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

参考文献 29

[1]	AURIAN-BLAJENI B, HALMANN M, MANASSEN J,et al. Photoreduction of carbon dioxide and water into formaldehyde and methanol on semiconductor materials.Solar Energy, 1980, 25(2): 165-170.
[2]	MATSUMOTO Y, OBATA M, HOMBO J,et al. Photocatalytic reduction of carbon dioxide on p-type CaFe2O4 powder.Journal of Physical Chemistry, 1994, 98(11): 2950-2951.
[3]	HUSSAIN S T, KHAN K, HUSSAIN R,et al. Size control synthesis of sulfur doped titanium dioxide (anatase) nanoparticles, its optical property and its photo catalytic reactivity for CO2+H2O conversion and phenol degradation.Journal of Energy Chenistry, 2009, 18(4): 383-391.
[4]	TSAI C W, CHEN H M, LIU R S,et al. Ni@NiO core-shell structure-modified nitrogen-doped in TaO4 for solar-driven highly efficient CO2 reduction to methanol.J. Phys. Chem. C, 2011, 115(20): 10180-10186.
[5]	GUAN G, KIDA T, HARADA T,et al. Photoreduction of carbon dioxide with water over K2Ti6O13 photocatalyst combined with Cu/ZnO catalyst under concentrated sunlight.Applied Catalysis A General, 2003, 249(1): 11-18.
[6]	SLAMET H W, NASUTION E, PURNAMA K,et al. Effect of copper species in a photocatalytic synthesis of methanol from carbon dioxide over copper-doped titania catalysts.World Applied Sciences Journal, 2009, 6(1): 112-122.
[7]	SLAMET, NASUTION H W, PURNAMA E,et al. Photocatalytic reduction of CO2 on copper-doped titania catalysts prepared by improved-impregnation method.Catalysis Communications, 2005, 6(5): 313-319.
[8]	ZHANG ZONG-WEI, FAN JUN.Effects of the photocatalytic activity of nano TiO2 doped with Tb. Petrochemical Technology. 2007, 36(9): 956-960.
[9]	YANG M C, YANG T S, WONG M S,et al.Nitrogen-doped titanium oxide films as visible light photocatalyst by vapor deposition. Thin Solid Films., 2004, 469-470: 1-5.
[10]	NONAMI T, HASE H, FUNAKOSHIK,et al. Apatite-coated titanium dioxide photocatalyst for air purification.Catal. Today, 2004, 96(3): 113-118.
[11]	KESHMIRI M, MOHSENI M, TROCZYNSKI T,et al. Development of novel TiO2, Sol-Gel-derived composite and its photocatalytic activities for trichloroethylene oxidation.Applied Catalysis B Environmental, 2004, 53(4): 209-219.
[12]	WANG YAN, YANG JIAN JUN.Study on the Origin of Nitrogen- doped TiO2 Visible Light Activity. National Conference on Solar Photochemistry and Photocatlysis. 2010.
[13]	ZHAO Z, FAN J, XIE M,et al.Photo-catalytic reduction of carbon dioxide with in-situ synthesized CoPc/TiO2 under visible light irradiation. Journal of Cleaner Production, 2009, 17(11): 1025-1029.
[14]	GAO S, GU B, JIAO X,et al. Highly efficient and exceptionally durable CO2 photoreduction to methanol over freestanding defective single-unit-cell bismuth vanadate layers. Journal of the American Chemical Society, 2017, 139(9): 3438-3445.
[15]	FORMO E, LEE E, CAMPBELL D,et al. Functionalization of electrospun TiO2 nanofibers with Pt nanoparticles and nanowires for catalytic applications.Nano Letters, 2008, 8(2): 668-672.
[16]	CHENG Y, HUANG W, ZHANG Y,et al. Preparation of TiO2 hollow nanofibers by electrospining combined with Sol-Gel process. Crystengcomm, 2010, 12(7): 2256-2260.
[17]	CAO T, LI Y, WANG C,et al. A facil. in situ hydrothermal method to SrTiO3/TiO2 nanofiber heterostructures with high photocatalytic activity. Langmuir, 2011, 27(6): 2946-2952.
[18]	LI X, LIU H, LUO D,et al. Adsorption of CO2 on heterostructure CdS(Bi2S3)/TiO2, nanotube photocatalysts and their photocatalytic activities in the reduction of CO2 to methanol under visible light irradiation.Chemical Engineering Journal, 2012, 180(6): 151-158.
[19]	HAMIDAH, ABDULLAH, MAKSUDUR,et al. CeO2-TiO2 as a visible light active catalyst for the photoreduction of CO2 to methanol.Journal of Rare Earths, 2015, 33(11): 1155-1161.
[20]	LI H, ZHU L, MA C,et al. TiO2, hollow microspheres: synthesis, photocatalytic activity, and selectivity for a mixture of organic dyes.Monatshefte für Chemie-Chemical Monthly, 2014, 145(1): 29-37.
[21]	徐伟. N-TiO2光催化剂的制备及其中孔炭负载研究. 上海: 华东理工大学硕士学位论文, 2013.
[22]	MOHAMED M A,SALLEH W N W, JAAFAR J,et al. Structural characterization of N-doped anatase-rutile mixed phase TiO2, nanorods assembled microspheres synthesized by simple Sol-Gel method.Journal of Sol-Gel Science and Technology, 2015, 74(2): 513-520.
[23]	SAYED F N, JAYAKUMAR O D, SASIKALA R,et al. Photochemical hydrogen generation using nitrogen-doped TiO2-Pd nanoparticles: facile synthesis and effect of Ti3+ incorporation.Journal of Physical Chemistry C, 2012, 116(23): 12462-12467.
[24]	YANG X, CAO C, ERICKSON L,et al. Synthesis of visible- light-active TiO2 based photocatalysts by carbon and nitrogen doping. Journal of Catalysis, 2008, 260(1): 128-133.
[25]	王岩. 可见光活性二氧化钛的制备及氧空位与掺杂的N(或修饰的金属)之间的协同作用机制研究. 郑州: 河南大学博士学位论文, 2012.
[26]	秦好丽. 氮掺杂二氧化钛的制备及可见光下对有机物的降解研究. 广州: 华南理工大学博士学位论文, 2006.
[27]	VALENTIN C D, FINAZZI E, PACCHIONI G,et al. N-doped TiO2: theory and experiment.Chemical Physics, 2007, 339(1/2/3): 44-56.
[28]	CAO YU-HUI, YAN YU-FEI, ZHANG JIAN,et al. Infrared assisted microwave preparation. of grahitephase carbon nitride and photo catalytic nitrogen firation performace.Chemical Journal of Chinese Universities, 2016, 37(7): 1357-1363.
[29]	WU X, ZHAO J, WANG L,et al. Carbon dots as solid-state electron mediator for BiVO4/CDs/CdS Z-scheme photocatalyst working under visible light. Applied Catalysis B Environmental, 2017, 206: 501-509.

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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