N掺杂TiO2纳米纤维高可见光催化CO2合成甲醇

doi:10.15541/jim20170540

摘要/Abstract

摘要：

采用气相生长法在介孔SiO₂球的表面上制备了ϕ 8~10 nm的TiO₂纳米纤维, 采用相同的方法, 还成功地制备了氮掺杂的TiO₂(N-TiO₂) 纳米纤维, 它具有更高的可见光催化活性。采用X射线光电子能谱(XPS)、紫外光电子能谱(UPS)、X射线衍射(XRD)、扫描电镜(SEM)、透射电子显微镜(TEM)、紫外–可见分光光度计(UV-Vis)、荧光分光光度计(PL)等对样品进行了测试分析。TiO₂纳米纤维具有高结晶度的锐钛矿晶型, 掺氮后的TiO₂纳米纤维带隙变窄, 在可见光波段有明显的吸收, 同时, 光生电子还原能力更强, 大大提高了可见光下催化还原CO₂合成甲醇的产率。在300 W氙灯光照2 h后, 用纯TiO₂纤维催化CO₂合成甲醇, 产率为493.4 μmol•g^-1∙h^-1, 转换频率(TOF) 为0.089 h^-1; 以N-TiO₂为催化剂合成甲醇产率提高了40.1%, 达695.1 μmol∙g^-1∙h^-1, 转换频率(TOF) 提高了40.4%, 为0.125 h^-1。

关键词: CO₂, 可见光, 甲醇, TiO₂纳米纤维

Abstract:

TiO₂ nanofibers with a diameter size of 8-10 nm were prepared on the surface of the mesoporous SiO₂ spheres through a vapor-phase growth method. And nitrogen doped TiO₂ (N-TiO₂) nanofibers were also successfully fabricated in the same way. The N atoms replaced the oxygen sites in the lattices of TiO₂. The N-TiO₂nanofibers exhibited a highly catalytic activity under visible irradiation. XPS, UPS, XRD, SEM, TEM, UV-Vis, and PL were used to analyze and characterize the nanofibers. The annealed nanofibers were composed of highly crystalline anatase phase. Nitrogen doping narrowed band gap of the TiO₂ nanofibers and enhanced absorption of the visible light. Meanwhile, photo-generated electrons over the N-TiO₂ nanofibers exhibited more reductive potential than those over the TiO₂ nanofibers. Thus, methanol yield was remarkably improved in CO₂ photocatalytic reduction. Upon irradiation of 300 W Xe lamp for 2 h, methanol yield was 493.4 μmol∙g^-1∙h^-1 over the N-doped TiO₂ nanofibers, and the corresponding turnover frequency (TOF) was 0.089 h^-1. Comparatively, methanol yield reached 695.1 μmol∙g^-1∙h^-1 for N-TiO₂ with a TOF of 0.125 h^-1, which enhanced by 40.1% and 40.4%, respectioely.

Key words: CO₂, visible light, methanol, TiO₂ nanofiber

中图分类号:

TQ174

柯银环, 曾敏, 姜宏, 熊春荣. N掺杂TiO₂纳米纤维高可见光催化CO₂合成甲醇[J]. 无机材料学报, 2018, 33(8): 839-844.

KE Yin-Huan, ZENG Min, JIANG Hong, XIONG Chun-Rong. Photocatalytic Reduction of Carbon Dioxide to Methanol over N-doped TiO₂ Nanofibers under Visible Irradiation[J]. Journal of Inorganic Materials, 2018, 33(8): 839-844.

图/表 12

图1 TiO2 纳米纤维的生长示意图

Fig. 1 Formation process of TiO2 nanofibers

图2 介孔SiO2球的SEM照片

Fig. 2 SEM image of mesoporous silica spheres

图3 TiO2 和N-TiO2纳米纤维的SEM和TEM照片

Fig. 3 SEM and TEM images of the nanofibers(a, b) TiO2; (c, d) N-TiO2

图4 TiO2和N-TiO2纳米纤维450℃焙烧8 h后的XRD图谱

Fig. 4 XRD patterns of TiO2 and N-TiO2 nanofibers annealed at 450℃for 8 h

表1 TiO2和N-TiO2纳米纤维晶胞参数

Table 1 Crystal cell parameters of TiO2 and N-TiO2 nanofibers

Cell parameters	TiO₂	N-TiO₂
a	3.7820	3.7851
c	9.5021	9.5140

图5 (a)Ti2p和(b)N1s的X射线光电子能谱图

Fig. 5 High-resolution XPS spectra of (a) Ti2p and (b) N1s

图6 催化剂样品的紫外-可见漫反射光谱

Fig. 6 UV-Vis diffuse reflection spectra of the samples

图7 TiO2和N-TiO2纳米纤维紫外禁带宽度

Fig. 7 Optical absorption edges of TiO2 and N-TiO2 nanofibers

图8 催化剂样品的荧光图谱

Fig. 8 Photoluminescence spectra of TiO2 and N-TiO2

图9 样品的光催化CO2合成甲醇催化活性

Fig. 9 Photocatalytic performances over the samples

图10 样品的紫外光电子能谱图

Fig. 10 Ultraviolet photoelectron spectra of the photocatalysts

图11 催化剂的能带结构图

Fig. 11 Band structure diagram of the photocatalysts

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N掺杂TiO₂纳米纤维高可见光催化CO₂合成甲醇

Photocatalytic Reduction of Carbon Dioxide to Methanol over N-doped TiO₂ Nanofibers under Visible Irradiation

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