CHINESE JOURNAL OF CATALYSIS

http://www.chxb.cn ISSN 0253-9837 CN 21-1195/O6 CODEN THHPD3

催化学报 CHINESE JOURNAL OF CATALYSIS

CHINESE JOURNAL OF CATALYSIS 主编

2012

林励吾

Editor-in-Chief

Vol. 33 No. 10

LIN Liwu

OH

H OH

October 2012

O

O

O

Vol. 33 No. 10

- eo - Hydroquinone

o - Semiquinone

pages 1611-1742

OH

OH

+ e-

e- e-

+ o - Quinone

HO

O

H2O2

中国化学会催化学会会刊

Transaction of the Catalysis Society of China

2012 年第 33 卷第 10 期

CHINESE JOURNAL OF CATALYSIS

2012 Vol. 33 No. 10

In This Issue

封面: 胡常伟等将活性炭催化剂用于过氧化氢氧化苯一步羟基化反应, 研究了活性炭表面含氧基团在反应中的作用, 发现表面酚羟基和羰基是羟基化反应的活性位. 见本期第 1622~1630 页. Cover: Hu and co-workers investigated the functions of the surface oxygen groups on an activated carbon catalyst in the hydroxylation of benzene. Adsorbed phenolic hydroxyl and quinone were proposed as the active sites for the hydroxylation. See the article on pages 1622–1630.

About the Journal Chinese Journal of Catalysis is published monthly by Chinese Chemical Society and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. The objective of the journal is to publish original, rigorous, and scholarly contributions in the fields of heterogeneous and homogeneous catalysis. The journal accepts papers in Chinese and English. Scope of the Journal

Impact Factor

 New trends in heterogeneous and homogeneous catalysis in relation to energy, environment, new materials, petroleum chemicals, and fine chemicals  Scientific bases for the preparation and activation of catalysts of commercial interest or that are representative models  Scientific methods for the characterization of heterogeneous catalysts, especially methods for in situ characterization  New heterogeneous and homogeneous catalytic reactions of potential practical interest in environment, energy, and fine chemicals applications  Relationship between homogeneous and heterogeneous catalysis  Theoretical studies on the structure and reactivity of catalysts  The journal also accepts contributions dealing with other issues related to catalysis, such as photo-catalysis, bio-catalysis, surface science, and chemical kinetics.

2011 SCI Impact Factor: 1.171 2011 SCI 5-Year Impact Factor: 0.945 2010 ISTIC Impact Factor: 0.777

Types of Contributions Reviews are surveys of recent progress on important topics of catalysis, with entire, systematic, and important information. Authors should have published articles in the field. More than 60 references are suggested. Communications rapidly report studies with significant innovation and major academic value. They are limited to four Journal pages. After publication, their full-text papers can also be submitted to this or other journals. Articles are original full-text reports on innovative, systematic, and complete results in catalysis.

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2012年第33卷第10期

月刊 SCI 收录 1980 年 3 月创刊中国化学会催化学会会刊 2012年10月20日出版

2012 Vol. 33 No. 10

CHINESE JOURNAL OF CATALYSIS 《催化学报》第四届编辑委员会

The Fourth Editorial Board of Chinese Journal of Catalysis 顾问 (Advisors)

主管主办

中国科学院中国化学会中国科学院大连化学物理研究所主编林励吾编辑《催化学报》编辑委员会出版

蔡启瑞 (CAI Qirui) 闵恩泽 (MIN Enze) 彭少逸 (PENG Shaoyi) 宋春山 (SONG Chunshan, 美国)

辛勤 (XIN Qin) 胥诲熊 (XU Huixiong) Jürgen CARO (德国) Michel CHE (法国)

Bernard DELMON (比利时) Gerhard ERTL (德国) Masaru ICHIKAWA (日本)

主编 (Editor-in-Chief) 林励吾 (LIN Liwu)

国内统一连续出版物号 CN 21-1195/O6 国际标准连续出版物号 ISSN 0253-9837 CODEN THHPD3 广告经营许可证号 2011004

副主编 (Associate Editors-in-Chief) 包信和 (BAO Xinhe) 高滋 (GAO Zi)

寇元 (KOU Yuan) 刘宇新 (LIU Yuxin)

张

涛 (ZHANG Tao)

李灿 (LI Can) 李大东 (LI Dadong) 李微雪 (LI Weixue) 林励吾 (LIN Liwu) 刘昌俊 (LIU Changjun) 刘宇新 (LIU Yuxin) 刘中民 (LIU Zhongmin) 卢冠忠 (LU Guanzhong) 罗锡辉 (LUO Xihui) 沈俭一 (SHEN Jianyi) 沈师孔 (SHEN Shikong) 沈之荃 (SHEN Zhiquan) 申文杰 (SHEN Wenjie) 苏宝连 (SU Baolian, 比利时) 孙予罕 (SUN Yuhan) 万惠霖 (WAN Huilin) 王德峥 (WANG Dezheng) 王国祯 (WANG Guozhen) 王建国 (WANG Jianguo) 王祥生 (WANG Xiangsheng)

吴凯 (WU Kai) 吴通好 (WU Tonghao) 夏春谷 (XIA Chungu) 肖丰收 (XIAO Fengshou) 谢在库 (XIE Zaiku) 熊国兴 (XIONG Guoxing) 徐柏庆 (XU Boqing) 许建和 (XU Jianhe) 徐杰 (XU Jie) 徐龙伢 (XU Longya) 严玉山 (YAN Yushan, 美国) 杨启华 (YANG Qihua) 杨维慎 (YANG Weishen) 杨向光 (YANG Xiangguang) 余林 (YU Lin) 袁友珠 (YUAN Youzhu) 张涛 (ZHANG Tao) 赵进才 (ZHAO Jincai) 郑小明 (ZHENG Xiaoming) 钟顺和 (ZHONG Shunhe)

编委 (Members) 总发行北京东黄城根北街 16 号邮编: 100717 电话: (010) 64017032 E-mail: [email protected] 国内订购全国各地邮政局邮发代号 8-93 国外订购中国国际图书贸易总公司北京 399 信箱邮编 100044 国外发行代号 M417 印刷大连海大印刷有限公司定价 36 元

