反气相色谱法对钛白粉表面性质的研究

王小慧; 郭杰; 胥金秀; 谭玲; 解莉花; 胡一杰

doi:10.7513/j.issn.1004-7638.2024.05.006

反气相色谱法对钛白粉表面性质的研究

doi: 10.7513/j.issn.1004-7638.2024.05.006

王小慧^{1, 2},
郭杰^{1, 2},
胥金秀^{1, 2},
谭玲^{1, 2},
解莉花^{1, 2},
胡一杰^{1, 2}

1.
攀钢集团研究院有限公司, 钒钛资源综合利用国家重点实验室, 四川攀枝花 617000
2.
成都先进金属材料产业技术研究院股份有限公司先进功能材料研究所, 四川成都 610305

详细信息

中图分类号: TF823,TQ621.1
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出版历程
- 收稿日期: 2024-02-05
- 网络出版日期: 2024-10-30
- 刊出日期: 2024-10-30

Characterization of surface properties of titanium dioxide by inverse gas chromatography

Wang Xiaohui^{1, 2},
Guo Jie^{1, 2},
Xu Jinxiu^{1, 2},
Tan Ling^{1, 2},
Xie Lihua^{1, 2},
Hu Yijie^{1, 2}

1.
Pangang Group Research Institute Co., Ltd., State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization, Panzhihua 617000, Sichuan, China
2.
Department of Advanced Functional Materials, Chengdu Advanced Metallic Materials Industry Technology Research Institute Co., Ltd., Chengdu 610305, Sichuan, China

摘要

摘要: 采用反气相色谱法（IGC）测试了3种钛白粉的表面能和酸碱常数，研究有机表面处理对钛白粉表面性质的影响。通过不同温度下不同分子探针试验计算研究了样品的非极性表面能。结果表明：在同一温度下（测试温度范围内），随着包覆有机物的增加，样品的非极性表面能$ {\gamma }_{s}^{d} $减小；样品的$ {\gamma }_{s}^{d} $随着温度的升高而减小。同时通过以极性分子为探针分子计算研究表面能的酸碱分量，结果表明钛白粉表面呈两性偏酸性，有机处理剂与钛白表面羟基反应使得表面酸位点减少，酸性下降。但是过多地加入有机处理剂时，部分有机处理剂水解生成羟基未与钛白反应，反而增加样品表面酸性。
- 钛白粉 /
- 表面性质 /
- 反气相色谱法 /
- 有机处理剂
Abstract: The surface energy and acid/base constants of three kinds of titanium dioxide (TiO₂) were measured by inverse gas chromatography (IGC) to investigate the effect of organic treatment on the surface properties of TiO₂. The non-polar surface energy of the samples were calculated by using different molecular probes at different temperatures. The results indicate that non-polar surface energy $ \gamma\mathrm{_s^d} $of TiO₂ decreases with the increase of organic cladding amount at the same temperature (within the testing temperature range). As the temperature increases, $ \gamma\mathrm{_s^d} $of TiO₂ decreases. Meanwhile, the acid-base component of surface energy was studied by using polar molecules as probe molecules, revealing that the surface of titanium dioxide is amphoacid. Since the surface of TiO₂ presents acidic, the reaction between organic agents and the hydroxyl groups on the surface of TiO₂ leads to the decrease in the surface acid sites and thus the surface acidity of TiO₂. However, when excessive organic agent is added, some hydroxyl groups generated by organic agents hydrolyzation would not react with TiO₂, resulting in the increment of TiO₂ surface acidity.
- TiO₂ /
- surface properties /
- inverse gas chromatography (IGC) /
- organic agents

HTML全文

图 1 非极性溶剂作为探针分子，样品的$ \mathrm{l}\mathrm{n}{V}_{\mathrm{g}} $与$ 1/T $的相关性

Figure 1. Correlation between lnV_g and 1/T of samples while non-polar solvent acting as the probe molecule

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图 2 极性溶剂作为探针分子，样品的$ \mathrm{l}\mathrm{n}{V}_{\mathrm{g}} $与$ 1/T $的相关性

Figure 2. Plot of Correlation between lnV_g and 1/T of samples while polar solvent acting as the probe molecule

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图 3 非极性溶剂作为探针分子，不同温度下样品的RT$ \mathrm{l}\mathrm{n}{V}_{\mathrm{g}} $与碳个数相关性

