Synthesis and Twin Polymerization of Si(OCH2py)4 for Nitrogen‐containing Carbon Materials

Abstract The synthesis and twin polymerization (TP) of Si(OCH 2 py) 4 ( 3 a , py=2‐ c C 5 H 4 N; 3 b , py=3‐ c C 5 H 4 N; 3 c , py=4‐ c C 5 H 4 N) is discussed. The solid state structures of 3 b , c were confirmed by single‐crystal X‐ray crystallography showing non‐conventional H‐bonding, forming 2D chains ( 3 b ) or 3D networks ( 3 c ). Thermally induced TP of 3 a – c and their simultaneous polymerization with 2,2‘‐spiro‐bi[4 H ‐1,3,2‐benzodioxasiline] ( 4 ) is described. The resulting hybrid materials were characterized by 1 H, 13 C{ 1 H}, and 29 Si{ 1 H} CP MAS NMR spectroscopy confirming the transformation of the SiOCH 2 moieties into CH 2 groups enabling the formation of the respective polymers. These results were supported by HAADF‐STEM studies, displaying micro‐structuring. Nitrogen‐containing porous carbon materials C_1 – C_3 show surface areas of 1300 and 1700 m 2 g −1 , large pore volumes between 0.6–1.2 cm 3 g −1 , and nitrogen contents of up to 3.1 at‐%. X‐ray photoemission spectroscopy reveal that pyrrolic, pyridine, and pyridone nitrogen atoms are present. If equimolar amounts of 3 a – c and 4 are simultaneously polymerized in the presence of [Pd(OAc) 2 ] ( 5 ), then the Pd nanoparticle‐decorated material Pd@C_3 (900 m 2 g −1 ) was obtained, which showed k values of −0.083 and −0.066 min −1 in the reduction of methylene blue and methyl orange, proving the accessibility of the Pd NPs.