Preparation of Ti3C2/SrTiO3 composites and their photoelectrochemical cathodic protection
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摘要: 由于钛酸锶(SrTiO3)存在禁带宽度大、光生载流子分离率低等缺点，限制了其光电化学阴极保护性能，为解决此问题，可对其进行负载助催化剂Ti3C2进行改性。首先采用水热法制备了SrTiO3和蚀刻法制备了Ti3C2，然后通过机械法混合制备了Ti3C2/SrTiO3复合材料。通过XRD、XPS、SEM、UV-vis DRS、PL对样品物相结构、化学状态、微观形貌、光吸收性能等特征进行了表征。最后分析了Ti3C2/SrTiO3复合材料对304不锈钢(304SS)的光电化学阴极保护性能。结果表明，Ti3C2/SrTiO3复合材料拓宽了可见光利用范围；其中，加入Ti3C2含量为15wt%的15%-Ti3C2/SrTiO3复合材料的光生载流子分离率更高，光电流密度达到2.5 μA·cm−2；在3.5wt% NaCl溶液中，304SS与该复合材料偶联后，光照条件下，其电势电位下降了200 mV，可以有效保护304SS，经过4次开闭光循环测试，Ti3C2/SrTiO3复合材料性能稳定。Abstract: Due to the shortcomings of strontium titanate (SrTiO3) with large band gap and low separation rate of photogenerating carriers, its photoelectrochemical cathodic protection performance is limited. And in order to solve this problem, SrTiO3 can be modified with the supporting cocatalyst Ti3C2. Firstly, SrTiO3 was prepared by hydrothermal method and Ti3C2 was obtained by etching. Then, Ti3C2/SrTiO3 composites were prepared by mechanical mixing. XRD, XPS, SEM, UV-vis DRS, and PL had characterized the phase structure, chemical state, microscopic morphology, and light absorption performance of the samples. Finally, the photoelectrochemical cathodic protection performance of Ti3C2/SrTiO3 composites to 304 stainless steel (304SS) was analyzed. The results show that Ti3C2/SrTiO3 composites are broadened to absorb visible light. Among them, the photogenerated carrier separation rate of the 15%-Ti3C2/SrTiO3 composite with a mass fraction of 15wt% of Ti3C2 has a higher separation rate and an optical current density of 2.5 μA·cm−2. In the 3.5wt% NaCl solution, after the coupling of 304SS to the composite, its photomotive potential drops by 200 mV under light conditions, which can effectively protect 304SS. After four open and closed light cycle tests, the performance of Ti3C2/SrTiO3 composites are stable.
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Key words:
- SrTiO3 /
- Ti3C2 /
- composites /
- metallic conductivity /
- photoelectrochemical cathodic protection
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图 1 Ti3C2/SrTiO3复合材料制备流程图
Figure 1. Flowchart of preparation of Ti3C2/SrTiO3 composite
图 2 光电化学阴极保护测试装置图
Figure 2. Test device diagram for photoelectrochemical cathodic protection
GW—Ground wire; CE—Counter electrode; RE—Reference electrode; WE—Working electrode; SCE—Saturated calomel electrode; 304SS—304 stainless steel; hv—Light intensity
图 3 Ti3AlC2和Ti3C2 (a)，SrTiO3、Ti3C2和Ti3C2/SrTiO3复合材料 (b) 的 XRD 图谱
Figure 3. XRD patterns of Ti3AlC2 and Ti3C2 (a), SrTiO3, Ti3C2 and Ti3C2/SrTiO3 composites (b)
图 4 (a) SrTiO3、Ti3C2 和15%-Ti3C2/SrTiO3的XPS全谱图；SrTiO3和15%-Ti3C2/SrTiO3的Ti2p峰(b)、Sr3d峰(c)和O1s峰(d)的高分辨率XPS图谱；(e) Ti3C2 和15%-Ti3C2/SrTiO3的C1s峰的高分辨率XPS图谱
Figure 4. (a) XPS survey spectra of SrTiO3、Ti3C2 和15%-Ti3C2/SrTiO3; High-resolution XPS spectra of Ti2p (b)、Sr3d (c) and O1s (d) of SrTiO3 and 15%-Ti3C2/SrTiO3; (e) High-resolution XPS spectra of C1s of Ti3C2 and 15%-Ti3C2/SrTiO3
VO—Oxygen vacancy; LO—Lattice oxygen
图 5 SrTiO3 ((a),(b))、Ti3AlC2 ((c), (d))、Ti3C2 ((e), (f)) 和15%-Ti3C2/SrTiO3复合材料 ((g), (h)) 的SEM图像
Figure 5. SEM images of SrTiO3 ((a), (b)), Ti3AlC2 ((c), (d)), Ti3C2 ((e), (f)) and 15%-Ti3C2/SrTiO3 composite ((g), (h))
图 6 SrTiO3、Ti3C2和Ti3C2/SrTiO3复合材料UV-vis DRS图谱 (a) 及Tauc图谱 (b)
Figure 6. UV-vis DRS diagram (a) and Tauc diagram (b) of SrTiO3, Ti3C2 and Ti3C2/SrTiO3 composites
Ehv—Photon energy value; Eg—Band gap energy value; α—Absorbance
图 7 SrTiO3、Ti3C2和 Ti3C2/SrTiO3复合材料的光致发光图谱
Figure 7. Photoluminescent spectra of SrTiO3, Ti3C2 and Ti3C2/SrTiO3 composites
图 8 SrTiO3和Ti3C2/SrTiO3复合材料的电化学阻抗图谱
Figure 8. Electrochemical impedance spectra of SrTiO3 and Ti3C2/SrTiO3 composites
Z'—Real part of impedance; Z"—Imaginary part of impedance; Rs—electrolyte solution resistance; Ret—semiconductor depletion layer resistance; Zw—Charge transfer resistance; Cdl—Electrochemical capacitance
图 9 SrTiO3和 Ti3C2/SrTiO3复合材料的光电流密度-时间曲线
Figure 9. Photocurrent density-time curves of SrTiO3 and Ti3C2/SrTiO3 composites
图 10 SrTiO3和 Ti3C2/SrTiO3复合材料的开路电位-时间曲线
Figure 10. Open-circuit potential-time curves of SrTiO3 and Ti3C2/SrTiO3 composites
E304SS—Self-corrosion potential of 304SS
图 11 Ti3C2/SrTiO3复合材料的光电化学阴极保护机制图
Figure 11. Photochemical cathodic protection mechanism diagram of Ti3C2/SrTiO3 composites
EF—Energy of the fermi level; ECB—Energy of the conduction band (CB); EVB—Energy of the valence band (VB); NHE—Normal hydrogen electrode
表 1 Ti3C2/SrTiO3复合材料配比表
Table 1. Ti3C2/SrTiO3 composites material ratio table
Samples SrTiO3/g Ti3C2/g SrTiO3 1 0 5%-Ti3C2/SrTiO3 1 0.053 10%-Ti3C2/SrTiO3 1 0.111 15%-Ti3C2/SrTiO3 1 0.176 20%-Ti3C2/SrTiO3 1 0.25 Ti3C2 0 0.2 
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