Figure 3. Correlation between RTlnV_g and arbon numbers of samples at different temperatures while non-polar solvent acting as the probe molecule

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图 4 钛白粉样品的$ {\gamma }_{\mathrm{s}}^{\mathrm{d}} $随温度的变化

Figure 4. The $ {\gamma }_{\mathrm{s}}^{\mathrm{d}} $ changes of TiO₂ samples with temperatures

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图 5 以$ -\Delta {\mathrm{G}} $对探针分子的极化度P_DP作图

Figure 5. Plot of $-\Delta {\mathrm{G}} $ versus P_DP for various probes

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图 6 极性溶剂作为探针分子，样品的$ -\Delta {G}^{\mathrm{s}}/T $与$ 1/T $的相关性

Figure 6. Plot of $ -\Delta {G}^{\mathrm{s}}/T $ versus 1/T for polar probes

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表 1 以非极性溶剂作为探针分子，钛白样品的吸附自由能

Table 1. ΔG of titanium dioxides while non-polar solvent acting as the probe molecule

探针分子	1^#		2^#		3^#
探针分子	$ -\Delta G/ $(kJ·mol⁻¹)	$ {R}^{2} $	$ -\Delta G/ $(kJ·mol⁻¹)	$ {R}^{2} $	$ -\Delta G/ $(kJ·mol⁻¹)	$ {R}^{2} $
正庚烷	25.6	0.968	33.0	0.984	39.9	0.998
正辛烷	34.1	0.970	45.3	0.992	48.9	0.999
正壬烷	42.1	0.975	56.1	0.994	56.5	0.999
正癸烷	54.1	0.991	64.89	0.995	63.1	0.999

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表 2 以极性溶剂作为探针分子，钛白样品的吸附自由能

Table 2. $ \Delta G $ of titanium dioxides while polar solvent acting as the probe molecule

探针分子	1^#		2^#		3^#
探针分子	$ -\Delta G/ $(kJ·mol⁻¹)	$ {R}^{2} $	$ -\Delta G/ $(kJ·mol⁻¹)	$ {R}^{2} $	$ -\Delta G/ $(kJ·mol⁻¹)	$ {R}^{2} $
二氯甲烷	14.3	0.926	21.4	0.930	30.9	0.960
甲苯	44.9	0.968	44.6	0.995	56.2	0.993

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表 3 不同温度下钛白粉样品的$ {\gamma }_{\mathrm{s}}^{\mathrm{d}} $

Table 3. The ${\gamma }_{\mathrm{s}}^{\mathrm{d}} $ of TiO₂ samples at different temperatures

编号	$ {\gamma }_{\mathrm{s}}^{\mathrm{d}} $/（mJ·m⁻²）
编号	383.15 K	373.15 K	363.15 K	353.15 K	343.15 K
1^#	10.72	15.25	17.80	22.53	26.75
2^#	14.08	17.44	23.65	31.58
3^#	25.27	28.64	33.58	37.11	38.44

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表 4 钛白样品表面的酸碱作用自由能

Table 4. $ \Delta {G}^{s} $ of acid-base interaction on the surface of TiO₂ samples

T/K	探针分子	$ -\Delta {G}^{\mathrm{s}} $/（kJ·mol⁻¹）
T/K	探针分子	1^#	2^#	3^#
383.15	二氯甲烷	5.540	6.280	7.442
383.15	甲苯	2.357	4.071	5.083
373.15	二氯甲烷	6.509	6.385	7.934
373.15	甲苯	2.903	4.611	5.466
363.15	二氯甲烷	6.995	7.703	8.425
363.15	甲苯	4.168	4.907	6.132
353.15	二氯甲烷	7.333	8.611	8.478
353.15	甲苯	3.998	5.066	6.367
343.15	二氯甲烷	7.843		9.152
343.15	甲苯	5.038		6.946

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表 5 钛白样品表面的酸碱性

Table 5. Surface acid/base characteristics of TiO₂ samples

编号	$ {K}_{\mathrm{a}} $	$ {K}_{\mathrm{b}} $	$ {K}_{\mathrm{a}}/{K}_{\mathrm{b}} $
1^#	64.72	1.62	40.02
2^#	39.52	2.1911	18.02
3^#	54.28	1.45	37.31

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