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.