Au掺杂浓度对WO_3微米球NO_2气敏特性的影响
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摘要
采用水热法制备不同Au掺杂浓度的分级多孔WO_3微米球,探讨其作为气敏材料对NO_2气体的气敏特性。利用XRD、SEM、EDS和XPS对制备的WO_3微米球的晶体结构、微观形貌以及元素组成进行结构分析。结果表明:Au掺杂浓度对WO_3微米球的结构和形貌没有明显影响,所获WO_3微米球的直径均为3～5μm,主要由直径为70～90 nm的六方相晶体结构的WO_3纳米棒组成。在相同的检测条件下,Au掺杂浓度为2%(摩尔分数)时,WO_3微米球可获得对NO_2气体的最佳气敏反应特性,且在工作温度50℃时获得最大气体灵敏度,这主要是由于该Au掺杂浓度条件下获得的WO_3微米球具有最小活化能的缘故。通过电子耗尽层理论和贵金属掺杂的化学效应对Au掺杂WO_3微米球的气敏机理进行分析和探讨。
The hierarchical porous WO_3 microspheres with different Au doping concentrations were synthesized by hydrothermal method and investigated as NO_2 sensing materials. The crystal structure, morphology and element composition of WO_3 microspheres were characterized by means of XRD, SEM, EDS and XPS measurements. The results show that the structure and morphology of WO_3 microspheres are not significantly affected by Au doping concentration. The obtained WO_3 microspheres with the diameters of 3-5 μm are assembled by numerous hexagonal nanorods with the diameters of 70-90 nm. 2%(mole fraction) Au-doped WO_3 microspheres obtain the maximal response-recovery properties under the same conditions. The peak response is achieved at operating temperature of 50 ℃ for 2%(mole fraction) Au-doped WO_3 microspheres, which is mainly due to its lowest activation energy. The gas sensing mechanism of Au-doped WO_3 microspheres was discussed in accordance with the electron depletion layer theory and chemical sensitization of noble metal doping.
The hierarchical porous WO_3 microspheres with different Au doping concentrations were synthesized by hydrothermal method and investigated as NO_2 sensing materials. The crystal structure, morphology and element composition of WO_3 microspheres were characterized by means of XRD, SEM, EDS and XPS measurements. The results show that the structure and morphology of WO_3 microspheres are not significantly affected by Au doping concentration. The obtained WO_3 microspheres with the diameters of 3-5 μm are assembled by numerous hexagonal nanorods with the diameters of 70-90 nm. 2%(mole fraction) Au-doped WO_3 microspheres obtain the maximal response-recovery properties under the same conditions. The peak response is achieved at operating temperature of 50 ℃ for 2%(mole fraction) Au-doped WO_3 microspheres, which is mainly due to its lowest activation energy. The gas sensing mechanism of Au-doped WO_3 microspheres was discussed in accordance with the electron depletion layer theory and chemical sensitization of noble metal doping.
引文
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[16]CHEN D L,YIN L,GE L F,FAN B J,ZHANG R,SUN J,SHAO G S.Low-temperature and highly selective NO-sensing performance of WO3 nanoplates decorated with silver nanoparticles[J].Sensors and Actuators B:Chemical,2013,185(8):445-455.
[17]CHEN L,TSANG S C.Ag doped WO3-based powder sensor for the detection of NO gas in air[J].Sensors and Actuators B:Chemical,2003,89(1):68-75.
[18]WANG Y Y,ZHANG B,LIU J,LU G Y.Au-loaded mesoporous WO3:Preparation and n-butanol sensing performances[J].Sensors and Actuators B:Chemical,2016,236(5):67-76.
[19]LIU X H,ZHANG J,YANG T,GUO X Z,WU S H,WANG S R.Synthesis of Pt nanoparticles functionalized WO3 nanorods and their gas sensing properties[J].Sensors and Actuators B:Chemical,2011,156(2):918-923.
[20]KABCUM S,KOTCHASAK N,CHANNEI D,TUANTRANONT A,WISITSORAAT A,PHANICHPHANT S.Highly sensitive and selective NO2 sensor based on Au-impregnated WO3 nanorods[J].Sensors and Actuators B:Chemical,2017,252(8):523-536.
[21]SHEN Y B,CHEN X X,WANG W,GONG Y,CHEN S H,LIU JT,WEI D Z,MENG D,SAN X G.Complexing surfactants-mediated hydrothermal synthesis of WO3microspheres for gas sensing applications[J].Materials Letters,2016,163:150-153.
[22]XIA H J,WANG Y,KONG F H,WANG S R,ZHU B L,GUO XZ,ZHANG J,WANG Y M,WU S H.Au-doped WO3-based sensor for NO2 detection at low operating temperature[J].Sensors&Actuators B Chemical,2008,134(1):133-139.
