微波辅助水热法快速合成介孔磷酸镍

doi:10.3724/SP.J.1077.2012.00501

摘要/Abstract

摘要：

采用微波辅助水热法快速合成了介孔磷酸镍(MW-NiPO-2), 详细研究了在微波水热条件下微波晶化温度、微波辐射时间、碱度及Ni/P摩尔比对MW-NiPO-2合成的影响, 优化了合成条件. 并利用ICP、FT-IR、TEM和N₂吸附等手段对比研究了溶胶-凝胶法和微波水热法合成样品的结构组成、比表面和孔道特征. 研究结果表明: 在微波辅助水热条件下, 在较低温度下(60℃)即可形成MW-NiPO-2; 在100℃下, 0.25 h即有MW-NiPO-2生成. 在微波辐射1 h, 碱度(OH^-/P)为2.0、原料Ni/P比为0.7条件下, 能够合成有序度较高的MW-NiPO-2. MW-NiPO-2和 SG-NiPO-2具有相似的骨架结构和组成, 但其纳米管簇结构特征不明显, 表现出类似虫孔结构的状态. 微波辅助水热法合成的MW-NiPO-2较溶胶-凝胶法合成样品具有更大的比表面和孔容, 分别为334.4 m²/g和0.318 cm³/g.

关键词: 介孔磷酸镍, NiPO, 微波辅助水热合成, 溶胶-凝胶法

Abstract:

Mesostructured nickel phosphate (MW-NiPO-2) was rapidly synthesized in the presence of cationic surfactant by a microwave assisted hydrothermal process. The synthesis parameters, microwave irradiation temperature and time, OH^-/P and Ni/P molar ratios of the precursor, were systematically investigated and optimized. The characterizations of the materials obtained by the two different procedures, Sol-Gel method and microwave assisted hydrothermal process, were carried out by ICP, FT-IR, TEM and N₂ physisorption. The results show that MW-NiPO-2 can be obtained at relatively low temperature (60℃). When the microwave radiation temperature was 100℃, the mesostructured phase formed in an extremely short period about 0.25 h. Ordered MW-NiPO-2 can be obtained under microwave irradiation for 1 h at 100℃, when OH^-/P and the Ni/P molar ratios of the precursor are 2.0 and 0.7, respectively. In contrast, it took at least 24 h for completion via Sol-Gel method. MW-NiPO-2 and SG-NiPO-2 possess similar structure and composition while MW-NiPO-2 exhibites a worm-like appearance other than piled nanotubes. In comparison with the sample synthesized via Sol-Gel method, MW-NiPO-2 possesses a relatively high BET surface area (334.4 m²/g) and pore volume (0.318 cm³/g).

Key words: mesoporous nickel phosphate, NiPO, microwave assisted hydrothermal synthesis, Sol-Gel method

中图分类号:

TQ426

李旭影, 谭涓, 杨建华, 刘靖, 杨菲. 微波辅助水热法快速合成介孔磷酸镍[J]. 无机材料学报, 2012, 27(5): 501-506.

LI Xu-Ying, TAN Juan, YANG Jian-Hua, LIU Jing, YANG Fei. Rapid Synthesis of Mesoporous Nickel Phosphates under Microwave Assisted Hydrothermal Condition[J]. Journal of Inorganic Materials, 2012, 27(5): 501-506.

图/表 9

图1 MW-NiPO-2(a)和SG-NiPO-2(b)样品的XRD图谱

Fig. 1 XRD patterns of as-synthesized MW-NiPO-2 (a) and SG-NiPO-2 (b) samples

图2 微波辐射温度对合成样品[100]衍射峰相对强度的影响(插图为120℃时合成样品的XRD图谱)

Fig. 2 Effect of radiation temperature on the evolution of Is/I0 of MW-NiPO-2 (Inset is XRD pattern of sample synthesized at 120℃)

图3 微波辐射时间对合成样品[100]衍射峰相对强度的影响

Fig. 3 Effect of radiation time on the evolution of Is/I0 of MW-NiPO-2

图4 不同碱度条件下合成MW-NiPO-2样品的XRD图谱

Fig. 4 XRD patterns of as-synthesized MW-NiPO-2 samples with different OH-/P (a) 1.9; (b) 2.0; (c) 2.1; (d) 2.3

图5 不同原料Ni/P条件下合成MW-NiPO-2样品的XRD图谱

Fig. 5 XRD patterns of MW-NiPO-2 samples synthesized with different Ni/P molar ratios (a) 0.3, (b) 0.5, (c) 0.7, (d) 0.9

Table 1 ICP data of MW-NiPO-2 samples synthesized with different Ni/P molar ratios in initial gel

Ni/P of initial gel	Ni content /wt%	P content /wt%	Ni/P of MW-NiPO-2
0.3	35.10	11.39	1.63
0.5	34.98	11.87	1.55
0.7	37.69	11.97	1.66

图6 MW-NiPO-2 (a)和SG-NiPO-2 (b) 样品的FT-IR图谱

Fig. 6 FT-IR spectra of as-synthesized (a) MW-NiPO-2; (b) SG-NiPO-2 MW-Nipo-2 preparation condition OH-/P=2.0, Ni/P=0.7, 100℃/1 h

图7 MW-NiPO-2 (a)和 SG-NiPO-2 (b)样品的TEM照片

Fig. 7 TEM images of as-synthesized mesoporous nickel phosphate samples

图8 MW-NiPO-2(a)和SG-NiPO-2(b)样品的吸附-脱附曲线

Fig. 8 Adsorption-desorption isotherm of extracted samples (a) MW-NiPO-2; (b) SG-NiPO-2

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