<br>CO2 还原催化下纳米晶介孔 TiO2 和 TiO2/铁卟啉敏化膜中的电致和光致界面电荷转移,ACS Applied Materials & Interfaces

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CO2 还原催化下纳米晶介孔 TiO2 和 TiO2/铁卟啉敏化膜中的电致和光致界面电荷转移
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2023-03-07 , DOI: 10.1021/acsami.2c22458
Beatriu Domingo-Tafalla _{1,

2} , Tamal Chatterjee ₁ , Federico Franco ₁ , Javier Perez Hernandez ₁ , Eugenia Martinez-Ferrero ₁ , Pablo Ballester _{1,

3} , Emilio Palomares _{1,

3}

Affiliation

电化学和光化学CO ₂还原(CO ₂ R) 是现代可持续研究的精髓。我们报告了在CO ₂ R条件下纳米晶介孔TiO ₂薄膜和两个TiO ₂ /铁卟啉杂化薄膜（分别为内消旋芳基和β-吡咯取代的卟啉）中发生的电致和光致界面电荷转移的研究。我们使用瞬态吸收光谱 (TAS) 证明，在 355 nm 激光激发和施加偏压（0 至 -0.8 V vs Ag/AgCl）下， TiO ₂薄膜表现出瞬态吸收减少（在 -0.5 V当实验在惰性 N ₂变为 CO ₂气氛下进行时，光生电子的寿命减少了 35%（在 -0.5 V 时减少了 50%）。 TiO ₂ /铁卟啉薄膜表现出更快的电荷复合动力学，其瞬态信号衰减速度比TiO ₂薄膜快100倍。 TiO ₂和TiO ₂ /铁卟啉薄膜的电、光和光电化学CO ₂ R性能在-0.5至-1.8V vs Ag/AgCl的偏置范围内进行评估。裸露的TiO ₂膜产生CO和CH ₄以及H ₂ ，具体取决于所施加的偏压。相比之下， TiO ₂ /铁卟啉薄膜在相同条件下仅形成CO（100%选择性）。在CO ₂ R期间，在光照射条件下获得了过电势值的增益。这一发现表明光生电子从薄膜直接转移到吸收的CO ₂分子，并且观察到TAS信号的衰减减少。在TiO ₂ /铁卟啉薄膜中，我们确定了氧化铁卟啉与TiO ₂导带电子之间的界面电荷复合过程。这些竞争过程被认为是薄膜与吸附的CO ₂分子之间直接电荷转移减少的原因，解释了混合薄膜对于CO ₂ R的中等性能。

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Electro- and Photoinduced Interfacial Charge Transfers in Nanocrystalline Mesoporous TiO2 and TiO2/Iron Porphyrin Sensitized Films under CO2 Reduction Catalysis

Electro- and photochemical CO₂ reduction (CO₂R) is the quintessence of modern-day sustainable research. We report our studies on the electro- and photoinduced interfacial charge transfer occurring in a nanocrystalline mesoporous TiO₂ film and two TiO₂/iron porphyrin hybrid films (meso-aryl- and β-pyrrole-substituted porphyrins, respectively) under CO₂R conditions. We used transient absorption spectroscopy (TAS) to demonstrate that, under 355 nm laser excitation and an applied voltage bias (0 to −0.8 V vs Ag/AgCl), the TiO₂ film exhibited a diminution in the transient absorption (at −0.5 V by 35%), as well as a reduction of the lifetime of the photogenerated electrons (at −0.5 V by 50%) when the experiments were conducted under a CO₂ atmosphere changing from inert N₂. The TiO₂/iron porphyrin films showed faster charge recombination kinetics, featuring 100-fold faster transient signal decays than that of the TiO₂ film. The electro-, photo-, and photoelectrochemical CO₂R performance of the TiO₂ and TiO₂/iron porphyrin films are evaluated within the bias range of −0.5 to −1.8 V vs Ag/AgCl. The bare TiO₂ film produced CO and CH₄ as well as H₂, depending on the applied voltage bias. In contrast, the TiO₂/iron porphyrin films showed the exclusive formation of CO (100% selectivity) under identical conditions. During the CO₂R, a gain in the overpotential values is obtained under light irradiation conditions. This finding was indicative of a direct transfer of the photogenerated electrons from the film to absorbed CO₂ molecules and an observed decrease in the decay of the TAS signals. In the TiO₂/iron porphyrin films, we identified the interfacial charge recombination processes between the oxidized iron porphyrin and the electrons of the TiO₂ conduction band. These competitive processes are considered to be responsible for the diminution of direct charge transfer between the film and the adsorbed CO₂ molecules, explaining the moderate performances of the hybrid films for the CO₂R.

更新日期：2023-03-07

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