类水滑石Ti/Li/Al-LDHs的制备及其CO<sub>2</sub>吸附性能

孔婷婷; 董羿蘩; 张颖萍; 张亚刚; 周安宁

类水滑石Ti/Li/Al-LDHs的制备及其CO₂吸附性能

西安科技大学化学与化工学院, 陕西西安 710054

基金项目:

国家自然科学基金资助 51074122

详细信息

中图分类号: TQ424.1
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出版历程
- 收稿日期: 2016-04-07
- 修回日期: 2016-06-18
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-08-10

Preparation of hydrotalcite-like Ti/Li/Al-LDHs and its performance in CO₂ adsorption

College of Chemistry and Chemical Engineering, Xi'an University of Science and Technology, Xi'an 710054, China

More Information

Corresponding author: Tel: 13609282106, E-mail: psu564@139.com

摘要

摘要: 采用共沉淀法制备了一系列新型的类水滑石Ti/Li/Al-LDHs材料，通过原子吸收光谱（AAS）、X射线衍射（XRD）、扫描电镜（SEM）、热重分析（TG）和傅里叶变换红外光谱（FT-IR）等技术对其进行了表征，研究了不同金属元素比例和焙烧温度对该Ti/Li/Al-LDHs材料的结构、形貌及其CO₂吸附性能的影响。结果表明，当Ti/Li/Al比为1：3：4时，水滑石Ti/Li/Al-LDHs的结晶度最好，形貌最规整，而Ti/Li/Al比为1：3：2、300℃下焙烧后得到的Ti₁Li₃Al₂-LDHs₃₀₀的CO₂吸附性能最好。Ti₁Li₃Al₂-LDHs₃₀₀上CO₂吸附量可达53.5mg/g，10次循环吸附后，CO₂吸附量仅下降了2.4%。
- 水滑石 /
- Ti/Li/Al-LDHs /
- 金属元素 /
- 焙烧 /
- 二氧化碳 /
- 吸附
Abstract: A series of hydrotalcite-like Ti/Li/Al-LDHs materials were prepared by co-precipitation method and characterized by atomic absorption spectrophotometer (AAS), X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal gravimetric analysis (TG) and Fourier transform infrared (FT-IR); the influence of metal composition and calcination temperature on the structure, morphology and CO₂ adsorption capacity of Ti/Li/Al-LDHs was investigated. The results showed that Ti₁Li₃Al₄-LDHs obtained with a Ti/Li/Al ratio of 1:3:4 displays the highest crystallinity and regular morphology, whereas Ti₁Li₃Al₂-LDHs₃₀₀ prepared with a Ti/Li/Al ratio of 1:3:2 and calcined at 300℃ exhibits the best adsorption performance towards CO₂. The CO₂ adsorption capacity over Ti₁Li₃Al₂-LDHs₃₀₀ reaches 53.5mg/g; in addition, the adsorption capacity is only decreased by 2.4% after adsorption for 10 cycles.
- layered double hydroxides /
- Ti/Li/Al-LDHs /
- metal element /
- calcination /
- carbon dioxide /
- adsorption

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图 1 固定床反应器实验装置示意图

Figure 1 Schematic diagram of the fixed bed reactor system

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图 2 不同Ti⁴⁺/ Li⁺/ Al³⁺物质的量比的Ti/Li/Al-LDHs的XRD谱图

Figure 2 XRD patterns of Ti/Li/Al-LDHs with different Ti⁴⁺/ Li⁺/Al³⁺mol ratio

a: Ti₁Li₃Al₁-LDHs; b: Ti₁Li₃Al₂-LDHs; c: Ti₁Li₃Al₃-LDHs; d: Ti₁Li₃Al₄-LDHs; e: Ti₂Li₃Al₃-LDHs; f: Ti₃Li₃Al₂-LDHs

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图 3 不同Ti⁴⁺/Li⁺/Al³⁺物质的量比的Ti/Li/Al-LDHs的TG-DSC曲线

Figure 3 TG-DSC profiles of Ti/Li/Al-LDHs with different Ti⁴⁺/Li⁺/Al³⁺ mol ratio

a: Ti₁Li₃Al₄-LDHs; b: Ti₁Li₃Al₃-LDHs; c: Ti₁Li₃Al₂-LDHs; d: Ti₁Li₃Al₁-LDHs

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图 4 Ti₁Li₃Al₂-LDHs的干燥样及不同温度下焙烧样的XRD谱图

a: dried sample; b: 180 ℃；c: 300 ℃; d: 500 ℃; e: 600 ℃

Figure 4 XRD patterns of Ti₁Li₃Al₂-LDHs calcined at different temperatures

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图 5 Ti₁Li₃Al₂-LDHs的干燥样及不同温度下焙烧样的SEM照片

Figure 5 SEM images of Ti₁Li₃Al₂-LDHs calcined at different temperatures

(a): dried sample; (b): 180 ℃; (c): 300 ℃; (d): 500 ℃; (e): 600 ℃

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图 6 Ti₁Li₃Al₂-LDHs的干燥样及不同温度下焙烧样的FT-IR谱图

