Photoexcited carrier dynamics of bismuth tungstate (Bi2WO6) photocatalysts was investigated by time-resolved infrared (IR) absorption spectroscopy. Monotonic absorption at the mid-IR region, which is attributable to absorption by photoexcited electrons, was monitored as a function of time delay from the microsecond to millisecond range after photoexcitation. Bi2WO6 particles with different crystalline content were prepared by hydrothermal reaction at several temperatures and used to elucidate the relation between density of photoexcited carriers and steadystate photocatalytic efficiency. Photocatalytic efficiency was tested using two reactions: oxidative decomposition of acetic acid in an aqueous solution (reaction 1) and oxidative decomposition of acetaldehyde in air (reaction 2). Crystallization of Bi2WO6 particles suppressed the fast recombination of photoexcited electrons and holes within 1 μs. In the case of crystallized particles, the density of the photoexcited electron increased with an increase in the crystalline content, and the photocatalytic efficiency for reaction 1 strongly depended on the crystalline content, indicating that photoexcited electrons remaining in the submillisecond time range significantly affect the reaction rate. On the other hand, photocatalytic efficiency for reaction 2 showed a proportional relation with specific surface area rather than crystalline content. The difference in a decisive factor depending on reaction condition is considered to be the slower rate of reaction of photoexcited electrons with molecular oxygen, which might occur within a time range between 200 μs and 3 ms over Bi2WO6.
展开▼
机译:通过时间分辨红外(IR)吸收光谱研究了钨酸铋(Bi2WO6)光催化剂的光激发载流子动力学。监测中红外区域的单调吸收,这归因于光激发电子的吸收,它是光激发后从微秒到毫秒范围的时间延迟的函数。通过在几个温度下的水热反应制备了具有不同晶体含量的Bi 2 WO 6颗粒,并用于阐明光激发载体的密度与稳态光催化效率之间的关系。使用两个反应测试了光催化效率:乙酸在水溶液中的氧化分解(反应1)和乙醛在空气中的氧化分解(反应2)。 Bi2WO6颗粒的结晶在1μs内抑制了光激发电子和空穴的快速复合。在结晶颗粒的情况下,光激发电子的密度随结晶含量的增加而增加,反应1的光催化效率强烈依赖于结晶含量,表明残留在亚毫秒级时间范围内的光激发电子会显着影响反应率。另一方面,反应2的光催化效率显示出与比表面积而不是结晶含量成比例的关系。取决于反应条件的决定性因素的差异被认为是光激发电子与分子氧的较慢反应速率,这可能发生在Bi2WO6的200 µs至3 ms的时间范围内。
展开▼