Publication Monthly (12 issues) Started in March 1980 Transaction of the Catalysis Society of China Superintended by Chinese Academy of Sciences Sponsored by Chinese Chemical Society and Dalian Institute of Chemical Physics of CAS Editor-in-Chief LIN Liwu Edited by Editorial Board of Chinese Journal of Catalysis Published by Science Press

Distributed by Science Press 16 Donghuangchenggen North Street, Beijing 100717, China Tel: +86-10-64017032 E-mail: [email protected] Subscription Agents Domestic All Local Post Offices in China Foreign China International Book Trading Corporation, P.O.Box 399, Beijing 100044, China Printed by Dalian Haida Printing Company, Limited Price $36

公开发行

安立敦 (AN Lidun) 包信和 (BAO Xinhe) 陈德 (CHEN De, 挪威) 陈经广 (CHEN Jingguang,美国) 陈庆龄 (CHEN Qingling) 陈诵英 (CHEN Songying) 陈耀强 (CHEN Yaoqiang) 陈懿 (CHEN Yi) 椿范立 (Noritatsu TSUBAKI, 日本) 邓友全 (DENG Youquan) 方佑龄 (FANG Youling) 伏义路 (FU Yilu) 高滋 (GAO Zi) 关乃佳 (GUAN Naijia) 郭新闻 (GUO Xinwen) 何鸣元 (HE Mingyuan) 贺鹤勇 (HE Heyong) 胡友良 (HU Youliang) 贾继飞 (JIA Jifei, 美国) 寇元 (KOU Yuan)

编辑部成员 (Editorial Office Staff) 主任 (Managing Editor) 资深编辑 (Senior Editor) 编辑 (Editor) 编辑 (Editor)

尹红梅 (YIN Hongmei) 刘宇新 (LIU Yuxin) 初人合 (CHU Renhe) 张艳 (ZHANG Yan)

编辑部联系方式 (Editorial Office Address) 地址: 大连市中山路 457 号中国科学院大连化学物理研究所邮编: 116023 电话: (0411)84379240 传真: (0411)84379600 电子信箱: [email protected] 中文版 http://www.chxb.cn

Add.: Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, Liaoning, China Tel: +86-411-84379240 Fax: +86-411-84379600 E-mail: [email protected]

国际版 http://www.sciencedirect.com/science/journal/18722067

(CUIHUA XUEBAO) Supported by the Science Publication Foundation of the CAS

CHINESE JOURNAL OF CATALYSIS Monthly

Vol. 33 No. 10

October 2012

Contents Review Chin. J. Catal., 2012, 33: 1611–1621

doi: 10.1016/S1872-2067(11)60440-3

Ceramics in Environmental Catalysis: Applications and Possibilities

CO2

Soot (C) CO2

CO

Nitin LABHSETWAR*, P. DOGGALI, S. RAYALU, R. YADAV, T. MITSUHASHI, H. HANEDA National Environmental Engineering Research Institute (CSIR-NEERI), India; National Institute for Materials Science (NIMS), Japan

Soot Soot Oxidation Oxidation Honeycomb Honeycombsupported supported perovskites perovskites

CO COOxidation Oxidation Ceramic Ceramicsupported supported mixed mixedoxides oxides Ceramics Ceramicsfor for chemical chemicallooping looping combustion combustion

The article deals with various environmental applications of ceramic based materials and structures. Synthesis, characterization, and catalytic properties of various ceramic materials including catalyst supports are discussed.

Ceramics in environmental catalysis

N2O

N2+O2

NN2OODecomposition Decomposition 2 Zeolite Zeolitebased based honeycomb honeycomb supported supportedcatalysts catalysts

Metal Oxide (MeO) Metal (M) + O2

CO CO22Sequestration Sequestrationto tocarbonates carbonates (Carbonic (Carbonicanhydrase) anhydrase)

H+ + HCO-3

CO2 + H2O

Articles Chin. J. Catal., 2012, 33: 1622–1630

doi: 10.1016/S1872-2067(11)60444-0

Hydroxylation of Benzene by Activated Carbon Catalyst XU Jiaquan, LIU Huihui, YANG Ruiguang, LI Guiying*, HU Changwei* Sichuan University H OH

OH

Activated carbon (AC)

O

O

O

O

HO -

OH

+e e o-Semiquinone on AC o-Hydroquinone on AC

-

-

o-Quinone on AC

- -

-

+e e

OH

H2O2

The reaction between phenolic hydroxyl and quinone on the surface of activated carbon activated H2O2 to form a OH radical, which then reacts with benzene to form phenol.

Chin. J. Catal., 2012, 33: 1631–1635

doi: 10.1016/S1872-2067(11)60416-6

Temperature-Programmed Surface Reaction Study of Adsorption and Reaction of H2S on Ceria LIU Bing, XU Hengyong*, ZHANG Zehui* South-Central University for Nationalities; Dalian Institute of Chemical Physics, Chinese Academy of Sciences

H 2O

S

H 2S SO2



O

O

O

SO42-

CeO2 Some adsorbed H2S desorbed below 673 K, sulfur and water were formed below 473 K, SO2 was formed from 473 to 673 K, and sulfate was formed above 673 K when H2S was adsorbed on ceria.

Chin. J. Catal., 2012, 33: 1636–1641

doi: 10.1016/S1872-2067(11)60414-2

Yb(OTf)3-Catalyzed Addition of 2-Methyl Azaarenes to Isatins via C–H Functionalization NIU Rui, YANG Shiying, XIAO Jian*, LIANG Tao, LI Xingwei* Ocean University of China; Dalian Institute of Chemical Physics, Chinese Academy of Science

MX R

-HX

R

N N

M

R N

H X

O

M

O N R' R R

N

N OH O

M O

O N R'

R'

N

Yb(OTf)3-catalyzed sp3 C–H functionalization of 2- and 4-methyl azaarenes has been developed for efficient synthesis of biologically important azaarene-substituted 3-hydroxy-2-oxindoles in one step. Moderate to good yields were obtained for various isatins and azaarenes.

