Tin Nanoparticles in Carbon/Silica Hybrid Materials by the Use of Twin Polymerization

Abstract

Simultaneous twin polymerization was used to synthesize hybrid materials composed of tin oxide, silica, and a phenolic resin starting from a mixture of 2,2′‐spirobi[4H‐1,3,2‐benzodioxasiline] (Si‐spiro) with either the tin(IV) alkoxides 2,2′‐spirobi[4H‐1,3,2‐benzodioxastannine] (A), 2,2′‐spirobi[6‐methyl‐4H‐1,3,2‐benzodioxastannine] (B), and 2,2′‐spirobi[6‐methoxy‐4H‐1,3,2‐benzodioxastannine] (C) or the novel tin(II) alkoxides tin(II)‐2‐(oxidomethyl)‐4‐methoxyphenolate (D) and tin(II)‐2‐(oxidomethyl)‐5‐methoxyphenolate (E). In addition, the twin polymerization of the twin monomer Si‐spiro in the presence of tin‐containing additives, such as Sn(OtBu)4, Sn(OnBu)2, Sn(OAc)4, and Sn(OAc)2, was investigated for comparison. The as‐prepared hybrid materials were characterized using solid‐state NMR spectroscopy (13C, 29Si, 119Sn) and high‐angle annular dark field scanning transmission electron microscopy, and were finally converted under Ar/H2 atmosphere at 600 °C to tin nanoparticles (10–200 nm) in porous carbon/silica hybrid materials (Sn/C/SiO2) with BET surface areas up to 352 m2 g−1.

Zirconium and Hafnium Twin Monomers for Mixed Oxides

“…This concept was recently extended to transition-metal-containing monomers from titanium and tungsten [20][21][22][23] and was also adapted to tin and germanium. [24][25][26][27] …”

Porous Ge@C materials via twin polymerization of germanium(ii) salicyl alcoholates for Li-ion batteries

“…[55][56][57][58][59][60][61][62][63] Diverse metal salicyl alcoholates (M ¼ Si, Ge and Sn) have been demonstrated to provide nanostructured organic-inorganic hybrid materials by this novel concept. 55,[64][65][66][67] Conversion of such hybrid materials gave e.g., mesoporous metal oxides, 64,65 microporous carbon 65 and mesoporous/microporous nanocomposites such as Sn@C/ SiO 2 . 66 We anticipated that porous materials composed of germanium incorporated in a carbon matrix (Ge@C material) are accessible by applying the concept of twin polymerization to the germanium(II) salicyl alcoholates 1-3 (Scheme 1).…”

Synthesis and Characterization of the Germanium Sulfonate Ge(CH3SO3)2 – a 3D Coordination Network Solid

“…Anhydrous Ge(CH 3 SO 3 ) 2 was obtained first as a byproduct while studying metal benzyl alcoholates for proton assisted twin polymerization using various acids as proton source 18. While reaction of Si IV and Sn II benzyl alcoholates with CH 3 SO 3 H provide organic‐inorganic hybrid materials via polymerization,19–21 reaction of germanium(II)‐bis(2‐methoxyphenyl)methoxide22 with methanesulfonic acid gave Ge(CH 3 SO 3 ) 2 ( 1 ). Herein, the synthesis, crystal structure, and characterization of compound 1 as well as its thermal behavior are reported.…”