Chuiko Institute of Surface Chemistry, General Naumov Street 17, 03164 Kyiv, Ukraine.
J Colloid Interface Sci. 2012 Feb 15;368(1):263-72. doi: 10.1016/j.jcis.2011.11.018. Epub 2011 Nov 16.
Low-temperature (1)Н NMR spectroscopy was used to study states of water bound to phosphoric and phosphonic acids (phosporus oxyacids, POA) alone or adsorbed onto nanosilica OX-50 (specific surface area S(BET)=52 m(2)/g) or A-300 (S(BET)=297 m(2)/g). Concentrated solutions or weakly hydrated solid POA or dried silica/POA powders placed in CCl(4) medium are characterized by different temperature dependences of the chemical shift of the proton resonance (δ(H)) because of partial dissociation of PO-H bonds strongly affected by water amounts and temperature. NMR cryoporometry results show that both small water clusters and nanodomains are present at the interfaces of hydrated solid POA and silica/POA powders. Quantum chemical calculations of the (1)H NMR spectra demonstrate the influence of POA/water cluster structure and dissociation of the PO-H bonds on the δ(H) values.
低温 (1)Н NMR 光谱学被用来研究单独结合于磷酸和膦酸(磷含氧酸,POA)的水的状态,或者被吸附到纳米二氧化硅 OX-50(比表面积 S(BET)=52 m(2)/g)或 A-300(比表面积 S(BET)=297 m(2)/g)上的水的状态。由于 PO-H 键的部分解离强烈地受到水的量和温度的影响,因此在 CCl(4) 介质中处于浓缩溶液或弱水合固体 POA 或干燥的二氧化硅/POA 粉末的状态,其质子共振(δ(H))的化学位移具有不同的温度依赖性。NMR 冷冻量热法的结果表明,在水合固体 POA 和二氧化硅/POA 粉末的界面处存在小的水分子簇和纳米区。(1)H NMR 光谱的量子化学计算证明了 POA/水簇结构和 PO-H 键的解离对 δ(H)值的影响。