Extensive composition engineering research has been conducted on bandgap tunability, but the combination of two mechanisms for better photon harvesting over a wide range has rarely happened; this is of great importance for improving photocatalytic efficiency with sunlight. In order to enable concurrent heterogenic Fenton and Fenton-like reactions for dye degradation, two novel ferrocene-functionalized clusters, [(PPh₃)₃CuO₂CFcCO₂Cu(PPh₃)₃]·3CH₃OH (D₁) and [(PPh₃)₂AgO₂CFcCO₂Ag(PPh₃)₂]₂·7CH₃OH (D₂) were designed, synthesized and characterized by multiple techniques. These chemically and thermally stable coinage clusters exhibit high photocatalytic activity towards the degradation of methylene blue as a model dye in the presence of H₂O₂ under direct sunlight irradiation. The degradation performance of complex D₁ is about twice that of complex D₂. The catalytic performance of D₁ (15 000 mg g⁻¹ in less than 20 min) is superior to those of other reported complexes, which can be attributed to the high level of generated hydroxyl radicals which are the most active species for dye degradation in the combination of Fenton and Fenton-like mechanisms. In addition to the degradation carried out with the aid of the Fe(III) of ferrocene, based on the Fenton mechanism, the photogenerated holes trapped by Cu(I) act as catalysts in the Fenton-like mechanism to produce an excess of hydroxyl radicals, adding to those formed via scavenging of photogenerated electrons by hydrogen peroxide. Furthermore, the performance of D₁ in the presence of H₂O₂ as a dual photocatalyst under natural sunlight irradiation needs no pH adjustment which is a unique characteristic. This bilateral compound offers a promising strategy for the design of new photocatalysts.

中文翻译：

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自然阳光下设计的二茂铁官能团降解染料的双边光催化机理

关于带隙可调谐性已经进行了广泛的组成工程研究，但是很少有两种机制可以在较宽的范围内实现更好的光子收集。这对于提高阳光的光催化效率非常重要。为了使染料降解同时发生异源Fenton和类似Fenton的反应，两个新的二茂铁官能化簇[[（PPh ₃）₃ CuO ₂ CFcCO ₂ Cu（PPh ₃）₃ ]·3CH ₃ OH（D ₁）和[ （PPh ₃）₂ AgO ₂ CFcCO ₂ Ag（PPh ₃）₂通过多种技术设计，合成和表征了] ₂ ·7CH ₃ OH（D ₂）。这些化学和热稳定的造币簇在直接阳光照射下在H ₂ O ₂存在下，对作为模型染料的亚甲基蓝的降解显示出高的光催化活性。配合物D ₁的降解性能约为配合物D ₂的降解性能的两倍。D ₁（15000 mg g ^-1在不到20分钟的时间内）优于其他报道的配合物，这可以归因于高水平的生成的羟基自由基，它们是Fenton和类似Fenton机理结合的染料降解最活跃的物种。除了借助二茂铁的Fe（III）进行降解以外，还基于Fenton机理，被Cu（I）捕获的光生空穴在Fenton样机理中起催化剂的作用，产生过量的羟基自由基，加入到与形成通过由过氧化氢清除光生电子。此外，在H ₂ O ₂存在下D ₁的性能作为天然光照射下的双重光催化剂，无需调节pH，这是其独特的特性。这种双边化合物为新型光催化剂的设计提供了一种有希望的策略。