Chin. J. Catal., 2012, 33: 1642–1649

doi: 10.1016/S1872-2067(11)60434-8

Effect of Metal Additives on the Structure and Properties of a Co/SiO2 Hydrogenation Catalyst CoCu/SiO2 Intensity

XUE Jingjing, CUI Fang, HUANG Zhiwei, ZUO Jianliang, CHEN Jing*, XIA Chungu* Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences

H2-TPR

CoSn/SiO2 CoFe/SiO2

Incorporation of metal additives in a Co/SiO2 catalyst accelerated the formation of cobalt phyllosilicate, which markedly decreased the reducibility of the catalyst as well as its activity and 1,2-propanediol selectivity in the hydrogenation of ethyl lactate.

CoZn/SiO2 Co/SiO2

0

100

200

300

400

500

Temperature (oC)

600

700

800

Chin. J. Catal., 2012, 33: 1650–1660

doi: 10.1016/S1872-2067(11)60436-1

Two-Enzyme Coexpressed Recombinant Strain for Asymmetric Synthesis of Ethyl (R)-2-Hydroxy-4-phenylbutyrate SU Yuning, NI Ye*, WANG Junchao, XU Zhihao, SUN Zhihao Jiangnan University

IolS

COOEt

OPBE

(R)-HPBE >99% ee NAD(P)H

NAD(P)+

80 60 40

T7

pET-G-T7-I 7000bp T7 Kan

0

2

4

gdh

40 20

ori

0

GDH

80 60

f1

20

glucose

gluconic acid

Yield ee

iolS

Yield (%)

COOEt

100

100

OH

ee (%)

O

0 6 8 10 12 14 16 Time (h)

A carbonyl reductase (IolS) exhibiting high enantioselectivity in the reduction of OPBE to (R)-HPBE was cloned, characterized, and coexpressed with glucose dehydrogenase to construct recombinant E. coli with cofactor regeneration.

Chin. J. Catal., 2012, 33: 1661–1664

doi: 10.1016/S1872-2067(11)60441-5

An Efficient and Facile Procedure for Synthesis of Acetates from Alcohols Catalyzed by Poly(4-vinylpyridinium tribromide) Maryam HAJJAMI*, Arash GHORBANI-CHOGHAMARANI, Masoomeh NOROUZI Ilam University, Iran

H2 H C C

R

H +

-

O O

n + N H Br3

O O

o

Acetone, 35 C

R

O

COCH3

R = Alkyl or Benzyl Acetylation of alcohols has been introduced using acetic anhydride in the presence of a catalytic amount of poly(4-vinylpyridinium tribromide).

Chin. J. Catal., 2012, 33: 1665–1671

doi: 10.1016/S1872-2067(11)60437-3

Fabrication and Photocatalytic Activity of Highly Crystalline Nitrogen Doped Mesoporous TiO2

PEG

PAM

LIU Erqiang, GUO Xiaoling, QIN Lei, SHEN Guodong, WANG Xiangdong* Xi’an Jiaotong University; Xi’an Polytechnic University Nitrogen doped mesoporous TiO2 photocatalysts with high crystallinity were fabricated by the sol-gel method using polyacrylamide and polyethylene glycol as templates, and then calcining in nitrogen and air.

Decompose PEG

Decompose PAM and remove carbon

Chin. J. Catal., 2012, 33: 1672–1680

doi: 10.1016/S1872-2067(11)60446-4

LED Irradiation of a Photocatalyst for Benzene, Toluene, Ethyl Benzene, and Xylene Decomposition JO Wan-Kuen*, KANG Hyun-Jung Kyungpook National University, Korea 3.4 cm

0.5 cm

Photocatalytic degradation 2.4 cm

Wavelength

Light intensity

(nm)

(mW/cm)

efficiency to power

Lamp

consumption (mg/kW) inlet

Fluorescent

400700

1.2

0.005

White-LED

450

2.3

0.007

Blue-LED

470

2.4

0.007

26.5 cm

outlet

Green-LED

252

1.5

0.003

Yellow-LED

600615

1.9

0.004

Red-LED

645700

0.8



The use of chips of visible light emitting diodes to irradiate an annular reactor coated with a nitrogen doped titania catalyst to decompose gaseous aromatic compounds was studied.

Chin. J. Catal., 2012, 33: 1681–1688

doi: 10.3724/SP.J.1088.2012.20532

Preparation of Mesoporous TiO2 Spheres via Sol-Gel Assisted Hydrothermal Method Using Double Templates WANG Dianping, LIU Shouxin Northeast Forestry University Ti(OBu)n(CH4COO)*

TBT + PEG + F127

Micellzation in solution

Stir and Hydrothermal

Calcination

+ HAc

Mesoporous TiO2 (MS-TiO2) spheres were synthesized with double surfactant (PEG and F127) as templates, which showed higher reliability than single template.

Chin. J. Catal., 2012, 33: 1689–1695

doi: 10.3724/SP.J.1088.2012.20520

Immobilization of Vanadyl Acetylacetonate on Amino Functionalized Hollow Silica Nanospheres and Its Catalytic Performance for Selective Oxidation of Thioanisole WANG Peng, BAI Shiyang, LI Bo, YANG Qihua* Dalian Institute of Chemical Physics, Chinese Academy of Sciences Vanadyl acetylacetonate was immobilized on amino functionalized mesoporous silica hollow nanospheres, as well as on amino functionalized SBA-15 and SBA-16. Under mild reaction conditions, the vanadium nanospheres show an enhanced catalytic performance than the bulk mesoporous counterparts.

Chin. J. Catal., 2012, 33: 1696–1705

doi: 10.3724/SP.J.1088.2012.20533

Conversion of Biomass-Derived Carbohydrates to Methyl Lactate Using Sn-MCM-41 and SnO2/SiO2 LIU Zhen, FENG Gang, PAN Chunyan, LI Wang, CHEN Ping, LOU Hui*, ZHENG Xiaoming Zhejiang University; Shaoxing Testing Institute of Quality Technical Supervision HO HO

OHHO

O

HO OH

HO Glucose

O HO Glyceraldehyde

OH

O

retro-aldol condensation

OH O

O

OH

1,2 hydride shif t Methyl lactate

HO HO

O -H2O

O O

OH

O

OHHO

OH HO

HO

OH Sucrose

HO

OH

OH

1,3-dihydroxyacetone

Biomass-derived carbohydrates were used as feedstock and methyl lactate was obtained in higher yield of 40%. Catalysts used in this work are easy synthesis, operational simplicity, reusability, and safe handling.

