Co(C_3H_6NS_2)_3·C_6H_(12)N_2S_3单晶的制备及催化性能的研究  

Preparation and Catalysis Capability of Single Crystal Co(C_3H_6NS_2)_3·C_6H_(12)N_2S_3

作　　者：郑怀礼[1,2] 黄小红[1,3] 蒋绍阶[1,2] 杨铀[1,3] 蒋小东[1,2] 

机构地区：[1]重庆大学三峡库区生态环境教育部重点实验室,重庆400045 [2]重庆大学城市建设与环境工程学院,重庆400045 [3]重庆大学化学化工学院,重庆400044

出　　处：《环境科学》2008年第12期3450-3456,共7页Environmental Science

基　　金：国家自然科学基金项目(20777095);重庆市自然科学基金重点项目(CSTC-2006BA7029);三峡库区生态环境教育部重点实验室访问学者基金项目;重庆大学研究生创新基金项目(200706A1A0110231);重庆大学大型设备开放基金项目

摘　　要：采用常温饱和溶液蒸发法,一硫化四甲基秋兰姆与钴（Ⅱ）发生原位反应得到一种新型非均相Fenton催化剂单晶Co（C3H6NS2）3.C6H12N2S3;通过单晶X衍射、红外光谱和C、N和H元素分析对该单晶结构进行了表征;该单晶的空间群为P-1,在不对称单元中有1个Co（Ⅲ）中心,3个新配体C3H7NS2和1个TMTM;Co（Ⅲ）呈现出稍微偏斜的八面体的配位几何构型.利用该单晶催化氧化降解了直接蓝6和直接绿28;结果显示,在酸性和碱性条件下,染料的降解率和矿化率都较高,这是因为活性中心Co（Ⅲ）提高了H2O2的效率.当投加量在1 200--1 600 mg.L^-1之间时,处理90 min后,直接蓝6和直接绿28的降解效率可分别达到94.39%和94.78%.相比之下,不加该单晶光催化剂,其它条件完全相同时,处理90 min后2种染料的降解率均不到45%,降解缓慢.使用后的单晶,通过过滤,可反复使用,有利于降低处理成本.此外还研究了催化反应的动力学,反应遵从Langmuir-Hinshelwood动力学模型;2种染料降解反应速率常数k分别为3.03×10^2和6.25×10^2mg.（L.min）^-1,吸附常数K分别为1.52×10^-4和7.23×10^-5L.mg^-1.A novel heterogeneous Fenton catalyst Co（ C3 H6 NS2 ） 3. C6 H12 N2S3 was synthesized in an in-situ reaction with tetramethyl thiuram monosulfide and cobalt（ Ⅱ ） slowly evaporating at room temperature. Its structure was characterized by single crystal X-ray diffraction（XRD）. Infrared spectrum （IR） and CNH elemental analysis. The catalyst crystallizes in P-1 space group with one cobalt（ Ⅲ ） ion, three new ligands and one dissociated TMTM molecule in the asymmetric unit, presenting a distorted octahedral geometry. Using the single crystal, the results of photocatalytic degradation of direct orchid 6 and direct green 28, as a model reaction, show that when adding between 1 600 and 1 200 mg.L^- 1 of photocatalys, the degradation rate of direct orchid 6 and direct green 28 reach 94.39 % and 94.78 %. The single crystal by filtered after the Fenton reaction can be used repeatedly. Thus the cost of water treatment was reduced. The photocatalytic degradation of direct orchid 6 and direct green 28 have been experimentally demonstrated to follow the Langmuir-Hinshelwood kinetic model, meanwhile the reaction rate constants[3.03 × 10^2 and 6.25 × 10^2 mg.（L.min）^-1] and the adsorption constants （1.52 × 10^-4 and 7.23 × 10^-5 L.mg^-1） have been determined, respectively.

关 键 词：单晶 非均相Fenton法 高级氧化法 染料废水 降解 

分 类 号：X703.1[环境科学与工程—环境工程]