Mechanistic Insights into Hydrogen Evolution by Photocatalytic Reforming of Naphthalene,ACS Catalysis

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Mechanistic Insights into Hydrogen Evolution by Photocatalytic Reforming of Naphthalene
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-06-01 , DOI: 10.1021/acscatal.0c01713
Osama Al-Madanat _{1,

2} , Yamen AlSalka _{1,

3} , Mariano Curti ₁ , Ralf Dillert _{1,

3} , Detlef W. Bahnemann _{1,

3,

4}

Affiliation

Heterogeneous photocatalysis has been widely considered, among other applications, for environmental remediation and hydrogen production. While these applications have been traditionally seen as well-separated areas, recent examples have highlighted the possibility of coupling them. Here, we demonstrate the simultaneous production of H₂ and naphthalene removal from aqueous solutions with (unoptimized) photonic efficiencies of 0.97 and 0.33%, respectively, over Pt–TiO₂ under simulated sunlight. Photocatalytic and spin-trapping experiments in the presence of a hydroxyl radical and hole scavengers evinced that only the photogenerated holes play a significant role in the oxidation of naphthalene. Isotopic labeling analyses showed that the evolved H₂ isotopologues match those of the solvent and that deuterated water (but not deuterated naphthalene) decreases the reaction rate, suggesting its involvement in the rate-determining step. Moreover, the use of Ti¹⁸O₂ does not lead to the significant formation of ¹⁸O-enriched CO₂, suggesting that water is the source of the oxygen atoms. Ultimately, by considering the stable and transient reaction intermediates, we propose a plausible reaction pathway. Our work illustrates that environmental remediation can be effectively coupled to solar fuel production, providing a double purpose to photocatalytic reactions, while the mechanistic insights will be of use for the further development of this strategy.

中文翻译：

萘通过光催化重整制氢过程的机理研究

在其他应用中，非均相光催化已被广泛考虑用于环境修复和制氢。传统上将这些应用程序视为分隔良好的区域，但最近的示例强调了将它们耦合的可能性。在这里，我们证明了在模拟阳光下，Pt-TiO _2上同时发生的H ₂和萘从水溶液中的去除（未优化）的光子效率分别为0.97和0.33％。在羟基自由基和空穴清除剂的存在下的光催化和自旋捕获实验表明，只有光生空穴在萘的氧化中起重要作用。同位素标记分析表明，析出的H ₂同位素相匹配的溶剂和氘化水（但不是氘化萘）会降低反应速率，表明它参与了速率确定步骤。而且，使用Ti ¹⁸ O ₂不会导致明显形成富含¹⁸ O的CO ₂，这表明水是氧原子的来源。最终，通过考虑稳定和短暂的反应中间体，我们提出了一条合理的反应途径。我们的工作表明，环境修复可以有效地与太阳能燃料生产结合，为光催化反应提供双重目的，而机械的见解将有助于该策略的进一步发展。

更新日期：2020-07-02

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