A comparative pyrolysis study of tetraethoxysilane and tetraethoxymethane: Insight into congener substitution effects on pyrolysis chemistry of siloxane flame synthesis precursors

The pyrolysis of siloxane precursors, such as tetraethoxysilane (TEOS), is commonly employed in the flame synthesis and chemical vapor deposition of silica nanoparticles. In this work, the flow reactor pyrolysis of TEOS is studied using gas chromatography (GC) and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS), and the congener substitution effects from the central C atom to the central Si atom are investigated through comparison with its hydrocarbon counterpart tetraethoxymethane (TEOM). Pyrolysis models of TEOS and TEOM are constructed and validated against the measured results. Modeling analysis, including rate of production analysis and sensitivity analysis, provides insights into chemistry in fuel consumption and product formation. In contrast, the observations of silicon-containing products in SVUV-PIMS experiments provide evidence for crucial decomposition pathways of TEOS. It is observed that TEOS exhibits significantly higher stability than TEOM under pyrolysis conditions. The most abundant products in the pyrolysis of TEOS and TEOM are ethylene and ethanol, and TEOS produces more hydrocarbon products than TEOM. The lower pyrolysis reactivity of TEOS is attributed to the slower unimolecular decomposition reaction which dominates the decomposition of TEOS than TEOM. This can be explained by the hindrance of the extremely strong Si-O bond resulting from the significantly different electronegativity between Si and O. The higher initial decomposition temperature of TEOS enhances the contribution of other decomposition channels, such as C-C bond dissociation and H-abstraction reactions, in TEOS consumption. This leads to the abundant formation of hydrocarbon productions such as methane, ethane, and acetaldehyde. As the main pyrolysis product, the ethanol produced by TEOM pyrolysis is four times that of TEOS due to the congener substitution effects. The ethanol formation pathway in TEOS pyrolysis is different from that in TEOM pyrolysis, which is mainly formed via a newly proposed multi-step mechanism, resulting in a lower yield in TEOS pyrolysis.