93Nb核磁共振研究铌酸纳米棒的水热晶化机理
收稿日期: 2023-03-27
网络出版日期: 2023-05-15
基金资助
国家自然科学基金资助项目(21773056);国家自然科学基金资助项目(21703056);河南省科技攻关项目(212102210608);河南省科技攻关项目(202102110289);河南工业大学青年骨干教师项目(0503/21420046);河南工业大学青年骨干教师项目(0503/21420110);河南工业大学创新基金支持计划专项资助(2021ZKCJ01)
Hydrothermal Crystallization of Niobium Oxide Nanorods Studied by 93Nb Nuclear Magnetic Resonance
Received date: 2023-03-27
Online published: 2023-05-15
氧化铌（Nb2O5）及其水合物铌酸（Nb2O5·nH2O）代表了一类重要的多相催化剂，然而其水热合成过程和机理尚不明确．本文采用93Nb NMR，结合X射线粉末衍射、透射电镜等技术和量化计算，研究了以草酸铌铵为前驱体水热生成铌酸纳米棒的晶化过程．结果表明草酸铌铵水热晶化过程中发生了水解-聚合反应，先是草酸铌铵水解，接着铌氧单体之间发生缩水聚合反应，最终生成了层内无序、层间有序结构的固体铌酸纳米棒．晶化过程符合“液相成核”机理，层状结构铌酸纳米棒在180 ℃下1 h内即可生成，后续水热处理并未使其明显长大，新的固体产物不断由溶液中独立生成．
申长志 , 张琳琳 , 李新 , 申万岭 . 93Nb核磁共振研究铌酸纳米棒的水热晶化机理[J]. 波谱学杂志, 2023 , 40(4) : 376 -384 . DOI: 10.11938/cjmr20233061
The crystallization process of hydrothermally synthesizing niobium oxide nanorods with ammonium niobium oxalate precursor was investigated using 93Nb NMR, combined with X-ray powder diffraction, transmission electron microscopy and quantum chemistry calculations. The results showed that the hydrothermal crystallization of ammonium niobium oxalate underwent a hydrolysis-polymerization reaction, starting with the hydrolysis of ammonium niobium oxalate, followed by the polymerization of the niobium-oxide monomers by condensation, resulting in dimers, trimers and multimers, and finally generating solid niobium oxide nanorods with disordered intra-layer and ordered inter-layer structures. The mechanism of crystallization process is “liquid phase nucleation”, with the layer-structured niobium oxide nanorods being produced within 1 h at 180 ℃. The subsequent hydrothermal treatment does not lead to significant growth of the nanorods, and new solid products are continuously generated independently from the solution.
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