g-C_3N_4/TiO_2纳米管阵列的制备及光催化性能的研究
|
摘要
目的获得在可见光下光催化活性较好,且可回收、可重复利用的光催化材料。方法在钛基底上采用阳极氧化法制备Ti O2纳米管阵列(Ti O2 NTAs),将Ti O2 NTAs在10%尿素溶液中浸渍不同时间后,在氮气保护下高温热分解,制备g-C_3N_4/TiO_2 NTAs复合薄膜。采用XRD、SEM、TEM对复合薄膜进行物相及形貌的表征,在可见光照射下,通过亚甲基蓝溶液的催化降解实验来评估复合薄膜的光催化活性。结果在10%尿素溶液中浸渍不同时间后所获得的g-C_3N_4/TiO_2 NTAs样品,其可见光催化活性均较纯Ti O2 NTAs有所提高,而且随浸渍时间的增加,其可见光催化活性依次增加。浸渍时间为6 h的g-C_3N_4/TiO_2 NTAs样品,在可见光下的光催化活性最高,在120min内对亚甲基蓝的降解率可达73%。继续增加浸渍时间,所获得的Ti O2 NTAs样品的可见光催化活性有所降低。结论 g-C3N4与Ti O2 NTAs复合,可以有效提高Ti O2 NTAs的光催化活性,其原因是g-C3N4的复合提高了载流子的传递效率,同时也提高了对可见光的吸收。
The work aims to obtain a kind of photocatalytic material with high activity and able to be recycled and reused under visible light. Firstly, TiO2 nanotubes arrays(TiO2 NTAs) were prepared on titanium substrate by anodic oxidation method. Then, g-C_3N_4/TiO_2 NTAs composite films were prepared through high temperature thermal decomposition under nitrogen protection by dipping TiO2 NTAs in 10% urea solution for different time. XRD, SEM and TEM were used to characterize the phase and morphology of the composite films. Under visible light irradiation, the photocatalytic properties of composite films were evaluated by the catalytic degradation experiments of methylene blue solution. The photocatalytic activity of g-C_3N_4/TiO_2 NTAs dipped in the 10 % urea solution for different time was higher than that of pure TiO2 NTAs. Simultaneously, the photocatalytic activity of g-C_3N_4/TiO_2 NTAs was increasing with the increase of dipping time. Moreover, the photocatalytic activity of g-C_3N_4/TiO_2 NTAs dipped in the urea solution for 6 h was the highest under the visible light and the degradation rate of methylene blue could reach 73% for 120 min. With the continuous prolonging of dipping time in urea solution, the photocatalytic ac-tivity of g-C_3N_4/TiO_2 NTAs decreased. g-C3 N4 combined with TiO2 NTAs can improve the photocatalytic activity of TiO2 NTAs, because the composite g-C3 N4 improves the transmission efficiency of carrier and also promotes the absorptance of visible light.
The work aims to obtain a kind of photocatalytic material with high activity and able to be recycled and reused under visible light. Firstly, TiO2 nanotubes arrays(TiO2 NTAs) were prepared on titanium substrate by anodic oxidation method. Then, g-C_3N_4/TiO_2 NTAs composite films were prepared through high temperature thermal decomposition under nitrogen protection by dipping TiO2 NTAs in 10% urea solution for different time. XRD, SEM and TEM were used to characterize the phase and morphology of the composite films. Under visible light irradiation, the photocatalytic properties of composite films were evaluated by the catalytic degradation experiments of methylene blue solution. The photocatalytic activity of g-C_3N_4/TiO_2 NTAs dipped in the 10 % urea solution for different time was higher than that of pure TiO2 NTAs. Simultaneously, the photocatalytic activity of g-C_3N_4/TiO_2 NTAs was increasing with the increase of dipping time. Moreover, the photocatalytic activity of g-C_3N_4/TiO_2 NTAs dipped in the urea solution for 6 h was the highest under the visible light and the degradation rate of methylene blue could reach 73% for 120 min. With the continuous prolonging of dipping time in urea solution, the photocatalytic ac-tivity of g-C_3N_4/TiO_2 NTAs decreased. g-C3 N4 combined with TiO2 NTAs can improve the photocatalytic activity of TiO2 NTAs, because the composite g-C3 N4 improves the transmission efficiency of carrier and also promotes the absorptance of visible light.
