Microporosity and CO(2) Capture Properties of Amorphous Silicon Oxynitride Derived from Novel Polyalkoxysilsesquiazanes

Polyalkoxysilsesquiazanes ([ROSi(NH)(1.5)](n), ROSZ, R = Et, nPr, iPr, nBu, sBu, nHex, sHex, cHex, decahydronaphthyl (DHNp)) were synthesized by ammonolysis at −78 °C of alkoxytrichlorosilane (ROSiCl(3)), which was isolated by distillation as a reaction product of SiCl(4) and ROH. The simultaneous thermogravimetric and mass spectrometry analyses of the ROSZs under helium revealed a common decomposition reaction, the cleavage of the oxygen–carbon bond of the RO group to evolve alkene as a main gaseous species formed in-situ, leading to the formation of microporous amorphous Si–O–N at 550 °C to 800 °C. The microporosity in terms of the peak of the pore size distribution curve located within the micropore size range (<2 nm) and the total micropore volume, as well as the specific surface area (SSA) of the Si–O–N, increased consistently with the molecular size estimated for the alkene formed in-situ during the pyrolysis. The CO(2) capture capacity at 0 °C of the Si–O–N material increased consistently with its SSA, and an excellent CO(2) capture capacity of 3.9 mmol·g(−1) at 0 °C and CO(2) 1 atm was achieved for the Si–O–N derived from DHNpOSZ having an SSA of 750 m(2)·g(−1). The CO(2) capture properties were further discussed based on their temperature dependency, and a surface functional group of the Si–O–N formed in-situ during the polymer/ceramics thermal conversion.