93Nb核磁共振研究铌酸纳米棒的水热晶化机理

doi:10.11938/cjmr20233061

摘要/Abstract

摘要：

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．

关键词: ⁹³Nb核磁共振, 纳米氧化铌, 草酸铌铵, 水热, 晶化机理

Abstract:

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.

Key words: ⁹³Nb NMR, nano niobium oxide, ammonium niobium oxalate, hydrothermal, crystallization mechanism

中图分类号:

O482.53

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.

SHEN Changzhi, ZHANG Linlin, LI Xin, SHEN Wanling. Hydrothermal Crystallization of Niobium Oxide Nanorods Studied by ⁹³Nb Nuclear Magnetic Resonance[J]. Chinese Journal of Magnetic Resonance, 2023, 40(4): 376-384.

图/表 4

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⁹³Nb核磁共振研究铌酸纳米棒的水热晶化机理

Hydrothermal Crystallization of Niobium Oxide Nanorods Studied by ⁹³Nb Nuclear Magnetic Resonance

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