The effective utilization of light is crucial in the use of the solar energy for CO₂ conversion into valuable fuels and chemicals, in which improving the photocatalytic materials’ capacity to absorb light is a key. Herein, a 2D copper–porphyrin metal−organic framework (MOF)-photosensitized titania, TiO₂/Zn–CuTCPP, is reported, which can absorb wide range of light and photoreduce CO₂ with high efficiency under full spectrum irradiation. Fluorescence spectral analysis elucidates the relationship between the photocatalytic activity and the electron–hole separation efficiency. In addition, mechanistic information obtained from electron paramagnetic resonance and in situ infrared analyses demonstrates that the presence of Cu–N₄ site in the MOF structure is conducive to the generation of hydrogen free radicals (•H), which plays a key role in the formation of intermediates, thus facilitating the hydrogenation in the reaction process. Consequently, TiO₂/Zn–CuTCPP significantly enhances the photocatalytic conversion of CO₂ into CH₄ with a yield 14 times higher than that of P25.

中文翻译：

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二维铜-卟啉金属-有机框架纳米片-光敏化 TiO2 用于高效宽带光驱动 CO2 转化为 CH4

光的有效利用对于利用太阳能将CO ₂转化为有价值的燃料和化学品至关重要，其中提高光催化材料吸收光的能力是关键。在此，报道了一种二维铜-卟啉金属-有机骨架（MOF）光敏二氧化钛，TiO ₂ /Zn-CuTCPP，它可以吸收大范围的光并在全光谱照射下高效地光还原CO ₂ 。荧光光谱分析阐明了光催化活性与电子空穴分离效率之间的关系。此外，从电子顺磁共振和原位红外分析获得的机理信息表明，MOF结构中Cu-N ₄位点的存在有利于氢自由基（·H）的产生，在氢自由基（·H）的生成中发挥着关键作用。形成中间体，从而促进反应过程中的氢化。因此，TiO _{2 /Zn-CuTCPP显着增强了CO 2}光催化转化为CH ₄的能力，产率比P25高14倍。