新型多金属氧酸盐K7BiW11O39Sn·11H2O制备及光催化降解模拟染料废水
Synthesis of novel polyoxomatalate K7BiW11O39Sn·11H2O and Photocatalytic degradation of simulated dye wastewater
-
摘要: 本文采用水热合成法首次制备了一种新型多金属氧酸盐,采用扫描电镜(SEM)、扫描电镜-能谱(SEM-EDS)、X射线光电子能谱(XPS)、X射线衍射(XRD)、热重-差热分析(TG-DSC)、紫外可见吸收光谱(UV-Vis)、傅里叶变换红外光谱(FTIR),电感耦合等离子体发射光谱(ICP)等技术对其进行了表征,结果表明,所制备的化合物具有Keggin结构,为非晶体化合物,其分子式为K7BiW11O39Sn·11H2O (BiW11Sn).以酸性红299(AR299)为目标降解污染物,研究了自然日光辐照下BiW11Sn均相光催化AR299水溶液脱色降解活性.结果表明,BiW11Sn能有效的光催化AR299脱色降解.AR299溶液的初使pH值、初始浓度、催化剂投加量、光解时间对AR299光催化降解效果均有影响.20 mL,4 mg·L-1,初始pH值为5.4的AR299水溶液(溶液中BiW11Sn浓度为0.5 g·L-1),阳光下辐照3 h,其脱色率达到93.1%;其光催化降解反应遵循Langmuir-Hinshelwood准一级动力学方程;超氧负离子自由基为光催化降解过程中的重要活性物种.Abstract: A new polyoxometallate photocatalyst was synthesized by hydrothermal coprecipitation in this paper. It was characterized by SEM, SEM-EDS, XPS, XRD, TG-DSC, UV-Vis, FTIR, and ICP. The results indicated that the synthesized compound exhibited a Keggin structure and non-crystalline. The molecular formula of the compound is K7BiW11O39Sn·11H2O (BiW11Sn). Acid red 299 (AR299) was selected as the target degradation pollutant. The photocatalytic activities of BiW11Sn were evaluated by its photocatalytic degradation of AR299 with natural sunlight irradiation in aqueous solution. Results indicated that BiW11Sn effectively and photocatalytically decolorized AR299. The photocatalytic degradation of AR299 was influenced by the dosage of the catalyst, the photolysis time, the initial pH and the initial concentration of AR299. AR299 solution (20 mL, 4 mg·L-1, initial pH 5.4) with BiW11Sn (0.5 g·L-1) was irradiated for 3 h under sunlight, and the decoloration rate was 93.1%. BiW11Sn-mediated photocatalytic degradation of AR299 was a pseudo-first-order reaction and modeled by Langmuir-Hinshelwood-type kinetics. Superoxide anion radical (·O2-) was the important active species in the photocatalytic reaction.
-
Key words:
- photocatalysis /
- polyoxometallate /
- degradation /
- dye waste water
-
-
[1] SHENG F,ZHU X H,WANG W,et al. Synthesis of novel polyoxometalate K6ZrW11O39Sn·12H2O and photocatalytic degradation aqueous azo dye solutions with solar irradiation[J]. Journal of Molecular Catalysis A: Chemical,2014,393:232-239. [2] 邓玲娟,杨春. SnⅡ取代的Keggin型多金属氧酸盐的合成及光催化性能[J]. 应用化学,2007,24(2): 139-143 DENG L J,YANG C. Synthesis of SnⅡ-substituted Keggin-type polyoxometalates and their photocatalytic performance[J]. Chinese Journal of Applied Chemistry,2007,24(2): 139-143(in Chinese).
[3] GARCIA J C,SIMIONATO J I,DA SILVA A E C,et al. Solar photocatalytic degradation of real textile effluents by associated titanium dioxide and hydrogen peroxide[J]. Solar Energy,2009,83(3): 316-322. [4] ZHANG C,ZHU Y. Synthesis of square Bi2WO6 nanoplates as high-activity visible-light-driven photocatalysts[J]. Chemistry of Materials,2005,17(13): 3537-3545. [5] PAN C,ZHU Y. New type of BiPO4 oxy-acid salt photocatalyst with high photocatalytic activity on degradation of dye[J]. Environmental Science and Technology,2010,44(14): 5570-5574. [6] KUDO A,OMORI K,KATO H. A novel aqueous process for preparation of crystal form-controlled and highly crystalline BiVO4 powder from layered vanadates at room temperature and its photocatalytic and photophysical properties[J]. Journal of the American Chemical Society,1999,121(49): 11459-11467. [7] YAO W F,WANG H,XU X H,et al. Photocatalytic property of bismuth titanate Bi2Ti2O7[J]. Applied Catalysis A: General,2004,259(1): 29-33. [8] HUANG H,CHEN G,ZHANG Y. Two Bi-based phosphate photocatalysts: Crystal structure,optical property and photocatalytic activity[J]. Inorganic Chemistry Communications,2014,44: 46-49. [9] 熊世威,方艳芬,李新玉,等. BiPO4纳米棒制备及光催化降解罗丹明B[J]. 环境化学,2013,32(10): 1856-1862. XIONG S W,FANG Y F,LI X Y, et al. Synthesis of BiPO4 and its photocatalytic degradation rhodamine B toxic organic pollutants[J]. Environmental Chemistry,2013,32(10): 1856-1862(in Chinese).