Chin. J. Catal., 2012, 33: 1706–1711

doi: 10.3724/SP.J.1088.2012.20617

Ea = 1.38 eV

Theoretical Study of Selectivity of Ethylene Hydroformylation on Rh(111) and Rh@Cu(111) Surfaces MA Xiufang, ZHAO Yonghui, SU Haiyan, LI Weixue* Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Ea = 0.62 eV Rh@Cu(111)

Due to the ensemble and ligand effects on Rh@Cu(111) destabilizing the reactants (CO and C2H5), the RhCu alloy catalyst has a low CO insertion barrier with improved hydroformylation selectivity compared with the pristine Rh(111).

Chin. J. Catal., 2012, 33: 1712–1716

Rh(111) CO+C2H5C2H5CO

doi: 10.3724/SP.J.1088.2012.20640

Growth and Interfacial Interaction of Cu on ZrO2(111) Thin Film HOU Jianbo, HAN Yong, PAN Yonghe, XU Qian, PAN Haibin, ZHU Junfa* University of Science and Technology of China

Cu source

Cu O Zr Pt

analyzer

hv hν

e +

+

+

Cu grows two-dimensionally on ZrO2(111)/Pt(111) up to 0.15 ML at 300 K, followed by three-dimensional growth. At low coverages, Cu(I) state appears. Above 1 ML, Cu becomes metallic state.

Chin. J. Catal., 2012, 33: 1717–1723

doi: 10.3724/SP.J.1088.2012.20606

Probing the Essential Catalytic Residues and Substrate Affinity in Thermophilic L-Arabinose Isomerase by Homology Modeling and Site-Directed Mutagenesis LI Guixiang, XU Zheng, LI Sha, XU Hong* Nanjing University of Technology

By means of site-directed mutagenesis, the LFAI native enzyme has been successfully mutated. Among the obtained mutants, some exhibited an enhancement on substrate conversion rate. For mutants relevant to amino acid residue No. 311, we found that the number of hydrogen bonds between substrate (D-galactose) and the catalytic center has an influence on the D-galactose conversion rate.

Chin. J. Catal., 2012, 33: 1724–1729

doi: 10.3724/SP.J.1088.2012.20650

Synthesis and Growth Mechanism of the Core-Shell SAPO-34/AlPO-18 Molecular Sieves ZHANG Lin, TIAN Peng, SU Xiong, FAN Dong, WANG Dehua, LIU Zhongmin* Dalian Institute of Chemical Physics, Chinese Academy of Sciences

AlPO-18 Shell

SAPO-34 Core The core-shell SAPO-34/AlPO-18 molecular sieves were hydrothermally synthesized through the epitaxial growth of AlPO-18 shell induced rationally by the microstructure on the SAPO-34 external surface.

Chin. J. Catal., 2012, 33: 1730–1735

doi: 10.3724/SP.J.1088.2012.20427

Preparation of Hyperbranched Polyethyleneimine Composite Membrane Using Interfacial Polymerization Catalyzed by 4-Dimethylaminopryidine ZHANG Lin, LIN Saisai, WEI Ping, CHENG Lihua*, CHEN Huanlin Zhejiang University

H3C

H3C

N

CH3

N

CH3

N

N

H3C

N

CH3

N H3C

N

CH3

N

The promoting effect of 4-dimethylaminopryidine (DMAP) on the interfacial polymerization between trimesoyl chloride (TMC) and hyperbranched polyethyleneimine(PEI) to prepare reverse osmosis membrane was investigated. The rejection against NaCl of PEI/TMC reverse osmosis composite membrane was improved from 45.2% to 85.4%.

Chin. J. Catal., 2012, 33: 1736–1741

doi: 10.3724/SP.J.1088.2012.20756

Photo-Fenton Degradation of RhB over Nano-fibre Iron Oxides Interacted Montmorillonite under Visible Light Irradiation ZHANG Shilong, HU Xiaoming, WANG Xiaowei, LIANG Shijing, WU Ling Fuzhou University; Western Geological Exploration Brigade of Jiangxi Geology & Mineral Resources Development Bureau

Tetrahedral Octahedral

Tetrahedral O Al, Fe, Mg Si OH Li, Na, K, Ca [Fe3O(CH3CO2)6(H 2O)3]+

A large iron cluster was intercalated into the lays of montmorillonite via a facile cation exchange method. The SEM image shows that a few amorphous nano-fibre iron oxides were anchored on the surface of the intercalated montmorillonite.

(CUIHUA XUEBAO) 中国科学院科学出版基金资助出版

CHINESE JOURNAL OF CATALYSIS 月刊

SCI 收录

2012 年 10 月第 33 卷第 10 期

目综

述

1611 (国际版) 环境催化中的陶瓷材料: 应用与可能性 Nitin LABHSETWAR, P. DOGGALI, S. RAYALU, R. YADAV1, T. MISTUHASHI, H. HANEDA

研究论文 1622 (国际版/封面文章) 活性炭催化苯一步羟基化制备苯酚徐加泉, 刘慧慧, 杨瑞光, 李桂英, 胡常伟 1631 (国际版) 程序升温表面反应技术研究氧化铈上 H2S 的吸附和转化刘冰, 徐恒泳, 张泽会 1636 (国际版) Yb(OTf)3 催化的碳氢键活化 2-甲基氮杂芳烃对靛红的加成反应牛瑞, 杨世迎, 肖建, 梁涛, 李兴伟 1642 (国际版) 第二金属对 Co/SiO2 加氢催化剂结构和性能的影响薛晶晶, 崔芳, 黄志威, 左建良, 陈静, 夏春谷 1650 (国际版) 不对称还原制备光学纯 (R)-2-羟基-4-苯基丁酸乙酯的双酶共表达重组菌的构建宿宇宁, 倪晔, 王骏超, 徐志豪, 孙志浩 1661 (国际版) 一种高效简易的聚(4-乙烯基三溴化吡啶)催化乙醇合成乙酸盐的方法 Maryam HAJJAMI, Arash GHORBANI-CHOGHAMARANI, Masoomeh NOROUZI 1665 (国际版) 高结晶度氮掺杂介孔 TiO2 的制备及光催化活性刘二强, 郭晓玲, 秦雷, 申国栋, 王向东 1672 (国际版) LED 照射光催化剂用于苯、甲苯、乙苯和二甲苯分解 JO Wan-Kuen, KANG Hyun-Jung

