Porphyrin based nanomaterials have attracted widespread attention due to their similarity of the key dyes of natural photosynthesis. To develop new chromophores for photoelectrochemical (PEC) devices, in this work, we synthesized 3 different aggregated nanostructures of meso-tetra(4-carboxyphenyl)porphine (TCPP) via self-assembly technique. The micro-environments of porphyrin self-assembly were modulated by using sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) as “soft template” respectively, aqueous solution without surfactant as control. Due to the different driving forces of self-assembly, the as-prepared TCPP nanostructures exhibited remarkably different morphologies, electrochemical and PEC properties. Among them, the self-assembled TCPP using SDS (SA-TCPP/SDS) possessed enhanced PEC performance. In presence of dopamine, a significant photocurrent response can be feasibly obtained in aqueous media at −0.4 V (vs. Ag/AgCl). Moreover, the self-assembly process was also investigated using in situ UV–visible spectroscopy and the corresponding structure formation mechanisms were proposed.

基于卟啉的纳米材料由于其与天然光合作用关键染料的相似性而受到广泛关注。为了开发用于光电化学（PEC）装置的新发色团，在这项工作中，我们通过自组装技术合成了3种不同的中观四（4-羧苯基）卟啉（TCPP）聚集纳米结构。以十二烷基硫酸钠（SDS）和十六烷基三甲基溴化铵（CTAB）为“软模板”，以无表面活性剂的水溶液为对照，调节卟啉自组装的微环境。由于自组装的驱动力不同，所制备的TCPP纳米结构表现出明显不同的形态，电化学和PEC性能。其中，使用SDS的自组装TCPP（SA-TCPP / SDS）具有增强的PEC性能。在多巴胺的存在下，可以在-0.4 V（vs. Ag / AgCl）的水性介质中获得明显的光电流响应。此外，还使用原位紫外-可见光谱对自组装过程进行了研究，并提出了相应的结构形成机理。