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·1062 工程科学学报,第37卷,第8期 0.8 [4]Ji T H,Yang F,Zhou J Y,et al.BiVO/TiO2 nanocomposite ·空白样 。Ti0, photocatalyst with visible light response.Spectrosc Spectral Anal, 2010,30(7):1944 0.6 BiVO ¥BiVO./TiO, (嵇天浩,杨芳,周娇艳,等.可见光响应的BVO4TO2纳米 BiVO/TiO,-GR 复合光催化剂.光谱学与光分析,2010,30(7):1944) 3T 0.4 Hu Y,Li D Z,Zheng Y,et al.BiVO/TiO,nanocrystalline hetero- structure:a wide spectrum responsive photocatalyst towards the highly efficient decomposition of gaseous benzene.Appl Catal B,2011,104 0.2 (1-2):30 [6]Guo L,Wang D J,Fu F,et al.Synthesis and photocatalytic prop- erties of TiO2/BivO photocatalyst by microwave-assisted hydro- 06 05 1.0152.025 3.0 thermal method.Appl Chem Ind.2012,41(2):259 时间小 (郭莉,王丹军,付蜂,等.TO2/BV04复合光催化剂的微波辅 图8不同光催化剂的动力学线性模拟曲线 助水热法合成及催化性能研.应用化工,2012,41(2):259) Fig.8 Kinetic linear simulation curves of different photocatalysts ] Cao B W,Peng J H,Xu Y H.Simulated sunlight-driven degrada- tion of Rhodamine B by porous peanut-ike Ti/BiVO compos- 表3各催化剂在可见光下的表观速率常数K和禁带宽度E ite.J Cluster Sci,2013,24(3):771 Table 3 Apparent rate constant K and the bandgap E of photocatalysts 8]Du A J,Ng Y H,Bell NJ,ct al.Hybrid graphene/titania nanocom- in visible light posite:interface charge transfer,hole doping,and sensitization for 样品名称 K/h-1 EleV visible light response.J Phys Chem Lett,2011,2(8):894 空白样 0.01871 9] Zhang Y H,Zhang N,Tang Z R,et al.Graphene transforms wide TiO2 0.02307 2.92 band gap ZnS to a visible light photocatalyst:the new role of gra- BiVO 0.06273 2.29 phene as a macromolecular photosensitizer.ACS Nano,2012,6 BiVO/TiO2 0.12545 2.25 (11):9777 BiVO,/TiO2-GR 0.12605 2.00 [10]Hu Y J,Jin J,Zhang H,et al.Graphene:synthesis,functional- ization and applications in chemistry.Acta Phys Chim Sin, -lg(C1C。)随1的变化呈现很好的线性关系,说 2010,26(8):2073 明各光催化剂降解亚甲基蓝溶液的反应基本符合一级 (胡耀娟,金娟,张卉,等.石墨烯的制备、功能化及在化学 动力学反应,遵从Langmuir--Hinshewood光催化动力学 中的应用.物理化学学报,2010.26(8):2073) 0] Wang J X.Wang P X,Cao Y T,et al.A high efficient photo- 模型.BiVO,/TiO2GR的表观速率常数K是TiO2的 catalyst Ags VOTiO/graphene nanocomposite with wide spee- 5.5倍,是BiV0,的2.0倍,说明BiVO,/Ti02GR复合 tral response.Appl Catal B,2013,136-137:94 光催化剂在可见光区具有优越的光催化活性 02] Marcano D C,Kosynkin D V,Berlin J M,et al.Improved syn- thesis of graphene oxide.ACS Nano,2010,4(8):4806 3结论 [13]Zhang Y H,Tang Z R,Fu X Z,et al.Ti02-graphene nanocom- (1)通过溶剂热法制备了在可见光具有光催化活 posites for gas-phase photocatalytic degradation of volatile aromatic pollutant:is TiO,-graphene truly different from other TiO,-carbon 性的BiV0,/TiO2GR复合光催化剂. composite materials?ACS Nano,2010,4(12):7303 (2)该复合光催化剂在530~800nm可见光范围 041 Zhang L W,Fu H B,Zhu Y F.Efficient Ti02 photocatalysts 具有很强的吸收能力,石墨烯作为光敏化材料能有效 from surface hybridization of TiO particles with graphite-ike car- 地将吸收波长向长波方向移动,拓宽光谱响应范围. bon.Adu Funct Mater,2008,18 (15)2180 05] (3)该复合光催化剂荧光强度低,石墨烯的引入 Liu K J.Chang Z D,Li WJ,et al.Visible-light-driven magnet- ic BiVO photocatalyst:synthesis and photocatalytic perform- 有效地抑制光生电子一空穴的复合,提高光生载流子 ance.Chin J Inorg Chem,2011,27(8):1465 的分离效率,从而增强复合光催化剂的催化活性 (刘坤杰,常志东,李文军,等.