具有高活性和稳定性的半导体光催化材料是太阳能光催化制氢领域的研究热点,其中CdS胶体颗粒催化剂因其合适的禁带宽度和带边位置以及较低的原料价格而广受关注.但它在水溶液中不稳定,易受光腐蚀,因而限制了其应用.目前人们致力于用各种方法提高其稳定性,包括各种纳米结构的应用、复合其他催化剂材料以及不同晶相结构复合.ZnS是一种宽禁宽半导体,禁带宽度为3.6 eV,常被用来与CdS形成固溶体调控其能带结构,从而提高其性能和稳定性.其中核壳结构CdS/ZnS异质结具有骑跨型(I型)能带结构,具有特殊的光学和电学性质,在量子点LED和量子点生物荧光显示剂方面获得关注和应用,同时也显示了良好的光催化性能.研究人员对核壳结构CdS/ZnS异质结材料中ZnS壳层厚度对其光学性能包括荧光效率等的影响进行了研究,然而ZnS壳层厚度、颗粒尺寸及其表面处理对光催化性能影响方面的报道很少.本文发展了一种简易的两步法,制备了核壳结构CdS/ZnS微米球光催化剂.首先采用超声喷雾热分解法制备CdS微米球,然后以水浴法在CdS微米球上生长ZnS壳层.采用扫描电镜(SEM)、X射线衍射(XRD)、紫外一可见吸收光谱(UV一vis)和透射电镜(TEM)对所得样品进行了表征.SEM和TEM结果显示,所得微米球为完整包裹的球形核壳结构;XRD表征证实CdS核与ZnS壳层皆为六角相晶型;光催化性能表征结果显示,该样品的光催化制氢性能远高于单独的CdS微米球以及同法所制的ZnS微米球.通过改变前驱液浓度(Zn源浓度分别为0.2,0.3和0.5 mol/L)获得了三种不同厚度的核壳结构CdS/ZnS微米球,X射线荧光光谱结果证实了其壳层厚度成功调控.UV一vis结果发现,其吸收边由内核CdS决定,受壳层厚度的影响不大.光致荧光发射光谱分析发现,随着壳层厚度的增加,其540 nm处的CdS带边发射峰强度逐渐增大.这可?
CdS/ZnS core-shell microparticles were prepared by a simple two-step method combining ultrasonic spray pyrolysis and chemical bath deposition.The core-shell structures showed enhanced photocatalytic properties compared with those of CdS or ZnS spherical particles.CdS/ZnS photocatalysts with different amount of ZnS loaded as shells were prepared by adjusting the concentrations of Zn and S precursors during synthesis.The optical properties and photocatalytic activity for hydrogen production were investigated and the amount of ZnS loaded as shell was optimized.Thermal annealing and hydrothermal sulfurization treatments were applied to the core-shell structure and both treatments enhanced the material's photocatalytic activity and stability by eliminating crystalline defects and surface states.The result showed that thermal annealing treatment improved the bulk crystallinity and hydrothermal sulfurization improved the surface properties.The sample subjected to both treatments showed the highest photocatalytic activity.These results indicate that CdS/ZnS core-shell microspheres are a simple structure that can be used as efficient photocatalysts.The hydrothermal sulfurization treatment may also be a useful surface treatment for metal sulfide photocatalysts.The simple two-step method provides a promising approach to the large-scale synthesis of core-shell microsphere catalysts.