D0I:10.13374/1.issnl00103.2008.05.007 第30卷第5期 北京科技大学学报 Vol.30 No.5 2008年5月 Journal of University of Science and Technology Beijing May 2008 可见光响应氮掺杂TO2光催化剂的水热法制备与性能 王宜超刘中清燕青芝李振华葛昌纯 北京科技大学特种陶瓷粉末治金研究室，北京100083 摘要以工业TO0:为原料，尿素为沉淀剂，采用水热均匀沉淀及其后续的掺氮热处理方法制备了氨掺杂的纳米TO2粉 体.分别采用XRD、XPS、BET,UV-Vis DRS,FTHR,TEM等方法对所制备的粉体进行了表征.以电子节能灯为光源，亚甲基 蓝溶液为目标污染物研究了所制备产物的光催化活性.结果表明，水热粉体产物在900℃以下均为纯锐钛矿相，1000℃时几 乎全部转变为金红石相：由XRD计算得出的颗粒尺寸与TEM的分析结果基本一致：以尿素为氮源，热处理水热粉体的XPS 分析表明，N1s峰在399eV处，红外光谱进一步确认是氮取代了二氧化钛中少量晶格氧，形成TiO2-xN,(y≥x):UV一Vis DRS分析显示，热处理并加入活性氮源对于吸收边的红移及降低光生电子的复合几率是必要的：水热粉体在热处理前BET 为266.490m2g1,热处理掺氨后为144.908m2g1:光催化实验结果显示热处理掺氮粉体表现出较高的可见光光催化活性. 关键词光催化剂：二氧化钛；水热均匀沉淀；氮掺杂：硫酸氧钛：光催化 分类号0614.41+1 Preparation and properties of visible light responding N doped TiOz nanopowder by hydrothermal synthesis WANG Yichao,LIU Zhongqing.YAN Qingzhi,LI Zhenhua,GE Changchun Laboratory of Special Ceramics and Powder Metallurgy.University of Science and Technology Beijing.Beijing 100083.China ABSTRACT By using technical grade TiOsO4 as the precursor and urea as the precipitating agent,N-doped TiOz nanopowders were prepared by hydrothermal homogeneous precipitation and heat treatment.The properties of the prepared powders were characterized by XRD.XPS,BET,UV-Vis absorbance spectra.FTIR.and BET methods.By using an electronic energy"saving lamp as the light source.taking methylene blue as the model pollutant,their photo catalytic activities under visible-light irradiation were also investi- gated.The result showed that the products after 900C heat treatment were all anatase.When the temperature came to 1000C.al- most all of them were converted into rutile.Taking urea as the nitrogen source.XPS analyses of particles prepared by hydrothermal powders after heat treatment indicated that the NIs peak was dlose to 399eV.Furthermore.N replacing a small amount of lattice oxygen to form TiO2-N,(yx)was further demonstrated by FTIR.UV-Vis absorbance spectra showed that adding the nitrogen source during heat treatment was necessary to the red-shifted in the absorption band-edge and the binding ratio of photo"generated electrons.The particle size calculated by XRD accorded with the result analyzed by TEM.All results show that nitrogen-doped TiO2 after heat treatment had a higher photo catalytic activity in visible light. KEY WORDS photocatalyst:titania:hydrothermal homogeneous precipitation:N-doped:TiOSO:photo catalysis 从Fujishima和Honda发表利用Ti02光解水的到总能量的近46%.为此，许多科研工作学者利用 实验结果以来山，依据光激发半导体产生原初电荷 各种办法对二氧化钛进行掺杂，以达到其在可见光 分离原理分解和矿化有机污染物得到了广泛的关注 区实现光催化的目的， 和研究2)].但是二氧化钛光催化剂的吸收仅限于紫 早在1986年Sato3]就发现氮的引入可使Ti02 外光区，太阳光谱中紫外光能(400nm以下)的含量 具有可见光活性.2001年Asahi等报道氮掺杂改 仅仅占不到5%，波长在400~700nm的可见光则占 性二氧化钛，在保持其在紫外光区光催化活性的同 收稿日期：2007-01-29修回日期：2007-03-05 时，在可见光区的光催化活性显著提高·迄今为止， 作者简介：王宜超(1981一)，男，硕士研究生：葛昌纯(1934一)男， 已发展了多种制备氮掺杂二氧化钛的方法，如Yin 教授，中国科学院院士，E-mail:cge@mater.usth-cd山cm 等以P一25和C6H12N4为原料，经高能球磨机作可见光响应氮掺杂 TiO2光催化剂的水热法制备与性能 王宜超 刘中清 燕青芝 李振华 葛昌纯 北京科技大学特种陶瓷粉末冶金研究室‚北京100083 摘 要 以工业 TiOSO4 为原料‚尿素为沉淀剂‚采用水热均匀沉淀及其后续的掺氮热处理方法制备了氮掺杂的纳米 TiO2 粉 体．