometry (TGA-MS) along with calculations (DFT, density functional theory) all converge on mechanisms of CO₂ capture and release that involve the vanadium centre, despite the end product of a 300 days study being bicarbonate and metavanadate. 

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