Kipkorir Anthony, DuBose Jeffrey, Cho Junsang, Kamat Prashant V
Radiation Laboratory, University of Notre Dame Notre Dame Indiana 46556 USA.
Department of Chemistry and Biochemistry, University of Notre Dame Notre Dame Indiana 46556 USA.
Chem Sci. 2021 Oct 22;12(44):14815-14825. doi: 10.1039/d1sc04305f. eCollection 2021 Nov 17.
The instability of cesium lead bromide (CsPbBr) nanocrystals (NCs) in polar solvents has hampered their use in photocatalysis. We have now succeeded in synthesizing CsPbBr-CdS heterostructures with improved stability and photocatalytic performance. While the CdS deposition provides solvent stability, the parent CsPbBr in the heterostructure harvests photons to generate charge carriers. This heterostructure exhibits longer emission lifetime ( = 47 ns) than pristine CsPbBr ( = 7 ns), indicating passivation of surface defects. We employed ethyl viologen (EV) as a probe molecule to elucidate excited state interactions and interfacial electron transfer of CsPbBr-CdS NCs in toluene/ethanol mixed solvent. The electron transfer rate constant as obtained from transient absorption spectroscopy was 9.5 × 10 s and the quantum efficiency of ethyl viologen reduction ( ) was found to be 8.4% under visible light excitation. The Fermi level equilibration between CsPbBr-CdS and EV/EV˙ redox couple has allowed us to estimate the apparent conduction band energy of the heterostructure as -0.365 V NHE. The insights into effective utilization of perovskite nanocrystals built around a quasi-type II heterostructures pave the way towards effective utilization in photocatalytic reduction and oxidation processes.
溴化铯铅(CsPbBr)纳米晶体(NCs)在极性溶剂中的不稳定性阻碍了它们在光催化中的应用。我们现已成功合成出具有更高稳定性和光催化性能的CsPbBr-CdS异质结构。CdS沉积提供了溶剂稳定性,而异质结构中的母体CsPbBr则捕获光子以产生电荷载流子。这种异质结构的发射寿命( = 47 ns)比原始CsPbBr( = 7 ns)更长,表明表面缺陷得到了钝化。我们使用乙基紫精(EV)作为探针分子,以阐明甲苯/乙醇混合溶剂中CsPbBr-CdS NCs的激发态相互作用和界面电子转移。通过瞬态吸收光谱法获得的电子转移速率常数为9.5 × 10 s,在可见光激发下,乙基紫精还原的量子效率( )为8.4%。CsPbBr-CdS与EV/EV˙氧化还原对之间的费米能级平衡使我们能够估计异质结构的表观导带能量为-0.365 V NHE。对准II型异质结构周围钙钛矿纳米晶体有效利用的深入了解为其在光催化还原和氧化过程中的有效利用铺平了道路。