[23]陈享享,沈岩柏,王玮,张宝庆,樊虹,魏德洲.用WO3纳米材料制备矿业安全用NO2气体传感器[J].金属矿山,2016,478(4):158-163.CHEN Xiang-xiang,SHEN Yan-bai,WANG Wei,ZHANGBao-qing,FAN Hong,WEI De-zhou.NO2 gas sensors made from WO3 nanomaterials used for mining safety[J].Metal Mine,2016,478(4):158-163.
[24]SHEN Y B,WANG W,FAN A F,WEI D Z,LIU W G,HAN C,SHEN Y S,MENG D,SAN X G.Highly sensitive hydrogen sensors based on SnO2 nanomaterials with different morphologies[J].International Journal of Hydrogen Energy,2015,40(45):15773-15779.
[25]XIA H J,WANG Y,KONG F H,WANG S R,ZHU B L,GUO XZ,ZHANG J,WANG Y M,WU S H.Au-doped WO3-based sensor for NO2 detection at low operating temperature[J].Sensors and Actuators B:Chemical,2008,134(1):133-139.
[26]LI F,LI C,ZHU L H,GUO W B,SHEN L,WEN S P,RUAN SP.Enhanced toluene sensing performance of gold-functionalized WO3·H2O nanosheets[J].Sensors and Actuators B:Chemical,2016,223(2):761-767.
[2]SHEN Y B,ZHANG B Q,CAO X M,WEI D Z,MA J W,JIA LJ,GAO S L,CUI B Y,JIN Y C.Microstructure and enhanced H2S sensing properties of Pt-loaded WO3 thin films[J].Sensors and Actuators B:Chemical,2014,193(3):273-279.
[3]魏少红,牛新书,蒋凯.WO3纳米材料的NO2气敏特性[J].传感器技术,2002,21(11):11-13.WEI Shao-hong,NIU Xin-shu,JIANG Kai.Gas sensitivity to NO2 of WO3 nanosized material[J].Journal of Transducer Technology,2002,21(11):11-13.
[4]沈岩柏,魏德洲,马嘉伟,张宝庆.TeO2纳米线的制备及其室温NO2气敏特性[J].东北大学学报(自然科学版),2014,35(7):1019-1022.SHEN Yan-bai,WEI De-zhou,MA Ja-wei,ZHANG Bao-qing.Preparation and room-temperature NO2 sensing Properties of Te O2 nanowires[J].Journal of Northeastern University(Natural Science),2014,35(7):1019-1022.
[5]GODBOLE R,GODBOLE V,ALEGAONKAR P,BHAGWATSM.Effect of film thickness on gas sensing properties of sprayed WO3 thin films[J].New Journal of Chemistry,2017,416(9):511-520.
[6]SHENDAGE S S,PATIL V L,PATIL S P,VANALAKAR S A,BHOSALE J L,KIM J H.NO2 sensing properties of porous fibrous reticulated WO3 thin films[J].Journal of Analytical&Applied Pyrolysis,2017,125(1):9-16.
[7]LIU L,SONG P,YANG Z X,WANG Q.Highly sensitive and selective trimethylamine sensors based on WO3 nanorods decorated with Au nanoparticles[J].Physica E:Low-dimensional Systems and Nanostructures,2017,90(2):109-115.
[8]沈岩柏,张宝庆,曹先敏,魏德洲,刘文刚,高淑玲.基片温度对WO3薄膜的微观结构和NO2气敏特性的影响[J].中国有色金属学报,2015,25(3):740-746.SHEN Yan-bai,ZHANG Bao-qing,CAO Xian-min,WEIDe-zhou,LIU Wen-gang,CAO Shu-ling.Effect of substrate temperature on microstructure and NO2 sensing properties of WO3 thin films[J].The Chinese Journal of Nonferrous Metals,2015,25(3):740-746.
[9]ZHANG J N,LU H B,LIU C,CHEN C J,XIN X.Ni O-WO3heterojunction nanofibers fabricated by electrospinning with enhanced gas sensing properties[J].RSC Advances,2017,7(64):40499-40509.
[10]陈香,李洁,李文章,陈启元.纳米多孔WO3薄膜电极的制备及其光电化学性质[J].中国有色金属学报,2012,22(12):3487-3494.CHEN Xiang,LI Jie,LI Wen-zhang,CHEN Qi-yuan.Preparation and photo electrochemical properties of nano-porous tungsten trioxide films electrode[J].The Chinese Journal of Nonferrous Metals,2012,22(12):3487-3494.