次 1681 溶胶-凝胶辅助水热双模板法制备球形介孔 TiO2 王殿平, 刘守新 1689 氨基功能化介孔氧化硅纳米中空球负载乙酰丙酮氧钒催化苯甲硫醚选择性氧化反应王鹏, 白诗扬, 李博, 杨启华 1696 Sn-MCM-41 与 SnO2/SiO2 催化转化生物质基碳水化合物制乳酸甲酯刘镇, 冯刚, 潘春燕, 李望, 陈平, 楼辉, 郑小明 1706 Rh(111) 及 Rh@Cu(111) 表面乙烯氢甲酰化反应选择性的理论研究马秀芳, 赵永慧, 苏海燕, 李微雪 1712 Cu 在 ZrO2(111) 薄膜载体上的生长与界面相互作用侯建波, 韩永, 潘永和, 徐倩, 潘海斌, 朱俊发 1717 基于同源建模和定点突变技术研究嗜热型 L-阿拉伯糖异构酶与 D-半乳糖的亲和作用李贵祥, 徐铮, 李莎, 徐虹 1724 核壳型 SAPO-34/AlPO-18 分子筛的制备及生长机理张琳, 田鹏, 苏雄, 樊栋, 王德花, 刘中民 1730 4-二甲氨基吡啶催化的界面聚合法制备超支化聚乙烯亚胺复合膜张林, 林赛赛, 魏平, 程丽华, 陈欢林 1736 纳米纤维铁氧化物柱撑蒙脱土可见光助芬顿降解罗丹明 B 张世龙, 胡小明, 王晓韡, 梁诗景, 吴棱

相关信息 1742

作者索引

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Chinese Journal of Catalysis

2012 文章编号: 0253-9837(2012)10-1665-07

国际版 DOI: 10.1016/S1872-2067(11)60437-3

Vol. 33 No. 10 研究论文: 1665–1671

高结晶度氮掺杂介孔 TiO2 的制备及光催化活性刘二强 1, 郭晓玲 2, 秦 1 2

雷 1, 申国栋 2, 王向东 1,*

西安交通大学理学院, 陕西西安 710049

西安工程大学纺织与材料学院, 陕西西安 710048

摘要: 以钛酸丁酯为钛源, 尿素为氮源, 聚丙烯酰胺 (PAM) 和聚乙二醇 (PEG) 为复合模板剂, 采用溶胶-凝胶法, 在氮气和空气气氛中分段煅烧, 制得高结晶度氮掺杂介孔 TiO2 光催化剂. 利用 X 射线衍射、透射电镜、N2 吸附-脱附、X 射线光电子能谱和紫外-可见漫反射光谱等技术对其进行了表征. 结果表明, 当 PAM 和 PEG 的质量比为 1:4 时, 先在氮气中 600 °C 煅烧, 后在空气中 500 °C 煅烧所得样品是锐钛矿相, 具有良好的孔隙结构和较高的结晶度, 平均孔径为 5.11 nm, 晶粒尺寸为 12.5 nm, 比表面积 110.8 m2/g. 掺杂介孔 TiO2 的氮主要以取代氮和化学吸附分子 γ-N2 的形式存在, 少量以间隙氮形式存在. 氮掺杂使 TiO2 的能带变窄, 吸收带边明显红移, 且使光吸收强度显著增大. 光催化降解甲基橙实验结果表明, 与未掺杂样品相比, 氮掺杂介孔 TiO2 在可见光作用下表现出较高的催化活性. 关键词: 介孔二氧化钛; 氮掺杂; 高结晶度; 光催化活性; 甲基橙中图分类号: O643

文献标识码: A

收稿日期: 2012-05-06. 接受日期: 2012-07-16. *通讯联系人. 电话: (029)82663913; 传真: (029)82663914; 电子信箱: [email protected] 基金来源: 国家自然科学基金 (50772082); 陕西高校省级重点实验室科研项目 (2010JS007). 本文的英文电子版(国际版)由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18722067).

Fabrication and Photocatalytic Activity of Highly Crystalline Nitrogen Doped Mesoporous TiO2 *

LIU Erqiang1, GUO Xiaoling2, QIN Lei1, SHEN Guodong2, WANG Xiangdong1, 1

School of Science, Xi’an Jiaotong University, Xi’an 710049, Shaanxi, China

2

School of Textile and Materials, Xi’an Polytechnic University, Xi’an 710048, Shaanxi, China

Abstract: Highly crystalline nitrogen doped mesoporous TiO2 photocatalysts were fabricated by the sol-gel method using tetrabutyl titanate as the Ti source, urea as the N source, and polyacrylamide (PAM) and polyethylene glycol (PEG) as the templates, and then by calcining in nitrogen and air. The photocatalysts were characterized by X-ray diffraction, transmission electron microscopy, N2 adsorption, X-ray photoelectron spectroscopy, and UV-Vis spectroscopy. When the mass ratio of PAM and PEG was 1:4, the sample prepared by calcining at 600 °C in nitrogen and 500 °C in air had the anatase phase and a mesoporous structure and high crystallinity. The average pore size, crystallite size, and specific surface area were 5.11 nm, 12.5 nm, and 110.8 m2/g, respectively. Nitrogen atoms were incorporated into the TiO2 lattice mainly as substitutional N and molecularly chemisorbed γ-N2, and a small amount of interstitial N. Nitrogen doping narrowed the band gap and allowed light absorption in the visible light region. Compared with undoped mesoporous TiO2, the absorption band edge of nitrogen doped samples exhibited a red shift and the light absorption intensity was increased. Photocatalytic degradation of methyl orange showed that the nitrogen doped mesoporous TiO2 had a higher photocatalytic activity than undoped mesoporous TiO2 under visible light. Key words: mesoporous titanium dioxide; nitrogen doped; high crystallinity; photocatalytic activity; methyl orange Received 6 May 2012. Accepted 16 July 2012. *Corresponding author. Tel: +86-29-82663913; Fax: +86-29-82663914; E-mail: [email protected] This work was supported by the National Natural Science Foundation of China (50772082) and the Scientific Research Project of the Provincial University’s Key Laboratory of Shaanxi Province (2010JS007). English edition available online at Elsevier ScienceDirect (http://www.sciencedirect.com/science/journal/18722067).

