使用锌卟啉敏化剂和 TEMPO 催化剂用于苯甲醇氧化的染料敏化光电合成细胞,ACS Catalysis

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使用锌卟啉敏化剂和 TEMPO 催化剂用于苯甲醇氧化的染料敏化光电合成细胞
ACS Catalysis ( IF 11.3 ) Pub Date : 2021-09-15 , DOI: 10.1021/acscatal.1c02609
Emmanouil Nikoloudakis ₁ , Palas Baran Pati ₂ , Georgios Charalambidis ₁ , Darya S. Budkina ₃ , Stéphane Diring ₂ , Aurélien Planchat ₂ , Denis Jacquemin ₂ , Eric Vauthey ₃ , Athanassios G. Coutsolelos ₁ , Fabrice Odobel ₂

Affiliation

在光电化学电池的光阳极探索除水氧化之外的催化反应可能是更有效地产生生产太阳能燃料所需电子的关键特征。在此框架中，我们在此描述了使用锌卟啉 (ZnP) 敏化剂和 2,2,6,6-四甲基-1-哌啶N制造基于TiO ₂的染料敏化光电合成电池 (DSPEC)。-oxyl (TEMPO) 有机催化剂，可非常有效地催化光驱动的甲氧基苄醇氧化为醛。制备了两个二元组 ZnP-TEMPO，其不同之处在于 ZnP 上的锚定基团（羧酸和异羟肟酸），并记录了它们的电化学、吸收和发射特性，并实现了量子化学建模。首先检查染料敏化太阳能电池的光伏性能，以优化染色条件并比较化合物的相对效率。用 TEMPO 取代的二元组比缺乏 TEMPO 的参考锌卟啉具有更高的J _sc和V _oc。TiO ₂固定化后的光催化性能在硼酸盐缓冲液和乙腈电解质中探索了对甲氧基苯甲醇氧化的纳米晶薄膜。在硼酸盐缓冲液中，最佳 pH 值为 8，使用以异羟肟酸为锚定的二元组 ZnP-TEMPO，选择性地产生对甲氧基苯甲醛，平均光电流密度为 200 μA/cm ²，法拉第效率为 82%，周转数（ TON) 为 26，周转频率 (TOF) 为 47 h ^–1。在乙腈中，在 0.1 M N-甲基-咪唑存在下，相同的二元组的平均光电流密度约为 100 μA/cm ²，法拉第效率为 76%，TON 为 13，TOF 为 24 h ^{– 1}. 锚的稳定性在乙腈电解质中至关重要，其中二元组非常易溶，因为只有用异羟肟酸官能化的二元组才与这些有机溶剂条件相容。总体而言，这项研究为开发更有效且可能更稳定的基于TiO ₂的用于醇氧化的 DSPEC铺平了道路，该DSPEC 可以有利地补充那些致力于水氧化的 DSPEC。

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Dye-Sensitized Photoelectrosynthesis Cells for Benzyl Alcohol Oxidation Using a Zinc Porphyrin Sensitizer and TEMPO Catalyst

Exploring a catalytic reaction other than water oxidation at the photoanode of a photoelectrochemical cell is probably a key feature to more efficiently generate the electrons needed to produce solar fuels. In this framework, we describe herein the fabrication of a TiO₂-based dye-sensitized photo-electrosynthesis cell (DSPEC) using a zinc porphyrin (ZnP) sensitizer and a 2,2,6,6-tetramethyl-1-piperidine N-oxyl (TEMPO) organo-catalyst that quite efficiently catalyzes light-driven oxidation of methoxybenzyl alcohol into aldehyde. Two dyads ZnP–TEMPO, differing by the anchoring group (carboxylic acid and hydroxamic acid) on ZnP, were prepared and their electrochemical, absorption, and emission properties were recorded and quantum chemical modeling was realized. The photovoltaic performances in dye-sensitized solar cells were first examined in order to optimize the dyeing conditions and compare the relative efficiencies of the compounds. The dyads substituted with TEMPO outperform the reference zinc porphyrin lacking TEMPO with a much higher J_sc and V_oc. The photocatalytic properties after immobilization on TiO₂ nanocrystalline films toward para-methoxy benzyl alcohol oxidation were explored in borate buffer and in an acetonitrile electrolyte. In borate buffer, the optimal pH was 8 and using dyad ZnP–TEMPO anchored with hydroxamic acid, para-methoxy benzaldehyde was selectively produced with an average photocurrent density of 200 μA/cm², a Faradaic efficiency of 82%, a turnover number (TON) of 26, and a turnover frequency (TOF) of 47 h^–1. In acetonitrile, in the presence of 0.1 M N-methyl-imidazole, the same dyad gives an average photocurrent density of about 100 μA/cm², a Faradaic efficiency of 76%, a TON of 13, and a TOF of 24 h^–1. The stability of the anchor is crucial in the acetonitrile electrolyte, where the dyad is quite soluble since only the dyad functionalized with hydroxamic acid is compatible with these organic solvent conditions. Overall, this study paves the way to the development of more efficient and probably more stable TiO₂-based DSPECs for alcohol oxidation that could advantageously complement those devoted to water oxidation.

更新日期：2021-10-01

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