TiO2/Ti3C2Tx复合材料的制备及其杂化电容脱盐特性的研究

doi:10.15541/jim20200243

摘要/Abstract

摘要：

人口的快速增长和工业经济迅猛发展导致全球淡水资源短缺, 对海水和苦咸水进行淡化是解决淡水资源短缺的有效方法。本工作通过直接煅烧Ti₃C₂T_x制备了TiO₂/Ti₃C₂T_x复合材料, 并研究了基于TiO₂/Ti₃C₂T_x复合电极的杂化电容脱盐特性(Hybrid capacitive deionization, HCDI)。研究表明, 煅烧温度对TiO₂/Ti₃C₂T_x的形貌、结构、电化学和脱盐特性有重要影响。以优化后的TiO₂/Ti₃C₂T_x作为负极, 酸化活性炭(Active carbon, AC)为正极, 构筑了HCDI装置。在恒压模式下, 当工作电压为1.2 V时, TiO₂/Ti₃C₂T_x‖AC在初始电导率为3000 μS·cm ^-1的NaCl溶液中的脱盐容量达到23.8 mg·g ^-1。经过20个循环后容量保持率为78%。此外, 通过研究TiO₂/Ti₃C₂T_x复合电极脱盐前后的形貌和晶相发现在脱盐过程中钠离子嵌入到Ti₃C₂T_x的层间。

关键词: TiO₂/Ti₃C₂T_x, 锐钛矿型TiO₂, 电容去离子, 吸附, 脱盐

Abstract:

The shortage of fresh water resources resultes from the rapid growth of population and industrial development. Desalination of seawater and brackish water is an effective way to alleviate the freshwater crisis. In this work, the TiO₂/Ti₃C₂T_x composites were prepared by directly calcinating Ti₃C₂T_x for hybrid capacitive deionization (HCDI). The results show that the calcination temperature has a significant impact on morphology, structure, electrochemical and desalination behavior of the TiO₂/Ti₃C₂T_x composites. To constitute the full HCDI device, the optimized TiO₂/Ti₃C₂T_x and acid treated activated carbon (AC) was employed as cathode and anode, respectively. In the constant voltage mode, the salt removal capacity of TiO₂/Ti₃C₂T_x‖AC reached 23.8 mg·g ^-1 under the cell voltage of 1.2 V in NaCl solution with an initial conductivity of 3000 μS·cm ^-1. After 20 cycles, the capacity retention rate remains at 78%. Besides, through exploring the morphology and crystal texture evolution of TiO₂/Ti₃C₂T_x electrodes before and after desalination, it is found that the desalination of TiO₂/Ti₃C₂T_x electrodes may be achieved due to the intercalation of sodium ions into the Ti₃C₂T_x interlayer.

Key words: TiO₂/Ti₃C₂T_x, anatase TiO₂, capacitive deionization, adsorption, desalination

中图分类号:

O647

席文, 李海波. TiO₂/Ti₃C₂T_x复合材料的制备及其杂化电容脱盐特性的研究[J]. 无机材料学报, 2021, 36(3): 283-291.

XI Wen, LI Haibo. Preparation of TiO₂/Ti₃C₂T_x Composite for Hybrid Capacitive Deionization[J]. Journal of Inorganic Materials, 2021, 36(3): 283-291.

图/表 10

图1 Ti3AlC2的煅烧过程

Fig. 1 Calcination process of Ti3AlC2

图2 TiO2/Ti3C2Tx复合材料制备流程图

Fig. 2 Synthesis flowchart of TiO2/Ti3C2Tx composites

图3 Ti3AlC2(A), Ti3C2Tx(B, C), TiO2/Ti3C2Tx-350(D), TiO2/Ti3C2Tx-450(E)和TiO2/Ti3C2Tx-550(F)的SEM照片, TiO2/Ti3C2Tx-450的HRTEM照片(G)和元素分布图像(H, I)

Fig. 3 SEM images of Ti3AlC2(A), Ti3C2Tx(B, C), TiO2/Ti3C2Tx-350(D), TiO2/Ti3C2Tx-450(E) and TiO2/Ti3C2Tx-550(F), HRTEM (G) and elemental mapping(H, I) of TiO2/Ti3C2Tx-450

图4 各样品的XRD图谱(A), 不同温度煅烧样品的XRD(B, C)、拉曼光谱(D)、N2吸脱附等温曲线(E)和孔径分布图(F)