引文
[1]YUAN Zhi-min,TANG Rui,ZHANG Yuan,et al.Enhanced photovoltaic performance of dye-sensitized solar cells based on Co9S8,nanotube array counter electrode and TiO2/g-C3N4,heterostructure nanosheet photoanode[J].Journal of alloys and compounds,2017,691:983-991.
[2]PHAM Van-viet,BUI Dai-phat,TRAN Hong-huy,et al.Photoreduction route for Cu2O/Ti O2 nanotubes junction for enhanced photocatalytic activity[J].RSC advanced,2018,8(22):12420-12427.
[3]PAN Chao,JIA Jia,HU Xiao-yun,et al.In-situ construction of g-C3N4/TiO2 heterojunction films with enhanced photocatalytic activity over magnetic driven rotating frame[J].Applied surface science,2018,430:283-292.
[4]NGUYEN Van-manh,LI Wi-li,PHAM Van-huan,et al.A Cd S/ZnSe/TiO2 nanotube array and its visible light photocatalytic activities[J].Journal of colloid and interface science,2016,462:389-396.
[5]邓安平,黄应平,方艳芬,等.TiO2纳米管的制备和光催化降解有毒有机污染物[J].环境化学,2009,28(2):202-205.DENG An-ping,HUANG Ying-ping,FANG Yan-fen,et al.Preparation of TiO2 nanotubes and photocatalytic degradation of toxic organic pollutants[J].Environmental chemistry,2009,28(2):202-205.
[6]ROY P,BERGER S,SCHMKI P.TiO2 nanotubes synthesis and applications[J].Angewandte chemie international edition,2011,50(13):2904-2939.
[7]李运涛,牛俊丽,许淑嫱,等.高铝玻璃减薄优化工艺研究[J].陕西科技大学学报(自然科学版),2017,35(3):86-89.LI Yun-tao,NIU Jun-li,XU Shu-qiang,et al.Study on optimizing process of thinning high-aluminum glass[J].Journal of Shaanxi University of Science and Technology(natural science edition),2017,35(3):86-89.
[8]段体岗,马力,侯健,等.花状形貌Ti O2-NTs@Sb-Sn O2电极的脉冲电沉积法制备及电催化性能研究[J].表面技术,2018,47(2):36-41.DUAN Ti-gang,MA Li,HOU Jian,et al.Pulse electrodeposition of Ti O2-NTs@Sb-SnO2 electrode with flower shape and electrocatalytic performance[J].Surface technology,2018,47(2):36-41.
[9]高岩.钙和二氧化钛负载石墨烯储氢性能力第一性原理研究[D].天津:天津大学,2012.GAO Yan.First-principles study of the ability of calcium and titania to support graphene hydrogen storage[D].Tianjing:Tianjin University,2012.
[10]李雪飞.二氧化钛纳米材料合成及其氢敏特性与光催化性能研究[D].北京:北京理工大学,2018.LI Xue-fei.Synthesis hydrogen sensing properties and photocatalytic properties of titanium dioxide nanomaterials[D].Beijing:Beijing Institute of Technology,2018.
[11]GOUVEA C A K,WYPYCH F,MORAES S G,et al.Semiconductor-assisted photocatalytic degradation of reactive dyes in aqueous solution[J].Chemosphere,2000,40:433-440.
[12]杨冰洋.二氧化钛及其复合物的光催化性能研究[D].北京:北京交通大学,2016.YANG Bing-yang.Photocatalytic performance of titanium dioxide and its composites[D].Beijing:Beijing Jiaotong University,2016.
[13]LU Zhao,ZENG Lei,SONG Wu-lin,et al.In-situ synthesis of C-Ti O2/g-C3N4,heterojunction nanocomposite as highly visible light active photocatalyst originated from effective interfacial charge transfer[J].Applied catalysis B:Environmental,2017,202:489-499.