分别采用 XRD、XPS、BET、UV－Vis DRS、FT－IR、T EM 等方法对所制备的粉体进行了表征．以电子节能灯为光源、亚甲基 蓝溶液为目标污染物研究了所制备产物的光催化活性．结果表明‚水热粉体产物在900℃以下均为纯锐钛矿相‚1000℃时几 乎全部转变为金红石相；由 XRD 计算得出的颗粒尺寸与 T EM 的分析结果基本一致；以尿素为氮源‚热处理水热粉体的 XPS 分析表明‚N 1s 峰在399eV 处‚红外光谱进一步确认是氮取代了二氧化钛中少量晶格氧‚形成 TiO2－ xNy（ y≥ x）；UV－Vis DRS 分析显示‚热处理并加入活性氮源对于吸收边的红移及降低光生电子的复合几率是必要的；水热粉体在热处理前 BET 为266∙490m 2·g －1‚热处理掺氮后为144∙908m 2·g －1；光催化实验结果显示热处理掺氮粉体表现出较高的可见光光催化活性． 关键词 光催化剂；二氧化钛；水热均匀沉淀；氮掺杂；硫酸氧钛；光催化 分类号 O614∙41＋1 Preparation and properties of visible light responding N－doped TiO2 nanopowder by hydrothermal synthesis W A NG Y ichao‚LIU Zhongqing‚Y A N Qingz hi‚LI Zhenhua‚GE Changchun Laboratory of Special Ceramics and Powder Metallurgy‚University of Science and Technology Beijing‚Beijing100083‚China ABSTRACT By using technical grade TiOSO4as the precursor and urea as the precipitating agent‚N-doped TiO2nanopowders were prepared by hydrothermal homogeneous precipitation and heat treatment．T he properties of the prepared powders were characterized by XRD‚XPS‚BET‚UV-Vis absorbance spectra‚FTIR‚and BET methods．By using an electronic energy-saving lamp as the light source‚taking methylene blue as the model pollutant‚their photo catalytic activities under visible-light irradiation were also investi￾gated．T he result showed that the products after900℃ heat treatment were all anatase．When the temperature came to1000℃‚al￾most all of them were converted into rutile．Taking urea as the nitrogen source‚XPS analyses of particles prepared by hydrothermal powders after heat treatment indicated that the N1s peak was close to 399eV．Furthermore‚N replacing a small amount of lattice oxygen to form TiO2－ xNy（ y≥ x） was further demonstrated by FTIR．UV-Vis absorbance spectra showed that adding the nitrogen source during heat treatment was necessary to the red-shifted in the absorption band-edge and the binding ratio of photo-generated electrons．T he particle size calculated by XRD accorded with the result analyzed by T EM．All results show that nitrogen-doped TiO2 after heat treatment had a higher photo catalytic activity in visible light． KEY WORDS photocatalyst；titania；hydrothermal homogeneous precipitation；N-doped；TiOSO4；photo catalysis 收稿日期：2007-01-29 修回日期：2007-03-05 作者简介：王宜超（1981－）‚男‚硕士研究生；葛昌纯（1934－）‚男‚ 教授‚中国科学院院士‚E-mail：ccge＠mater．ustb．edu．cn 从Fujishima 和 Honda 发表利用 TiO2 光解水的 实验结果以来［1］‚依据光激发半导体产生原初电荷 分离原理分解和矿化有机污染物得到了广泛的关注 和研究［2］．但是二氧化钛光催化剂的吸收仅限于紫 外光区‚太阳光谱中紫外光能（400nm 以下）的含量 仅仅占不到5％‚波长在400～700nm的可见光则占 到总能量的近46％．为此‚许多科研工作学者利用 各种办法对二氧化钛进行掺杂‚以达到其在可见光 区实现光催化的目的． 早在1986年 Sato ［3］就发现氮的引入可使 TiO2 具有可见光活性．2001年 Asahi 等［4］报道氮掺杂改 性二氧化钛‚在保持其在紫外光区光催化活性的同 时‚在可见光区的光催化活性显著提高．迄今为止‚ 已发展了多种制备氮掺杂二氧化钛的方法．如 Yin 等［5］以 P－25和 C6H12N4 为原料‚经高能球磨机作 第30卷 第5期 2008年 5月 北 京 科 技 大 学 学 报 Journal of University of Science and Technology Beijing Vol．30No．5 May2008 DOI:10．13374／j．issn1001－053x．2008．05．007