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Mesoporous TiO2 is well studied because of its photocatalytic activity, which is used in photoelectrochemical applications [17]. Mesoporous TiO2 prepared by traditional methods still has some disadvantages such as low crystallinity, low thermostability, and low visible light response. Mesoporous TiO2 with enhanced crystallinity and thermostability is required in many demanding applications, such as solar energy conversion, batteries, and photocatalysis, because the semiconducting and photovoltaic behavior is largely dependent on the crystallinity of the TiO2. Many approaches have been taken to improve the crystallinity of mesoporous TiO2, including using several block copolymers as templates to give a much thicker pore wall composed of nanocrystals embedded in an amorphous material [810]. When these materials are converted into the completely crystalline state at high temperature, the mesoporous structure collapses due to the growth of the nanocrystals. Despite much effort, it is a major challenge to successfully convert the amorphous walls of mesoporous TiO2 to crystalline walls while retaining the original mesoporous structure. To solve the above problem, Lee et al. [11] reported a new method in which an amphiphilic diblock copolymer, poly(isoprene-block-ethylene oxide), was used as the template to synthesize mesoporous TiO2, which was then calcined in an Ar atmosphere first and then recalcined in air. The mesoporous TiO2 prepared by this method has high crystallinity, high thermostability, and high surface area. However, the disadvantage of the method is the cost of the template. Their study did not report about TiO2 doping especially with nonmetal elements such as N [1215], F [16,17], S [18], and C [19,20], which can create a mid-gap state that acts as electron donor or acceptor in the band gap of TiO2. The doping can narrow the band gap of TiO2 and extend its light absorption into the visible region, which would then enhance the quantum efficiency of the material, improving its photocatalytic activity under visible light. In the present paper, we report a sol-gel method using polyacrylamide (PAM) and polyethylene glycol (PEG) as templates to synthesis nitrogen doped mesoporous TiO2 with high surface area and high crystallinity. The materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption, X-ray photoelectron spectroscopy, and UV-Vis spectroscopy. The photocatalytic activities of the undoped and nitrogen doped mesoporous TiO2 were evaluated by the photocatalytic degradation of methyl orange (MO) in water.

1

Experimental

1.1

Photocatalyst synthesis

The sol-gel preparation of the nitrogen doped mesopor-

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Chin. J. Catal., 2012, 33: 1665–1671

ous TiO2 was performed as follows. Deionized water (10 ml), nitric acid (5 wt%, 6 ml), and 0.56.0 g of urea dissolved in 280 ml of absolute ethanol were added into 10 ml of tetrabutyl titanate. After the mixture was stirred at ambient temperature for 1 h, the resulting solution was slowly added into a solution of 0.2 g PAM (Wt = 3000000) and 0.8 g PEG (Wt = 20000) dissolved in 30 ml of deionized water under vigorously stirring. A white gel was formed, which was dried at 60 °C for 12 h. The light yellow powder obtained was calcined in a N2 atmosphere and 400800 °C, and then recalcined in air at 400700 °C. For comparison, undoped mesoporous TiO2 was prepared according to the above procedure with the absence of urea. 1.2

Photocatalyst characterization

XRD patterns of the photocatalysts were recorded at room temperature by a Bruker D8 Advance X-ray diffractometer using Cu Kα radiation and a scan rate of 2º/min. TEM image was recorded on a JEM-2100F made in Japan. N2 adsorption isotherms were collected on an AUTOSORB-1 nitrogen adsorption apparatus at 196 °C. XPS analysis was performed using a PHI 5300 ESCA instrument with an Mg Kα X-ray source at a power of 250 W. The binding energy was calibrated with respect to the C 1s peak of hydrocarbon contamination at 284.6 eV. Diffuse reflectance UV-visible absorption spectra of the powder samples were obtained using a Shimadzu-2501 spectrophotometer. BaSO4 was the reference sample, and the spectra were recorded in the range of 200900 nm. 1.3

Photocatalytic activity

Photocatalytic activity was tested by the photocatalytic degradation of MO solutions under visible light irradiation at room temperature. The reactor was a 100 ml cylindrical vessel containing 60 ml of MO solution with a water-cooled quartz jacket. Irradiation was by a 300 W xenon lamp located in the center of the quartz jacket, which emitted a similar spectrum to visible light. This was equipped with a magnetic stirrer at the bottom of the reactor to achieve effective dispersion. The initial MO concentration was 10 mg/L and the amount of photocatalyst was 150 mg. Before irradiation, 30 min adsorption was allowed to reach adsorption equilibrium with the photocatalyst and MO solutions were kept in a dark condition. Then the mixed solution was irradiated. The solution (4 ml) was taken out at regular intervals and separated by centrifugal separation to determine the residual concentration of MO by a spectrophotometer (UV-7220, Beifenruili, China) at 464 nm. The change of relative absorbance was used to record the change of concentration of MO in the solution.

刘二强等: 高结晶度氮掺杂介孔 TiO2 的制备及光催化活性

2

Results and discussion

2.1

Photocatalyst synthesis

Figure 1 shows the synthesis mechanism of the photocatalysts. The nitrogen doped mesoporous TiO2 was prepared by two steps. First, a sol-gel process was conducted using tetrabutyl titanate as the Ti source, urea as the N source, and PAM and PEG as the templates. Due to its strong hydrophilicity, PEG readily combined with the titania sol obtained from the hydrolyzation to form composite grains. These composite grains were incorporated in PAM by hydrogen bonding, and the grains were confined in the molecule network of PAM. This bonding process can effectively accelerate the sol-gel reaction. Second, the precursor prepared by the sol-gel process was successively calcined in a N2 atmosphere and air atmosphere to synthesize the photocatalyst. Nitrogen doped mesoporous TiO2 with a high crystallinity and high surface area was obtained. This was because in this method, PEG was easily decomposed on heating, whereas the more thermally stable PAM was converted to a sturdy, amorphous carbon when calcined in N2. The amorphous carbon acted as a rigid support of the mesoporous structure that prevented its collapse when it was calcined to the temperature required for getting a highly crystalline material [11]. The carbon was subsequently eliminated by calcining in air, leaving a highly crystalline mesoporous material. PEG