[14]GUO Li-qing,HU Ya-wei,YU Bin,et al.Incorporating TiO2 nanotubes with a peptide of D-amino K122-4(D)for enhanced mechanical and photocatalytic properties[J].Scientific reports,2016,6:22247.
[15]ZHOU Dan-tong,ZENG Lei,SONG Wu-lin,et al.In-situ construction of all-solid-state Z-scheme g-C3N4/TiO2,nanotube arrays photocatalyst with enhanced visible light induced properties[J].Solar energy materials and solar cells,2016,157:399-405.
[16]BOONPRAKOB N,WETCHAKUN N,PHANICHPHANTS,et al.Enhanced visible light photocatalytic activity of g-C3N4/TiO2 films[J].Journal of colloid and interface science,2014,417:402-409.
[17]TONG Zhen-wei,YANG Dong,XIAO Tian-xiong,et al.Biomimetic fabrication of g-C3N4/TiO2,nanosheets with enhanced photocatalytic activity toward organic pollutant degradation[J].Amsterdam netherlands,2015,260:117-125.
[18]KANG Qi,WANG Xu-xiang,MA Xiao-long,et al.Sensitive detection of ascorbic acid and alkaline phosphatase activity by double-channel photoelectrochemical detection design based on g-C3N4/TiO2 nanotubes hybrid film[J].Sensors and actuators B chemical,2016,230:231-241.
[19]WEI Xiao-na,WANG Hui-long,WANG Xin-kui,et al.Facile fabrication of mesoporous g-C3N4/TiO2,photocatalyst for efficient degradation of DNBP under visible light irradiation[J].Applied surface science,2017,426:1271-1280.
[20]胡亚微,王晓芳,柯钰.TiO2纳米管阵列的制备及光催化活性[J].陕西科技大学学报,2018,36(1):63-67.HU Ya-wei,WANG Xiao-fang,KE Yu.Preparation of TiO2 nanotube arrays and their photocatalytic activity[J].Journal of Shaanxi University of Science and Technology,2018,36(1):63-67.
[21]NEZAR S,LAOUFI N A.Electron acceptors effect on photocatalytic degradation of metformin under sunlight irradiation[J].Solar energy,2018,164:267-275.
[22]PAN Cheng-si,ZHU Yong-fa.New type of Bi PO4oxy-acid salt photocatalyst with high photocatalytic activity on degradation of dye[J].Environmental science&technology,2010,44:5570-5574.
[2]PHAM Van-viet,BUI Dai-phat,TRAN Hong-huy,et al.Photoreduction route for Cu2O/Ti O2 nanotubes junction for enhanced photocatalytic activity[J].RSC advanced,2018,8(22):12420-12427.
[3]PAN Chao,JIA Jia,HU Xiao-yun,et al.In-situ construction of g-C3N4/TiO2 heterojunction films with enhanced photocatalytic activity over magnetic driven rotating frame[J].Applied surface science,2018,430:283-292.
[4]NGUYEN Van-manh,LI Wi-li,PHAM Van-huan,et al.A Cd S/ZnSe/TiO2 nanotube array and its visible light photocatalytic activities[J].Journal of colloid and interface science,2016,462:389-396.
[5]邓安平,黄应平,方艳芬,等.TiO2纳米管的制备和光催化降解有毒有机污染物[J].环境化学,2009,28(2):202-205.DENG An-ping,HUANG Ying-ping,FANG Yan-fen,et al.Preparation of TiO2 nanotubes and photocatalytic degradation of toxic organic pollutants[J].Environmental chemistry,2009,28(2):202-205.
[6]ROY P,BERGER S,SCHMKI P.TiO2 nanotubes synthesis and applications[J].Angewandte chemie international edition,2011,50(13):2904-2939.
[7]李运涛,牛俊丽,许淑嫱,等.高铝玻璃减薄优化工艺研究[J].陕西科技大学学报(自然科学版),2017,35(3):86-89.LI Yun-tao,NIU Jun-li,XU Shu-qiang,et al.Study on optimizing process of thinning high-aluminum glass[J].Journal of Shaanxi University of Science and Technology(natural science edition),2017,35(3):86-89.
