TNTs结构强化TNTs/SnO<sub>2</sub>-Sb电极电催化活性的影响机制

YANG Lisha; GUO Yanming

doi:10.1016/S1872-5813(23)60390-1

TNTs结构强化TNTs/SnO₂-Sb电极电催化活性的影响机制

doi: 10.1016/S1872-5813(23)60390-1

杨莉莎^,,
郭颜铭

黑龙江科技大学环境与化工学院, 黑龙江哈尔滨, 150022

详细信息

中图分类号: X703.1
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出版历程
- 收稿日期: 2023-09-04
- 修回日期: 2023-09-25
- 录用日期: 2023-09-26
- 网络出版日期: 2023-10-31

Enhanced electro-catalytic activity of TNTs/SnO₂-Sb electrode through the effect mechanism of TNTs architecture

YANG Lisha^,,
GUO Yanming

School of environmental and chemical engineering, Heilongjiang University of Science & Technology, Harbin 150022, China

Funds: The project was supported by National Natural Science Foundation of China （52000061） ( The strengthening mechanism of nano-metal oxide composite electrode on the electrocatalytic degradation of trace highly toxic organics).

More Information

Corresponding author: Tel: 18045044470, E-mail: lisha331229831@163.com

摘要

摘要: 采用溶剂热法成功制备了TNTs/SnO₂-Sb电极，通过调整氧化电压和氧化时间构建出不同结构的二氧化钛纳米管（TNTs）阵列，以探究其对电极结构和电化学性能的影响。SEM和接触角测试表明，相较于阳极氧化时间，阳极氧化电压是影响TNTs阵列形貌和表面亲水性的主要因素。SEM、XRD、LSV和EIS结果表明，TNTs阵列孔径的大小影响了催化涂层的形貌、晶粒尺寸以及电极的析氧电位。XPS、EPR和羟基自由基（·OH）生成测试表明，涂层表面致密且粒径较小有利于电极表面获得更多的氧空位，且氧空位浓度越高，吸附氧物种越多，从而增强了活性自由基的形成以及对有机物的降解。以长度950 nm，孔径100 nm 的TNTs 阵列层为基底时，所制备的电极TNTs (25 V) / SnO₂-Sb展现出了最佳的苯酚处理效果（92±4.6%，2h）。
- TNTs 结构 /
- SnO₂-Sb 电极 /
- 溶剂热 /
- 氧空位 /
- 电催化氧化
Abstract: The TiO₂ nanotubes arrays/SnO₂-Sb (TNTs/SnO₂-Sb) electrode is successfully fabricated using the solvothermal synthesis technique. Various architectures of TNTs are constructed by varying the anodization voltage and time, aiming to investigate their impact on the structural and electrochemical properties of the SnO₂-Sb electrode. The anodization voltage is identified as the primary influencing factor on the morphology and surface hydrophilia of TNTs arrays, which is evidenced by scanning electron microscopy (SEM) and contact angle testing. In contrast, the effect of anodization time is relatively small. SEM, X-ray diffraction (XRD), linear sweep voltammograms (LSV), and electrochemical impedance spectroscopy (EIS) results indicat that the morphology and crystal size of the catalytic coating, as well as the oxygen evolution potential of the electrode, are influenced by the pore size of TNTs arrays. The influencing mechanism of enhanced electrochemical activity by adjusting the architecture of TNTs arrays is investigated using X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and Hydroxyl radicals (·OH) generation test. The results reveal a higher concentration of oxygen vacancies on the sample with a compact and smaller particle coating, indicating the presence of more adsorbed oxygen species. Consequently, this enhancs the generation capacity of active radicals for organic matter degradation. The electrode featuring TNTs arrays with a length of 950 nm and a pore diameter of 100 nm exhibits the most effective remediation of phenol-containing wastewater, achieving approximately 92 ± 4.6% removal after a duration of 2 h.
- TNTs architecture /
- Sb-doped SnO₂ electrode /
- solvothermal synthesis method /
- oxygen vacancy /
- electrocatalytic oxidation

HTML全文

Figure 1 TNTs substrate architectures under different preparation conditions: (a) 15V-1h (b) 15V-2h (c) 15V-3h (d) 20V-1h (e) 20V-2h (f) 20V-3h (g) 25V-1h (h) 25V-2h (i) 25V-3h (j) 30V-1h (k) 30V-2h (l) 30V-3h

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Figure 2 Contact angle of (a) Ti, (b) TNTs (15 V-2 h), (c) TNTs (20 V-2 h), (d) TNTs (25 V-2 h), (e) TNTs (30 V-2 h), (f) TNTs (25 V-1 h) and (g) TNTs (25 V-3 h)