Figure 6 FT-IR patterns of Ti₁Li₃Al₂-LDHs calcined at different temperatures

a: dried sample; b: 180 ℃; c: 300 ℃; d: 500 ℃; e: 600 ℃

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图 7 不同Ti⁴⁺/Li⁺/Al³⁺物质的量比的Ti/Li/Al-LDHs经不同温度焙烧后样品的CO₂吸附

Figure 7 CO₂ adsorption capacity of Ti/Li/Al-LDHs with different Ti⁴⁺/Li⁺/Al³⁺ mol ratio and calcined at various temperatures

□: Ti₁Li₃Al₁-LDHs; ●: Ti₁Li₃Al₂-LDHs; ▲: Ti₁Li₃Al₃-LDHs; ▶: Li₁Al₂-LDHs; ∇: Ti₁Li₃Al₄-LDHs; ◇: Ti₂Li₃Al₄-LDHs; ◀: Ti₃Li₃Al₄-LDHs

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图 8 Ti₁Li₃Al₂-LDHs干燥样经10次循环后CO₂的吸附

Figure 8 CO₂ adsorption capacity of Ti₁Li₃Al₂-LDHs dried sample after 10 cycles (adsorption condition: room temperature; the inlet flow rate, 80 mL/min)

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图 9 Ti₁Li₃Al₂-LDHs₃₀₀经10次循环后CO₂的吸附

Figure 9 CO₂ adsorption capacity of Ti₁Li₃Al₂-LDHs₃₀₀ after 10 cycles

(adsorption condition: room temperature; the inlet flow rate, 80 mL/min)

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表 1 不同Ti⁴⁺/Li⁺/Al³⁺物质的量比的Ti/Li/Al-LDHs晶胞参数和晶粒粒径

Table 1 Lattice parameter and grain size of Ti/Li/Al-LDHs with different Ti⁴⁺/Li⁺/Al³⁺ mol ratio

Ti/Li/Al-LDHs	Ti/Li/Al in solution	Ti/Li/Al in solid	Cell parameters d/nm					Grain size d/nm
Ti/Li/Al-LDHs	Ti/Li/Al in solution	Ti/Li/Al in solid	d₀₀₃	d₀₀₆	d₁₁₀	a-axis	c-axis	d_a	d_c
Ti₁Li₃Al₁-LDHs	1:3:1	0.98:2.12:1.13	0.77	0.40	0.15	0.29	2.31	18.49	11.68
Ti₁Li₃Al₂-LDHs	1:3:2	0.99:2.37:2.14	0.75	0.38	0.15	0.29	2.25	16.42	16.84
Ti₁Li₃Al₃-LDHs	1:3:3	0.96:2.62:3.10	0.75	0.38	0.15	0.29	2.24	17.05	10.00
Ti₁Li₃Al₄-LDHs	1:3:4	1.02:2.72:3.96	0.74	0.37	0.15	0.29	2.18	19.52	10.21
Ti₂Li₃Al₄-LDHs	2:3:4	1.98:2.84:3.93	0.74	0.37	0.15	0.29	2.22	15.30	8.98
Ti₃Li₃Al₄-LDHs	3:3:4	2.98:2.92:4.01	0.75	0.38	0.15	0.29	2.24	15.50	9.47

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表 2 不同比例的Ti/Li/Al-LDHs的比表面积和孔结构参数

Table 2 Surface area and pore structure parameters of Ti/Li/Al-LDHs with different Ti⁴⁺/Li⁺/Al³⁺ molar ratios

Sample	BET surface area A/(m²·g^-1)	Pore volume v/(m³·g^-1)		Pore size d/nm
Sample	BET surface area A/(m²·g^-1)	total	micro	Pore size d/nm
Ti₁Li₃Al₁-LDHs₃₀₀	131.971	0.503	0.007	3.285
Ti₁Li₃Al₂-LDHs₃₀₀	138.621	0.522	0.008	3.427
Ti₁Li₃Al₃-LDHs₃₀₀	120.983	0.492	0.006	3.390
Ti₁Li₃Al₄-LDHs₃₀₀	121.454	0.391	0.005	3.575
Ti₂Li₃Al₄-LDHs₃₀₀	120.030	0.371	0.004	3.450
Ti₃Li₃Al₄-LDHs₃₀₀	112.581	0.377	0.004	3.569

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表 3 不同比例和不同温度焙烧下Ti/Li/Al-LDHs的比表面积和孔结构参数

Table 3 Surface area and pore structure parameters of Ti₁Li₃Al₂-LDHs calcined at different temperatures

Sample	BET surface area A/(m²·g^-1)	Pore volume v/(m³·g^-1)		Pore size d/nm
Sample	BET surface area A/(m²·g^-1)	total	micro	Pore size d/nm
Ti₁Li₃Al₂-LDHs	145.371	0.311	0.004	3.812
Ti₁Li₃Al₂-LDH₁₈₀	118.752	0.301	0.006	3.650
Ti₁Li₃Al₂-LDHs₃₀₀	138.621	0.522	0.008	3.427
Ti₁Li₃Al₂-LDHs₅₀₀	150.851	0.482	0.006	3.392
Ti₁Li₃Al₂-LDHs₆₀₀	155.900	0.304	0.006	3.306

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