Beijing Key Laboratory of Energy Conversion and Storage Materials, College of Chemistry, Beijing Normal University, Beijing 100875, China.
Molecules. 2023 Apr 4;28(7):3229. doi: 10.3390/molecules28073229.
A novel Re (I) complex of [Re(CO)Cl(L)], {L = 2-([2,2'-bithiophen]-5-yl)-1-phenyl-1-imidazo [4,5-][1,10]phenanthroline}, was synthesized, and its optical (UV-Visible absorption and emission spectroscopy), cyclovoltammetric and photoelectrochemical oxygen reduction properties were studied. The geometric and electronic properties were also investigated by density functional theory calculations. It was found that the ITO electrode coated with drop-casted [Re(CO)Cl(L)] film exhibited cathodic photocurrent generation characteristics. The illuminated film exhibited a maximum cathodic photocurrent up to 30.4 μA/cm with an illumination intensity of 100 mW/cm white light at a bias potential of -0.4 V vs. SCE in O-saturated electrolyte solution, which was reduced by 5.1-fold when thoroughly deoxygenated electrolyte solution was used, signaling that the electrode performed well on the photoelectrochemical oxygen reduction. The photo-electrocatalytic hydrogen peroxide production was proved with a maximum HO concentration of 6.39 μM during 5 h of the photoelectrocatalytic process. This work would guide the construction of more efficient rhenium-based photo(electro)catalytic molecular systems for O sensing, hydrogen peroxide production and other types of photoelectrochemical energy conversion and storage.
合成了一种新型的 Re（I）配合物[Re（CO）Cl（L）]，其中 L = 2-（[2,2'-联噻吩]-5-基）-1-苯基-1-咪唑并[4,5-][1,10]菲咯啉，并研究了其光学（紫外-可见吸收和发射光谱）、循环伏安法和光电化学氧还原性质。还通过密度泛函理论计算研究了其几何和电子性质。结果发现，涂有滴铸[Re（CO）Cl（L）]薄膜的 ITO 电极表现出阴极光电流产生特性。在 O2 饱和电解质溶液中，在 100 mW/cm 的白光照射下，在偏置电位为-0.4 V 对 SCE 时，照射薄膜的最大阴极光电流可达 30.4 μA/cm2，当使用彻底脱氧的电解质溶液时，其电流降低了 5.1 倍，表明该电极在光电化学氧还原方面表现良好。通过光电催化过程 5 h 内产生了最大 HO 浓度为 6.39 μM，证明了光电化学过氧化氢的产生。这项工作将为构建更高效的基于铼的光（电）催化分子体系，用于 O 传感、过氧化氢生产和其他类型的光电化学能量转换和存储提供指导。
