| Summary: | 碩士 === 國立臺灣科技大學 === 化學工程系 === 103 === The mechanistic study of hydrogen production by iron thiolate catalyst is reported. Complex [TBA][(μ,κ2-bdt)(μ-PPh2)Fe2(CO)5] [TBA][1] can be protonated which the first protonation generates the hydride between diiron and the second protonation occurs on the terminal sulfur. The [(μ,κ2-bdtH)(µ-PPh2)(µ-H)Fe2(CO)5]+ (1µHSH+) can react with decamethylferrocene (DMFc) to produce hydrogen, leading to [(μ,κ2-bdt)(µ-PPh2)(µ-H)Fe2(CO)5] (1µH) and DMFc+ as the final products. The yield of hydrogen production reached 75% in 15 minutes. It is shown that complex [TBA][1] active is an active catalyst for proton reduction. The yield of hydrogen production has decreased with concomitantly increasing amount of acids and electron donors. Furthermore, we studied the hydrogen production by the derivatives of complex [TBA][1] with steric functional groups in the bdt ligands The complex [TBA][(3,6-(OSitBuMe2)2bdt)Fe2(CO)5(PPh2)] ([TBA][2]) can catalyze the proton reduction. The rate of hydrogen production catalyzed by 2μHSH+ was slower than that by 1μHSH+. To study the mechanism of the hydrogen evolution reaction (HER), we investigated the possible mechanistic routes by DFT calculation to collaborate with the experimental observation. The results indicated that hydrogen is produced via proton coupled electron transfer (PCET) pathway.
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