磁性BVO4可见光催化材料 的制备及光催化性能.无机化学学报,2011,27(8):1465) 参考文献 [16]Yu C F,Dong S Y,Feng J L,et al.Controlled synthesis of uni- [1]Zhou K F,Zhu Y H,Yang X L,et al.Preparation of graphene- form BivO,microcolumns and advanced visible-ight-driven pho- Ti0,composites with enhanced photocatalytic activity.New J tocatalytic activity for the degradation of metronidazole-contained Chem,2011,35(2):353 wastewater.Enriron Sci Pollut Res,2014,21(4):2837 Zhang A P,Zhang JZ.Characterization and photocatalytic properties 17] Yang HH,Kershaw V,Wang Y,et al.Shuttling photoelectro- of Au/BiVO4 composites.J Alloys Compd,2010,491 (1-2):631 chemical electron transport in tricomponent Cds/rGO/TiO,nano- B3]Yan Y,Sun S F,Song Y,et al.Microwave-assisted in situ syn- composites.J Phys Chem C,2013,117(40):20406 thesis of reduced graphene oxide-BiVO composite photocatalysts 8] Yan X L,Ohno T,Nishijima K,et al.Is methylene blue an appro- and their enhanced photocatalytic performance for the degradation priate substrate for a photocatalytic activity test?A study with visi- of ciprofloxacin.J Hazard Mater,2013,250-251:106 ble-ight responsive titania.Chem Phys Lett,429(4-6):606工程科学学报,第 37 卷,第 8 期 图 8 不同光催化剂的动力学线性模拟曲线 Fig. 8 Kinetic linear simulation curves of different photocatalysts 表 3 各催化剂在可见光下的表观速率常数 K 和禁带宽度 E Table 3 Apparent rate constant K and the bandgap E of photocatalysts in visible light 样品名称 K/ h - 1 E /eV 空白样 0. 01871 — TiO2 0. 02307 2. 92 BiVO4 0. 06273 2. 29 BiVO4 /TiO2 0. 12545 2. 25 BiVO4 /TiO2 --GR 0. 12605 2. 00 - lg( C/C0 ) 随 t 的变化呈现很好的线性关系,说 明各光催化剂降解亚甲基蓝溶液的反应基本符合一级 动力学反应,遵从 Langmuir--Hinshewood 光催化动力学 模型. BiVO4 / TiO2 --GR 的表观速率常数 K 是 TiO2 的 5. 5 倍,是 BiVO4 的 2. 0 倍,说明 BiVO4 / TiO2 --GR 复合 光催化剂在可见光区具有优越的光催化活性. 3 结论 ( 1) 通过溶剂热法制备了在可见光具有光催化活 性的 BiVO4 / TiO2 --GR 复合光催化剂. ( 2) 该复合光催化剂在 530 ~ 800 nm 可见光范围 具有很强的吸收能力,石墨烯作为光敏化材料能有效 地将吸收波长向长波方向移动,拓宽光谱响应范围. ( 3) 该复合光催化剂荧光强度低,石墨烯的引入 有效地抑制光生电子--空穴的复合,提高光生载流子 的分离效率,从而增强复合光催化剂的催化活性. 参 考 文 献 [1] Zhou K F,Zhu Y H,Yang X L,et al. Preparation of graphene-- TiO2 composites with enhanced photocatalytic activity. New J Chem,2011,35( 2) : 353 [2] Zhang A P,Zhang J Z. Characterization and photocatalytic properties of Au/BiVO4 composites. J Alloys Compd,2010,491( 1--2) : 631 [3] Yan Y,Sun S F,Song Y,et al. Microwave-assisted in situ syn￾thesis of reduced graphene oxide--BiVO4 composite photocatalysts and their enhanced photocatalytic performance for the degradation of ciprofloxacin. J Hazard Mater,2013,250--251: 106 [4] Ji T H,Yang F,Zhou J Y,et al. BiVO4 /TiO2 nanocomposite photocatalyst with visible light response. Spectrosc Spectral Anal, 2010,30( 7) : 1944 ( 嵇天浩,杨芳,周娇艳,等. 可见光响应的 BiVO4 /TiO2 纳米 复合光催化剂. 