[10] 蔡伟民,龙明策. 环境光催化材料与光催化净化技术[M]. 上海: 上海交通大学出版社,2011. CAI W M,LONG Y M. Environmental photocatalytic material and photocatalytic purification technology[M]. Sahnghai: Shanghai Jiaotong University Press,2011(in Chinese). [11] 王恩波,胡长文,许林. 多酸化学导论[M]. 北京: 化学工业出版社,1998. Wang E B,HU C W,XU L. Introduction of Polyoxometalates Chemistry[M]. Beijing: Chemical Industrial Press,1998(in Chinese). [12] 朱秀华,朱敏,王炜等. 无机离子对磷钨酸光催化活性艳橙脱色降解的影响[J]. 环境化学,2010,29(1): 82-84. ZHU X H,ZHU M,WANG W,et al. The effect of inorganic ions on photolysis of reactive bright organge solution[J]. Environmental Chemistry,2010,29(1): 82-84(in Chinese).
[13] KORMALI P,TROUPIS A,TRIANTIS T,et al. Photocatalysis by polyoxometallate and TiO2: A comparative study[J]. Catalysis Today,2007,124(3-4):149-155. [14] TROUPIS A,TRIANTIS T M,GKIKA E. Photocatalytic reductive-oxidative degradation of Acid Orange 7 by polyoxometallate[J]. Applied Catalysis B: Environmental,2009,86:98-107. [15] HU M,XU Y. Photocatalytic degradation of tetile dye X3B by heteropolyoxometallate acids[J]. Chemosphere,2004,54(3):431-434. [16] [17] GHAEDI M,ANDIKAEY Z,DANESHFAR A,et al. Removal of Acid Red 299 dye on gold nanoparticles loaded on activated carbon: Kinetic and thermodynamic investigation of the removal process[J]. Desalination and Water Treatment,2014,52(28-30): 5494-5503. [18] XU Z H,WANG X L,LI Y G,et al. A novel bismuth ion-bridged chainlike assembly from paradodecatungstate[H2W12O42]10- anions:(NH4)7[Bi(H2W12O42)]·20 H2O[J]. Inorganic Chemistry Communications,2007,10(3): 276-278. [19] Palermo V,Sathicq Á G,Vázquez P G,et al. Doped Keggin heteropolyacids as catalysts in sulfide oxidation[J]. Reaction Kinetics,Mechanisms and Catalysis,2011,104(1): 181-195. [20] 崔克宇. 多钨铋酸盐和稀土、碱土金属的配位组装、多维结构和性质研究[D]. 长春: 东北师范大学博士学位论文,2013. CUI K Y. Coordination assembly multidimensional structures and properties of lanthanide,alkaline-earth containing tungstobismuthate coordination compounds[D]. Chang Chun: Northeast Normal University,2013(in Chinese). [21] 王永净,张汉辉,黄长沧,等. 两种含铋的杂多化合物的光谱研究[J]. 光谱学与光谱分析,2006,26(2): 287-290. WANG Y J,ZHANG H H,HUANG C C,et al. Spectral study of two Bi(Ⅲ) contained heteropolymate compounds[J]. Specroscopy and Spectral Analysis,2006,26(2): 287-290(in Chinese).
[22] 孙春艳. 过渡金属多钨酸盐的合成、结构及性质研究[D]. 长春: 东北师范大学硕士学位论文,2006. SUN C Y. Synthese,structures and properties of some new polyoxotungstates containing transition metal[D]. Chang Chun: Northeast Normal University,2013(in Chinese). [23] OZER R R,FERRY J L. Kinetic probes of the mechanism of polyoxometalate-mediated photocatalytic oxidation of chlorinated organics[J]. Journal of Physical Chemistry B,2000,104(40): 9444-9448. [24] JI H H,CHANG F,HU X F,et al. Photocatalytic degradation of 2,4,6-trichlorophenol over g-C3N4 under visible light irradiation[J]. Chemical Engineering Journal,2013,218: 183-190. [25] DOORSLAER X V,HEYNDERICKX P M,DEMEESTERE K,et al. TiO2 mediated heterogeneous photocatalytic degradation of moxifloxacin: Operational variables and scavenger study[J]. Applied Catalysis B: Environmental,2012,111-112:150-156. -

计量
- 文章访问数: 817
- HTML全文浏览数: 744
- PDF下载数: 664
- 施引文献: 0