[11]SAMERJAI T,LIEWHIRAN C,WISITSORAAT A,TUANTRANONT A,KHANTA C,PHANICHPHANT S.Highly selective hydrogen sensing of Pt-loaded WO3 synthesized by hydrothermal/impregnation methods[J].International Journal of Hydrogen Energy,2014,39(11):6120-6128.
[12]SRIVASTAVA V,JAIN K.Highly sensitive NH3 sensor using Pt catalyzed silica coating over WO3 thick films[J].Sensors and Actuators B:Chemical,2008,133(1):46-52.
[13]D’ARIENZO M,CRIPPA M,GENTILE P,MARI CM,POLIZZI S,RUFFO R.Sol-gel derived mesoporous Pt and Cr-doped WO3 thin films:the role played by mesoporosity and metal doping in enhancing the gas sensing properties[J].Journal of Sol-gel Science and Technology,2011,60(3):378-387.
[14]SICILIANO T,TEPORE A,MICOCCI G,SERRA A,MANNOD,FILIPPO E.WO3 gas sensors prepared by thermal oxidization of tungsten[J].Sensors and Actuators B:Chemical,2008,33(1):321-326.
[15]余华梁,李静玲,吴一纯,李玉良,周赢武.紫外光照下WO3的H2S气敏特性研究[J].电子元件与材料,2014,33(5):53-56.YU Hua-liang,LI Jing-ling,WU Yi-chuan,LI Yu-liang,ZHOUYing-wu.H2S gas sensitivity of UV light activated WO3 gas sensors[J].Electronic Components and Materials,2014,33(5):53-56.
[16]CHEN D L,YIN L,GE L F,FAN B J,ZHANG R,SUN J,SHAO G S.Low-temperature and highly selective NO-sensing performance of WO3 nanoplates decorated with silver nanoparticles[J].Sensors and Actuators B:Chemical,2013,185(8):445-455.
[17]CHEN L,TSANG S C.Ag doped WO3-based powder sensor for the detection of NO gas in air[J].Sensors and Actuators B:Chemical,2003,89(1):68-75.
[18]WANG Y Y,ZHANG B,LIU J,LU G Y.Au-loaded mesoporous WO3:Preparation and n-butanol sensing performances[J].Sensors and Actuators B:Chemical,2016,236(5):67-76.
[19]LIU X H,ZHANG J,YANG T,GUO X Z,WU S H,WANG S R.Synthesis of Pt nanoparticles functionalized WO3 nanorods and their gas sensing properties[J].Sensors and Actuators B:Chemical,2011,156(2):918-923.
[20]KABCUM S,KOTCHASAK N,CHANNEI D,TUANTRANONT A,WISITSORAAT A,PHANICHPHANT S.Highly sensitive and selective NO2 sensor based on Au-impregnated WO3 nanorods[J].Sensors and Actuators B:Chemical,2017,252(8):523-536.
[21]SHEN Y B,CHEN X X,WANG W,GONG Y,CHEN S H,LIU JT,WEI D Z,MENG D,SAN X G.Complexing surfactants-mediated hydrothermal synthesis of WO3microspheres for gas sensing applications[J].Materials Letters,2016,163:150-153.
[22]XIA H J,WANG Y,KONG F H,WANG S R,ZHU B L,GUO XZ,ZHANG J,WANG Y M,WU S H.Au-doped WO3-based sensor for NO2 detection at low operating temperature[J].Sensors&Actuators B Chemical,2008,134(1):133-139.
[23]陈享享,沈岩柏,王玮,张宝庆,樊虹,魏德洲.用WO3纳米材料制备矿业安全用NO2气体传感器[J].金属矿山,2016,478(4):158-163.CHEN Xiang-xiang,SHEN Yan-bai,WANG Wei,ZHANGBao-qing,FAN Hong,WEI De-zhou.NO2 gas sensors made from WO3 nanomaterials used for mining safety[J].Metal Mine,2016,478(4):158-163.
[24]SHEN Y B,WANG W,FAN A F,WEI D Z,LIU W G,HAN C,SHEN Y S,MENG D,SAN X G.Highly sensitive hydrogen sensors based on SnO2 nanomaterials with different morphologies[J].International Journal of Hydrogen Energy,2015,40(45):15773-15779.
[25]XIA H J,WANG Y,KONG F H,WANG S R,ZHU B L,GUO XZ,ZHANG J,WANG Y M,WU S H.Au-doped WO3-based sensor for NO2 detection at low operating temperature[J].Sensors and Actuators B:Chemical,2008,134(1):133-139.
[26]LI F,LI C,ZHU L H,GUO W B,SHEN L,WEN S P,RUAN SP.Enhanced toluene sensing performance of gold-functionalized WO3·H2O nanosheets[J].Sensors and Actuators B:Chemical,2016,223(2):761-767.