Efforts to limit rising concentrations of CO2 have motivated the development of negative emission technologies. Direct air capture (DAC) of CO2 is one of the negative emissions technologies that has been proposed for the direct removal of CO2 from the atmosphere. Phase-changing bis(iminonoguanidine) (BIG) sorbents have been developed for the direct air capture of CO2. These phase changing sorbents, specifically glyoxal-bis-(iminoguanidine) (GBIG), involve (1) CO2 absorption with aqueous amino acid salts, such as K- or Na-glycinate to yield bicarbonate-rich solutions, (2) crystallization of the bicarbonate anions with a BIG solid, which regenerates the amino acid, and (3) solid-state CO2 release from the carbonate crystals and BIG regeneration. Despite the promising potential of these materials, their structural evolution during the thermal regeneration of the BIG solids, chemical regeneration of the sodium or potassium glycinate solvents, and the crystallization behavior of CO2-loaded BIG bicarbonate remain to be evaluated and understood in detail. The aim of this study is to probe these knowledge gaps. In situ wide-angle X-ray Scattering (WAXS) results show that CO2 and water molecules in GBIG bicarbonate are simultaneously released in a single step during the thermal regeneration of the sorbent at 97 - 134 degrees C. In situ ATR-FTIR measurements showed that sodium glycinate and GBIG bicarbonate are simultaneously generated when GBIG, glycine, and sodium bicarbonate are reacted. The crystallization of GBIG bicarbonate from GBIG and CO2-loaded monoethanolamine (MEA) occurs rapidly in the first 10 min of the reaction, as determined using in situ GI-SAXS measurements. The insights from these studies are essential for the scalable implementation of CO2 capture technologies using these phase-changing sorbents.