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Figure 3 SEM images of (a) Ti/SnO₂-Sb, (b) TNTs (15 V)/SnO₂-Sb, (c) TNTs (20 V)/SnO₂-Sb, (d) TNTs (25 V)/SnO₂-Sb electrode, (e) TNTs (30 V)/SnO₂-Sb electrode

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Figure 4 XRD patterns of (a) TNTs (25 V) substrate and (b) TNTs/SnO₂-Sb electrodes with different substrate preparation voltages

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Figure 5 OEP of TNTs/SnO₂-Sb electrodes with different substrate preparation voltages

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Figure 6 EIS spectrums of TNTs/SnO₂-Sb electrodes with different substrate preparation voltages

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Figure 7 Electrochemical degradation of phenol on TNTs/SnO₂-Sb electrodes with TNTs substrates under different preparation conditions (a) Variations of concentration of phenol with electrolysis time (b) The first-order kinetics curves of phenol degradation.

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Figure 8 XPS pattern of Sn3d of SnO₂-Sb different electrodes

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Figure 9 XPS pattern of the fitted curves of O1s and Sb3d of electrodes prepared by different voltages

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Figure 10 EPR spectrums of TNTs/SnO₂-Sb electrodes with different substrate preparation voltages

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Figure 11 The hydroxyl radicals generation ability on the SnO₂-Sb electrode with different substrate preparation voltages

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Figure 12 The quenching experiment of the active radicals on the SnO₂-Sb electrodes with different substrate preparation voltages

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Table 1 Effect of preparation conditions for TNTs arrays on the average crystal size of SnO₂-Sb calculated by Scherrer Formula

Sample	Crystallite size (nm)
Ti/SnO₂-Sb	23±0.3
TNTs (15 V)/SnO₂-Sb	20±0.3
TNTs (20 V)/SnO₂-Sb	17±0.4
TNTs (25 V)/SnO₂-Sb	15±0.3
TNTs (30 V)/SnO₂-Sb	13±0.4
*Scherrer Formula: D=Kλ/(βcosθ), where D is the crystallite size, K is the Scherrer constant (0.89), λ is the wavelength of incident ray, β is the full width at half maximum of the peak, and θ is the position of plane peak^[30].

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Table 2 EIS fitting results of TNTs/SnO₂-Sb electrodes with different substrate preparation voltages

Sample	R_s (Ω)	C_h (F)	R_h (Ω)	C_t (F)	R_t (Ω)
Ti/SnO₂-Sb	4.72	5.33 E-8	49.3	2.02 E-5	49
TNTs (15 V)/SnO₂-Sb	4.71	5.62 E-8	47.6	2.06 E-5	48
TNTs (20 V)/SnO₂-Sb	4.69	5.84 E-8	46.9	2.11 E-5	47
TNTs (25 V)/SnO₂-Sb	4.67	6.33 E-8	44.3	2.20 E-5	45
TNTs (30 V)/SnO₂-Sb	4.74	6.12 E-8	45.4	2.16 E-5	46

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Table 3 Effect of preparation voltage of TNTs arrays on the contact angle of substrate surface and loading amount of SnO₂-Sb

Sample	contact angle (°)	Loading amount (mg·cm⁻²)
Ti	52	2.05±0.05
TNTs (15 V-2 h)	43	2.15±0.04
TNTs (20 V-2 h)	34	2.24±0.04
TNTs (25 V-2 h)	13	2.36±0.03
TNTs (30 V-2 h)	10	2.42±0.02

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Table 4 XPS analysis of TNTs/SnO₂-Sb electrodes with different substrate preparation voltages

Sample	Binding energy/eV				O_ads (at% = $ \dfrac{\rm{O}\mathrm{a}\mathrm{d}\mathrm{s}}{\mathrm{S}\mathrm{n} + \mathrm{S}\mathrm{b} + \mathrm{O}\mathrm{a}\mathrm{d}\mathrm{s} + \mathrm{O}\mathrm{l}\mathrm{a}\mathrm{t}} $ × 100% )	Atom ratio of O_lat/(Sn + Sb)
Sample	Sn3d_5/2	Sb3d_5/2	O_ads	O_lat		Atom ratio of O_lat/(Sn + Sb)
control	486.91	530.89	532.03	530.73	14.6	2.65
15V	486.84	530.90	531.98	530.69	17.9	2.41
20V	486.46	531.19	531.96	530.64	19.8	2.18
25V	486.21	531.12	531.89	530.55	25.6	1.88
30V	486.35	530.94	531.91	530.59	23.2	1.97

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Table 5 The computed result from the quenching experiment

Samples	The contribution to phenol degradation (%)
Samples	·O₂⁻	·OH
control	42.1	74
15V	45.7	76.3
20V	47	79
25V	50.5	84
30V	48.6	81

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