新型卟啉光敏剂和钴肟助催化剂的偶联用于高效光催化析氢,Journal of Materials Chemistry A

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新型卟啉光敏剂和钴肟助催化剂的偶联用于高效光催化析氢
Journal of Materials Chemistry A ( IF 10.7 ) Pub Date : 2021-08-11 , DOI: 10.1039/d1ta04517b
Govardhana Babu Bodedla _{1,

2,

3} , Wai-Yeung Wong _{2,

3} , Xunjin Zhu ₁

Affiliation

光催化析氢（PHE）是利用太阳能和水生产环保清洁能源的一种很有前景的策略。为此，开发包含高光捕获和光稳定性光敏剂的高效且无贵金属的光催化系统 (PS) 是一项重要且具有挑战性的任务。在此，为 PHE 开发了一种新的卟啉光敏剂 ZnDC( p -NI)PP，它含有两个萘酰亚胺 ( NI) 供体发色团和 4-羧基苯基取代基。在 pH 7.4 的磷酸盐缓冲液/THF 溶液中使用氯吡啶钴肟 (CoPyCl) 作为助催化剂，ZnDC( p -NI)PP的均相 PS表现出非常高的析氢速率 ( η _{H ₂} )，为 35.70 mmol g ^-1 h^-1，5958 的周转数 (TON) 和 10.01% 的表观量子效率 (AQE)。在相同条件下记录的这种性能显着高于缺少 NI 部分的 ZnDCPP 的 PS（ η _{H ₂}为 4.64 mmol g^-1 h^-1，TON 为 1397 和 AQE 为 1.30%），典型的 PS ZnTCPP具有四个4-羧基取代基（ η _{ħ ₂}的2.43毫摩尔克^-1 ħ^-1，562 TON和1.00％AQE），和先前报道ZND（ p含有-NI）PP只有两个发色团NI（ η _{ħ ₂} of 3.8 mmol g^-1 h^-1, TON 为 590，AQE 为 1.5%）。ZnDC( p- NI)PP 在 PHE 中的显着性能归因于从 NI 供体发色团到卟啉受体的分子内能量转移，这将促进长寿命的光激发状态。同时，由于静电力，4-羧基苯基取代基的阴离子形式 (-COO ^- ) 在 pH 7.4 下能够更快地从卟啉基团转移到阳离子 Co( III )。据我们所知，ZnDC( p- NI )PP的 PHE 结果代表了迄今为止报道的卟啉光敏剂和钴肟 PSs 的最佳结果。这项工作为通过简单的分子结构工程开发用于高效 PHE 的新型卟啉基材料开辟了新的方向。

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Coupling of a new porphyrin photosensitizer and cobaloxime cocatalyst for highly efficient photocatalytic H2 evolution

Photocatalytic hydrogen evolution (PHE) is a promising strategy to produce environmentally friendly clean energy with the use of solar power and water. For this, developing an efficient and noble metal free photocatalytic system (PS) comprising high light-harvesting and photostable photosensitizers is an important and challenging task. Herein, a new porphyrin photosensitizer ZnDC(p-NI)PP, containing two naphthalimide (NI) donor chromophores and 4-carboxyphenyl substituents is developed for PHE. Using chloropyridinecobaloxime (CoPyCl) as a cocatalyst in phosphate buffer/THF solution at pH 7.4, the homogeneous PS of ZnDC(p-NI)PP exhibits a very high hydrogen evolution rate (η_H₂) of 35.70 mmol g⁻¹ h⁻¹, turnover number (TON) of 5958 and apparent quantum efficiency (AQE) of 10.01%. This performance recorded under the same conditions is significantly higher than that of the PS of ZnDCPP which lacks the NI moieties (η_H₂ of 4.64 mmol g⁻¹ h⁻¹, TON of 1397 and AQE of 1.30%), the typical PS of ZnTCPP with four 4-carboxyphenyl substituent groups (η_H₂ of 2.43 mmol g⁻¹ h⁻¹, TON of 562 and AQE of 1.00%), and previously reported ZnD(p-NI)PP containing only two NI chromophores (η_H₂ of 3.8 mmol g⁻¹ h⁻¹, TON of 590 and AQE of 1.5%). The noticeable performance of ZnDC(p-NI)PP in PHE is attributed to the intramolecular energy transfer from the NI donor chromophore to the porphyrin acceptor that would promote the long-lived photoexcitation states. At the same time, the anionic form (–COO⁻) of 4-carboxyphenyl substituents at pH 7.4 enables a faster electron transfer from the porphyrin group to the cationic Co(III) due to electrostatic force. To the best of our knowledge, the PHE results of ZnDC(p-NI)PP represent the best one for porphyrin photosensitizers and cobaloxime PSs reported so far. This work paves a new direction for developing new porphyrin-based materials for efficient PHE through facile molecular structure engineering.

更新日期：2021-08-26

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