In comparison to traditional solar cells, the dye-sensitized photocatalytic system is one of the most appealing artificial photosynthesis mechanisms due to its low cost and straightforward fabrication. Herein, the photoelectrochemical and photocatalytic hydrogen evolution reactions of Zn-based phthalocyanine (Pc) derivatives, abbreviated as ZnPc-1 and ZnPc-2, were primarily studied in the presence of TEOA sacrificial electron donor. To this aim, the PC activities of ZnPc-1/TiO 2 and ZnPc-2/TiO 2 photocatalysts were investigated in the absence and presence of a cocatalyst. For the first hour, the amount of hydrogen generated by ZnPc derivatives (ZnPc-1/TiO 2 and ZnPc-2/TiO 2 ) was determined to be 1.221 and 0.864 mmol g −1 h −1 , respectively. Additionally, the solar-to-hydrogen conversion efficiencies of ZnPc-1/ TiO 2 and ZnPc-2/TiO 2 were ascertained to be 3.15% and 2.22%, respectively. Interestingly, STH efficiencies of photocatalysts were increased about 4-fold in the presence of a cocatalyst. Consequently, to elucidate the structural properties of ZnPc-1 and ZnPc-2, density functional theory (DFT) and time-dependent DFT studies were also conducted, and it was discovered that noncovalent interactions and steric hindrance effects on ZnPc-2 are tightly related to the experimentally determined PC activity differences between ZnPc-1 and ZnPc-2.

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Two zinc phthalocyanine derivatives (ZnPc 1 and 2) carrying bulky 2,6-diisopro-pylthiophenoxy peripheral substituents have been synthesized and their performances as photosensitizers in photochemical hydrogen production evaluated. To examine the influence of the spacer on the performance of ZnPc 1 and 2, the carboxyl group has been linked to the macrocycle ring either directly or via the phenyl ring, respectively. The photocatalytic activities of ZnPcs (ZnPc 1 and ZnPc 2) as sensitizers of TiO2 for hydrogen production were investigated in the presence of Pt. ZnPc 1 and ZnPc 2 sensitized TiO2 produced 0.687 mmolg[Formula: see text]h[Formula: see text] and 0.436 mmol g[Formula: see text]h[Formula: see text] hydrogens, which also reached 3.986 and 2.091 mmolg[Formula: see text] after 8h illumination, respectively, under visible light ([Formula: see text] 420 nm) irradiation. In addition, STH efficiencies of ZnPc 1/TiO2 and ZnPc 2/TiO2 were determined as 1.77% and 1.12%, respectively. ZnPc 1/TiO2 exhibited 1.9-fold more photocatalytic hydrogen amount than ZnPc 2/TiO2, and the hydrogen evolution performance of the photocatalyst in the presence of Pt enhanced to 3.021 mmol g[Formula: see text]h[Formula: see text] and 0.911mmol g[Formula: see text]h[Formula: see text] for ZnPc 1 and ZnPc 2, respectively.

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Chevrel phases consisted of abundant materials, are of great interest in a variety of energy conversion and storage technologies because of unique structural and electronic features. Herein, crystalline