A review on the photosensitizers used for enhancing the photoelectrochemical performance of hydrogen production with emphasis on a novel toxicity assessment framework

Khalkhali, Faezeh Sadat; Kowsari, Elaheh; Ramakrishna, Seeram; Eqbalpour, Mohammad; Gheibi, Mohammad; Esmaili, Hamed

doi:10.1016/j.ijhydene.2023.07.116

Cited by 8 publications

(1 citation statement)

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“…Nevertheless, most of these materials have disadvantages in their broad band gaps and restricted tunability, making them inappropriate for effectively harnessing solar energy in the visible (43% of solar flux) and infrared (52% of solar flux) regions. Integrating the photosensitizer can assist in resolving this problem. − Nevertheless, there is a significant demand for photocatalysts that can respond to visible light and demonstrate high efficiency in absorbing light.…”

Section: Introductionmentioning

confidence: 99%

Effect of Halogenation on the Photocatalytic Hydrogen Evolution Performance of Tetrazine Polymers

Kar,

Bhattacharyya

et al. 2024

ACS Appl. Polym. Mater.

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Developing highly efficient photocatalysts for water splitting is crucial in the conversion of solar energy into hydrogen. Improving the catalytic performance via substituents optimization on the photocatalyst is a desirable technique, as it requires minimum changes to its structure. In this study, we showcase the impact of halogenation on the efficiency of tetrazine-integrated 1D linear polymers in generating hydrogen using photocatalysis. This work utilizes three copolymers (PhTz, FTz, and ClTz) synthesized by the Pinner process, employing tetrazine and phenylene/tetrafluorophenylene/tetrachlorophenylene, respectively. The polymers have a πconjugated backbone and display significant absorption in the visible spectrum with an absorption red edge within the wavelength range of 820−640 nm with optical band gaps ranging from 1.51 to 1.94 eV. The photocatalytic hydrogen evolution of these polymers under metal-free conditions has revealed that the fluorine-substituted polymer (FTz) exhibited a significantly higher performance of 227 μmol g −1 h −1 , which is twice as high as that of ClTz (116.6 μmol g −1 h −1 ) and five times higher than that of the nonhalogenated polymer (PhTz) (46.2 μmol g −1 h −1 ). The presence of halogens substantially lowered the energy barrier for hydrogen adsorption on the polymer surface: ΔG°values for FTz, ClTz, and PhTz are 0.07, 0.11, and 0.19 eV, respectively. On the other hand, tetrazine is crucial for reducing the energy bandgap, augmenting the absorption of visible light, and facilitating the binding of hydrogen atoms.

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