光谱学与光分析,2010,30( 7) : 1944) [5] Hu Y,Li D Z,Zheng Y,et al. BiVO4 /TiO2 nanocrystalline hetero￾structure: a wide spectrum responsive photocatalyst towards the highly efficient decomposition of gaseous benzene. Appl Catal B,2011,104 ( 1--2) : 30 [6] Guo L,Wang D J,Fu F,et al. Synthesis and photocatalytic prop￾erties of TiO2 /BiVO4 photocatalyst by microwave-assisted hydro￾thermal method. Appl Chem Ind,2012,41( 2) : 259 ( 郭莉,王丹军,付峰,等. TiO2 /BiVO4 复合光催化剂的微波辅 助水热法合成及催化性能研. 应用化工,2012,41( 2) : 259) [7] Cao B W,Peng J H,Xu Y H. Simulated sunlight-driven degrada￾tion of Rhodamine B by porous peanut-like TiO2 /BiVO4 compos￾ite. J Cluster Sci,2013,24( 3) : 771 [8] Du A J,Ng Y H,Bell N J,et al. Hybrid graphene/titania nanocom￾posite: interface charge transfer,hole doping,and sensitization for visible light response. J Phys Chem Lett,2011,2( 8) : 894 [9] Zhang Y H,Zhang N,Tang Z R,et al. Graphene transforms wide band gap ZnS to a visible light photocatalyst: the new role of gra￾phene as a macromolecular photosensitizer. ACS Nano,2012,6 ( 11) : 9777 [10] Hu Y J,Jin J,Zhang H,et al. Graphene: synthesis,functional￾ization and applications in chemistry. Acta Phys Chim Sin, 2010,26( 8) : 2073 ( 胡耀娟,金娟,张卉,等. 石墨烯的制备、功能化及在化学 中的应用. 物理化学学报,2010,26( 8) : 2073) [11] Wang J X,Wang P X,Cao Y T,et al. A high efficient photo￾catalyst Ag3 VO4 /TiO2 /graphene nanocomposite with wide spec￾tral response. Appl Catal B,2013,136--137: 94 [12] Marcano D C,Kosynkin D V,Berlin J M,et al. Improved syn￾thesis of graphene oxide. ACS Nano,2010,4( 8) : 4806 [13] Zhang Y H,Tang Z R,Fu X Z,et al. TiO2 --graphene nanocom￾posites for gas--phase photocatalytic degradation of volatile aromatic pollutant: is TiO2 --graphene truly different from other TiO2 --carbon composite materials? ACS Nano,2010,4( 12) : 7303 [14] Zhang L W,Fu H B,Zhu Y F. Efficient TiO2 photocatalysts from surface hybridization of TiO2 particles with graphite-like car￾bon. Adv Funct Mater,2008,18( 15) : 2180 [15] Liu K J,Chang Z D,Li W J,et al. Visible-light-driven magnet￾ic BiVO4 photocatalyst: synthesis and photocatalytic perform￾ance. Chin J Inorg Chem,2011,27( 8) : 1465 ( 刘坤杰,常志东,李文军,等. 磁性 BiVO4 可见光催化材料 的制备及光催化性能. 无机化学学报,2011,27( 8) : 1465) [16] Yu C F,Dong S Y,Feng J L,et al. Controlled synthesis of uni￾form BiVO4 microcolumns and advanced visible-light-driven pho￾tocatalytic activity for the degradation of metronidazole-contained wastewater. Environ Sci Pollut Res,2014,21( 4) : 2837 [17] Yang H H,Kershaw S V,Wang Y,et al. Shuttling photoelectro￾chemical electron transport in tricomponent CdS / rGO /TiO2 nano￾composites. J Phys Chem C,2013,117( 40) : 20406 [18] Yan X L,Ohno T,Nishijima K,et al. Is methylene blue an appro￾priate substrate for a photocatalytic activity test? A study with visi￾ble-light responsive titania. Chem Phys Lett,2006,429( 4--6) : 606 · 2601 ·
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