[8]段体岗,马力,侯健,等.花状形貌Ti O2-NTs@Sb-Sn O2电极的脉冲电沉积法制备及电催化性能研究[J].表面技术,2018,47(2):36-41.DUAN Ti-gang,MA Li,HOU Jian,et al.Pulse electrodeposition of Ti O2-NTs@Sb-SnO2 electrode with flower shape and electrocatalytic performance[J].Surface technology,2018,47(2):36-41.
[9]高岩.钙和二氧化钛负载石墨烯储氢性能力第一性原理研究[D].天津:天津大学,2012.GAO Yan.First-principles study of the ability of calcium and titania to support graphene hydrogen storage[D].Tianjing:Tianjin University,2012.
[10]李雪飞.二氧化钛纳米材料合成及其氢敏特性与光催化性能研究[D].北京:北京理工大学,2018.LI Xue-fei.Synthesis hydrogen sensing properties and photocatalytic properties of titanium dioxide nanomaterials[D].Beijing:Beijing Institute of Technology,2018.
[11]GOUVEA C A K,WYPYCH F,MORAES S G,et al.Semiconductor-assisted photocatalytic degradation of reactive dyes in aqueous solution[J].Chemosphere,2000,40:433-440.
[12]杨冰洋.二氧化钛及其复合物的光催化性能研究[D].北京:北京交通大学,2016.YANG Bing-yang.Photocatalytic performance of titanium dioxide and its composites[D].Beijing:Beijing Jiaotong University,2016.
[13]LU Zhao,ZENG Lei,SONG Wu-lin,et al.In-situ synthesis of C-Ti O2/g-C3N4,heterojunction nanocomposite as highly visible light active photocatalyst originated from effective interfacial charge transfer[J].Applied catalysis B:Environmental,2017,202:489-499.
[14]GUO Li-qing,HU Ya-wei,YU Bin,et al.Incorporating TiO2 nanotubes with a peptide of D-amino K122-4(D)for enhanced mechanical and photocatalytic properties[J].Scientific reports,2016,6:22247.
[15]ZHOU Dan-tong,ZENG Lei,SONG Wu-lin,et al.In-situ construction of all-solid-state Z-scheme g-C3N4/TiO2,nanotube arrays photocatalyst with enhanced visible light induced properties[J].Solar energy materials and solar cells,2016,157:399-405.
[16]BOONPRAKOB N,WETCHAKUN N,PHANICHPHANTS,et al.Enhanced visible light photocatalytic activity of g-C3N4/TiO2 films[J].Journal of colloid and interface science,2014,417:402-409.
[17]TONG Zhen-wei,YANG Dong,XIAO Tian-xiong,et al.Biomimetic fabrication of g-C3N4/TiO2,nanosheets with enhanced photocatalytic activity toward organic pollutant degradation[J].Amsterdam netherlands,2015,260:117-125.
[18]KANG Qi,WANG Xu-xiang,MA Xiao-long,et al.Sensitive detection of ascorbic acid and alkaline phosphatase activity by double-channel photoelectrochemical detection design based on g-C3N4/TiO2 nanotubes hybrid film[J].Sensors and actuators B chemical,2016,230:231-241.
[19]WEI Xiao-na,WANG Hui-long,WANG Xin-kui,et al.Facile fabrication of mesoporous g-C3N4/TiO2,photocatalyst for efficient degradation of DNBP under visible light irradiation[J].Applied surface science,2017,426:1271-1280.
[20]胡亚微,王晓芳,柯钰.TiO2纳米管阵列的制备及光催化活性[J].陕西科技大学学报,2018,36(1):63-67.HU Ya-wei,WANG Xiao-fang,KE Yu.Preparation of TiO2 nanotube arrays and their photocatalytic activity[J].Journal of Shaanxi University of Science and Technology,2018,36(1):63-67.
[21]NEZAR S,LAOUFI N A.Electron acceptors effect on photocatalytic degradation of metformin under sunlight irradiation[J].Solar energy,2018,164:267-275.
[22]PAN Cheng-si,ZHU Yong-fa.New type of Bi PO4oxy-acid salt photocatalyst with high photocatalytic activity on degradation of dye[J].Environmental science&technology,2010,44:5570-5574.