PAM

(5) (4)

(3) (2) (1) 10

20

30

40

50

60

70

80

2/( ) o

Fig. 2. XRD patterns of samples calcined at different temperatures (N2/air). (1) 400/400 °C; (2) 500/400 °C; (3) 600/500 °C; (4) 700/600 °C; (5) 800/700 °C.

calcining temperature was 700/600 °C (Fig. 2(4)), and it was the main phase when the temperature was 800/700 °C (Fig. 2(5)). It was a good calcining temperature (600/500 °C, Fig. 2(3)) because the phase composition of the sample was mainly anatase and it has a high specific surface areas (Table 1). The diffraction peak became significantly sharper with the increase in calcining temperature, indicating an increase in crystallinity [13,21]. The average crystallite size of the anatase crystals, estimated from the X-ray peak width using the Scherrer equation, became larger with the increase of the calcining temperature (Table 1). The specific surface area decreased sharply with the increase in calcining temperature. So, in this method, the calcining temperature of 600 (in N2) and 500 °C (in air) were appropriate to optimize the crystallinity, crystal phase, and specific surface area. Table 1

Decompose PEG

Characterization results of samples prepared at different

temperatures ABET/

T/°C Decompose PAM and remove carbon

Fig. 1.

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Rutile Anatase

Intensity

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Illustration of the synthesis mechanism of the photocatalysts.

Phase

Crystallite size

N2

air

m2/g

400

400

171.2

A + Amors.

500

400

135.2

A + Amors.

9.36

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500

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(nm) 9.45

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21.35

800

700

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A+R

25.47 + 41.38

A: anatase phase; R: rutile phase; Amors: amorphous phase.

2.2

XRD analysis 2.3

Figure 2 shows the XRD patterns of the nitrogen doped mesoporous TiO2 prepared with the PAM:PEG mass ratio 1:4 after calcination at different temperatures. The phase composition of the samples was mainly anatase and an amorphous phase when the calcining temperature was low (Figs. 2(1) and (2)). The rutile phase appeared when the

TEM analysis

Figure 3 shows the TEM images of the sample prepared at the calcination temperature of 600/500 °C. It can be seen from Fig. 3(a) that the sample has a typical honeycomb porous structure with high crystallinity, in which the agglomeration of monodispersed TiO2 particles was clearly ob-

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average interplanar spacing of 0.35 nm, which is that of TiO2 (d101) in the corresponding wide angle XRD pattern [2224]. The pore size and grain size were, respectively, 57 nm and 1214 nm, which were in good agreement with the N2 adsorption and XRD results. The selected area electron diffraction (SAED) pattern of the sample (Fig. 3(d)) showed a sequence of diffraction rings consistent with those expected of anatase TiO2 [11,25].

(b)

(a)

Chin. J. Catal., 2012, 33: 1665–1671

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(d)

(c)

2.4

Fig. 3.

Samples characterized by TEM. (a,b) TEM images; (c)

HRTEM image; (d) SAED pattern.

served. Figure 3(b) shows that the sample has a wormhole-like pore structure. The pores were connected randomly and lack a discernible long range order in the pore arrangement. Anatase TiO2 nanocrystals were embedded in the disordered mesoporous framework. As seen in Fig. 3(c), the lattice fringe measured in the HRTEM image had an

N2 adsorption

Figure 4 shows the N2 adsorption isotherm and pore size distribution curve of the sample prepared at the calcining temperature of 600/500 °C. The specific surface area calculated from the linear part of the adsorption isotherm was 110.8 m2/g. The N2 adsorption-desorption isotherm was Type IV with a H2 hysteresis, which is typical of mesoporous materials [26,27]. The average mesopore size estimated using the Barrett-Joyner-Halenda (BJH) approach from the desorption branch was 5.11 nm (Fig. 4(b)), which was in agreement with the pore size estimated from TEM images (Fig. 3). From the crystallite size of the sample, the mesopores were probably formed by the agglomeration and connection of adjacent nanoparticles in the sample, which were seen in the TEM results (Figs. 3(a) and (b)). 0.06

80 (a)

5.11

70 Pore volume (cm3/g)

Vads/(cm3/g)

60 50 40 30 20 10 0.0

2.5

0.04 0.03 0.02 0.01 0.00

0.2

0.4

0.6

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1.0

p/p0 Fig. 4.

(b)

0.05

0

5

10

15

20

25

30

Pore diameter (nm)

N2 adsorption isotherm (a) and pore size distribution (b) for the sample prepared at the calcining temperature of 600/500 oC.

XPS analysis

Figure 5 shows the XPS spectra of the nitrogen doped mesoporous TiO2 sample prepared with the calcining temperature of 600/500 °C and mole proportion of urea and tetrabutyl titanate of 2:1. Obvious peaks of titanium, oxygen, nitrogen, and carbon were detected in Fig. 5(a). The binding energies of Ti 2p, O 1s, N 1s, and C 1s were 458.5, 531, 400, and 284 eV, respectively, which was approximately in agreement with the data of other researchers [2830]. The carbon signal was from the residual carbon from the precursor solution and adventitious hydrocarbon in the XPS instrument

itself. The total nitrogen concentration, estimated from the XPS data, was 0.6% (molar ratio of elements). Figure 5(b) shows the high resolution XPS spectra of the N 1s region. Three XPS peaks at 397.0, 398.8, and 402.4 eV were observed. Different N 1s peak positions represent various forms of nitrogen in doped TiO2. In most cases, the peak at 397.0 eV was ascribed to the TiNTi bond indicating that nitrogen atom was substitutionally doped into the TiO2 lattice [3133]. The peak at 400 eV is related to oxidized nitrogen such as TiON or TiNO bonding, so the peak at 398.8 eV can be attributed to anionic N in interstitial N [31,32,34]. The peak at 402.4 eV was observed and attrib-


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(b)

(a)

402.4

O 1s

C 1s

200

397.0

Intensity

Intensity

Ti 2p

N 1s

398.8

400

600

800

396

398

Binding energy (eV)

400

402

404

Binding energy (eV)