Fig. 4 XRD patterns (A) of various samples, XRD patterns (B, C) of TiO2/Ti3C2Tx calcined at different temperatures, Raman spectra (D), N2 adsorption-desorption isotherms (E) and pore size distributions (F) of various samples (A)Ti3AlC2, Ti3C2Tx, TiO2/Ti3C2Tx-350, TiO2/Ti3C2Tx-450 and TiO2/Ti3C2Tx-550; (B-D) Ti3C2Tx and TiO2/Ti3C2Tx-350, TiO2/Ti3C2Tx-450 and TiO2/Ti3C2Tx-550

表1 Ti3C2Tx、TiO2/Ti3C2Tx-350、TiO2/Ti3C2Tx-450和TiO2/Ti3C2Tx-550的比表面积、平均孔径和孔体积比较

Table 1 Comparison of specific surface areas, pore sizes and pore volumes of Ti3C2Tx, TiO2/Ti3C2Tx-350, TiO2/Ti3C2Tx-450 and TiO2/Ti3C2Tx-550

Sample	Specific surface area/(m²·g^-1)	Pore size /nm	Pore volume /(cm³·g^-1)
Ti₃C₂T_x	8.542	51.979	0.111
TiO₂-Ti₃C₂T_x-350	23.227	26.394	0.153
TiO₂-Ti₃C₂T_x-450	14.630	41.005	0.150
TiO₂-Ti₃C₂T_x-550	12.324	40.134	0.124

图5 Ti3C2Tx, TiO2/Ti3C2Tx-350, TiO2/Ti3C2Tx-450和TiO2/Ti3C2Tx-550的XPS图谱

Fig. 5 XPS spectra of Ti3C2Tx, TiO2/Ti3C2Tx-350, TiO2/Ti3C2Tx-450 and TiO2/Ti3C2Tx-550 (A) XPS survey spectra; (B) Ti2p; (C) C1s; (D) O1s

图6 Ti3C2Tx, TiO2/Ti3C2Tx-350, TiO2/Ti3C2Tx-450和TiO2/Ti3C2Tx-550的CV(A)、GCD(B)和EIS(C)曲线(内插图为等效电路图)

Fig. 6 CV curves(A), GCD(B) and EIS(C) of Ti3C2Tx, TiO2/Ti3C2Tx-350, TiO2/Ti3C2Tx-450 and TiO2/Ti3C2Tx-550 with inset in (C) representing the equivalent circuit

图7 TiO2/Ti3C2Tx-450‖AC HCDI装置的脱盐性能

Fig. 7 Desalination performance of TiO2/Ti3C2Tx-450‖AC device (A, B) Conductivity and current transient of TiO2/Ti3C2Tx-450‖AC device in NaCl solution with an initial conductivity of 3000 μS·cm-1 at 1.2 V; (C) Salt removal capacity of Ti3C2Tx, TiO2/Ti3C2Tx-350 and TiO2/Ti3C2Tx-450 at various voltages; (D) Regeneration curves of TiO2/Ti3C2Tx-450‖AC device

表2 各种CDI电极材料的脱盐性能比较

Table 2 Comparison of salt removal capacity among various CDI electrodes

Sample	Specific surface area/(m²·g^-1)	Initial conductivity /(mg·L^-1)	Voltage/V	Desalination capacity/(mg·g^-1)	Ref.
Pre-conditioned Ti₃C₂T_x MXene	-	585.0	-1.2 (discharge potential)	9.19	[42]
Ti₃C₂ MXene	6.0	292.5	1.2	13.00	[39]
Ar plasma modified Ti₃C₂T_x	-	500.0	1.4	26.80	[43]
LiH/HCl-etched Ti₃C₂T_x MXene	2.1	585.0	1.2	67.70	[44]
Porous Ti₃C₂T_x MXene	293.0	10000.0	1.2	45.00	[40]
Porous nitrogen-doped MXene sheets (N-Ti₃C₂T_x)	368.8	5000.0	1.2	43.50±1.70	[45]
TiO₂/Ti₃C₂T_x-450	14.6	1500.0	1.2	22.00	This work

图8 TiO2/Ti3C2Tx-450循环20圈后的SEM照片(A, B), 原始TiO2/Ti3C2Tx-450、脱盐后TiO2/Ti3C2Tx-450和再生后TiO2/Ti3C2Tx- 450的XRD图谱(C, D)

Fig. 8 SEM (A) and the enlarged (B) images of TiO2/Ti3C2Tx-450 after 20 cycling, XRD patterns(C, D) of TiO2/Ti3C2Tx-450 before and after desalting and regeneration (B) Enlarged image of (A); (D) Enlarged image of (C) within 2θ = 34°-44°

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TiO₂/Ti₃C₂T_x复合材料的制备及其杂化电容脱盐特性的研究

Preparation of TiO₂/Ti₃C₂T_x Composite for Hybrid Capacitive Deionization

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