Fig. 5. XPS spectra (a) and high resolution XPS spectra of N 1s (b) for the nitrogen doped mesoporous TiO2.

uted to molecularly chemisorbed γ-N2, in which N atoms were incorporated into the TiO2 lattice as N2 molecules [12,35]. In Fig. 5(b), the peaks at 402.4 and 397.0 eV have a higher intensity than the peak at 398.8 eV. From the XPS results, it was concluded that the forms of doped nitrogen incorporated into the TiO2 lattice were mainly substitutional N and molecularly chemisorbed γ-N2 molecules, with some interstitial N. According to the literature [31,36,37], interstitial nitrogen doping is favored with oxygen-rich and low calcining temperature conditions, while substitutional nitrogen doping is preferred with the absence of oxygen and high calcining temperature conditions. In the present work, the first calcining was performed in N2, which is an oxygen-deficient condition, and at a high calcining temperature (600 °C), so the nitrogen atoms were mainly incorporated into substitutional sites. 2.6

UV-Vis DRS spectra

Figure 6 shows the UV-Vis diffuse reflectance spectra of undoped and nitrogen doped mesoporous TiO2 photocatalysts prepared with different mole ratios of urea and

tetrabutyl titanate and at the calcining temperature of 600/500 °C. All the absorption band edges of the nitrogen doped mesoporous TiO2 samples exhibited an evident red shift, and the light absorption intensity of the nitrogen doped samples was higher than that with undoped TiO2 (S4). As seen in Fig. 6(a), pure anatase TiO2 showed absorption peaks at 400 nm. This may be because in the present work, the pure anatase TiO2 was prepared in a N2 atmosphere and high temperature and has oxygen vacancies, which contributed to the absorption red shift of oxygen-deficient TiO2 [38]. With the increase of the mole ratio of urea and tetrabutyl titanate, the absorption intensity of visible light of the nitrogen doped samples increased. When the mole ratio of urea and tetrabutyl titanate was 2:1 (S1), the absorption intensity of visible light was the highest. That is, absorption intensity increased with increasing nitrogen doping concentration. The light absorbance enhancement in the UV-visible light range was consistent with the yellow color of the sample. The enhanced light absorption in the visible range of the nitrogen doped samples was because nitrogen doping significantly shifted light absorption to the visible region through band gap narrowing [3639]. (b)

(Ephoto)

2

Absorbance

(a)

S2

S2

S1

S3

S3

S1 S4

S4 200

300

400

500

600

700

Wavelength (nm) Fig. 6.

800

900

2.2

2.4

2.6

2.8

3.0

3.2

3.4

3.6

3.8

4.0

Ephoto/eV

UV-Vis DRS spectra (a) and band gap from the plots of (αEphoton)2 vs energy of absorbed light (b) of samples prepared with different mole

ratios of urea and tetrabutyl titanate. S1: CO(NH2)2:TiO2 = 2:1; S2: CO(NH2)2:TiO2 = 1:1; S3: CO(NH2)2:TiO2 = 1:2; S4: TiO2.

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Figure 6(b) shows the absorption edge of the samples. The plots of (αEphoton)2 versus energy of absorbed light gave the band gap of the samples [32,40,41]. The band gap energies were measured to be 2.32.9 eV for the samples prepared with various mole proportion of urea and tetrabutyl titanate. The narrowed band gap was due to the contributions of the nitrogen dopant and oxygen vacancies in the TiO2 lattice. The nitrogen dopant induced local states above the valence band edge and oxygen vacancies gave rise to mid-gap states below the conduction band [31,33,34,42]. These were responsible for the photocatalytic degradation reaction under visible light irradiation. S3 has the lowest band gap energy, but its absorption intensity was also the lowest. So, taking into account band gap energy and absorption intensity, S2 was the best sample.

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while the undoped mesoporous TiO2 absorbed only in the UV region. From Fig. 7, the photocatalytic activity sequence of the nitrogen doped mesoporous TiO2 photocatalysts was S2 > S3 > S1. The sequence of the mole ratios of urea and tetrabutyl titanate of the three samples was S1 > S2 > S3. This result indicated that with an appropriate amount of nitrogen doping, photoexcited electrons and holes can be separated efficiently and the photocatalytic activity was enhanced, but excessive nitrogen doping may act as the recombination centers for photoexcited electrons and holes, which reduces the photocatalytic activity [43]. The photocatalytic activity of the nitrogen doped mesoporous TiO2 samples was in agreement with their UV-Vis diffuse reflectance spectra.

3 2.7

Conclusions

Photocatalytic activity

The photocatalytic activity of the samples was measured by the degradation of MO solutions under visible light irradiation at room temperature. Figure 7 shows the degradation kinetics of the MO solutions. A blank test indicated that in the absence of a photocatalyst, decoloration of the MO solution was negligible. Compared with undoped mesoporous TiO2, the nitrogen doped mesoporous TiO2 photocatalysts showed obviously promoted photocatalytic activity. The degradation rates of all the nitrogen doped mesoporous TiO2 photocatalysts were more than 60% for 12 h of irradiation time, while it was below 20% for undoped mesoporous TiO2. The higher photocatalytic activity of the nitrogen doped TiO2 photocatalysts under visible light irradiation was explained by the following. Nitrogen doping resulted in the shift of the absorbance of light towards longer wavelength. As shown in Fig. 6, the nitrogen doped mesoporous TiO2 exhibited strong absorption in the visible light region,

Nitrogen doped mesoporous TiO2 with high crystallinity and a large specific surface area was fabricated using a sol-gel method in which PAM and PEG were used as templates. When calcined in N2, PAM was converted into a sturdy, and the amorphous carbon that prevented the collapse of the mesoporous structure when the sample was calcined to the temperature required for getting high crystallinity. When the mass ratio of PAM and PEG was 1:4, the sample prepared at 600 °C in nitrogen and at 500 °C in air has the anatase phase, and it has a mesoporous structure with high crystallinity and a high specific surface area. The absorption band edges of the nitrogen doped mesoporous TiO2 samples exhibited a red shift and their absorption intensity was higher than that of the undoped sample, that is, nitrogen doping made the band gap of TiO2 narrower. Compared with the undoped sample, nitrogen doped mesoporous TiO2 has a higher photocatalytic activity under irradiation of visible light.

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