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CdSe-AuPd量子点0D/0D杂化光催化剂的构建:通过电化学分析进行电荷转移动力学研究以提高光催化活性

Construction of CdSe-AuPd quantum dot 0D/0D hybrid photocatalysts: charge transfer dynamic study with electrochemical analysis for improved photocatalytic activity.

作者信息

Panigrahy Bharati, Sahoo Prasanta Kumar, Sahoo Bibhuti Bhusan

机构信息

Solid State and Structural Chemistry Unit, Indian Institute of Science, Bengaluru 560 012, India.

Department of Mechanical Engineering, Siksha 'O' Anusandhan, Deemed to be University, Bhubaneswar-751030, India.

出版信息

Dalton Trans. 2022 Jan 4;51(2):664-674. doi: 10.1039/d1dt02761a.

Abstract

The integration of semiconductor quantum dots and noble metal nanoparticles can efficiently couple numerous effects corresponding to the individual domains of the hybrid system for a variety of applications. Herein, we establish a direct correlation between the electronic band structure and optical band gap of monometallic and bimetallic alloy nanoparticle decorated CdSe quantum dots, which in turn regulate the charge shuttling dynamics in a quantum dot hybrid (QDH) system. Directly coupled Au, Pd, AuPd, and CdSe QDHs were prepared a simple fabrication technique. The photoluminescence intensity of the QDHs was quenched compared to that of CdSe quantum dots with a maximumally diminished CdSe-AuPd system. Broadening of the absorbance peak along with a blue shift for QDHs confirm the interaction of the energy levels of the QDs and metal domains. AuPd decorated CdSe QDs demonstrate enhanced photocatalytic activity compared to their monometallic counterparts, which has made them interesting catalysts reported for the first time. Lifetime decay measurements, which isolated the individual charge-transfer steps, showed that a maximum amount of photoexcitons can be separated by bimetallic alloy decoration compared to monometallic ones. Cyclic voltammetry results offer insight into the change in the conduction band edge energy position for both monometallic and bimetallic incorporating semiconductor hybrid systems. Our findings reveal that photoexcited semiconductor quantum dots undergo charge equilibration when the QDs are in contact with metallic domains, influencing the shifting of the conduction band energy level of the hybrid to a more negative potential, and this is a maximum for the CdSe-AuPd hybrid, resulting in the best photocatalytic activity. Shuttling of electrons around the conduction band of CdSe and the Fermi level of the metallic domains is the main deciding factor for an efficient photocatalyst hybrid system.

摘要

半导体量子点与贵金属纳米粒子的整合能够有效地耦合与混合系统各个领域相对应的多种效应,从而实现各种应用。在此,我们建立了单金属和双金属合金纳米粒子修饰的CdSe量子点的电子能带结构与光学带隙之间的直接关联,进而调控量子点混合(QDH)系统中的电荷穿梭动力学。通过一种简单的制备技术制备了直接耦合的Au、Pd、AuPd和CdSe QDHs。与CdSe量子点相比,QDHs的光致发光强度猝灭,其中CdSe-AuPd系统的猝灭程度最大。QDHs的吸收峰展宽以及蓝移证实了量子点和金属域能级之间的相互作用。与单金属修饰的CdSe量子点相比,AuPd修饰的CdSe量子点表现出增强的光催化活性,这使其成为首次报道的有趣催化剂。寿命衰减测量分离了各个电荷转移步骤,结果表明与单金属修饰相比,双金属合金修饰能够分离出最大量的光激子。循环伏安法结果为单金属和双金属半导体混合系统的导带边缘能量位置变化提供了深入了解。我们的研究结果表明,当量子点与金属域接触时,光激发的半导体量子点会经历电荷平衡,这会影响混合体系导带能级向更负电位的移动,而对于CdSe-AuPd混合体系来说这种移动最大,从而导致最佳的光催化活性。CdSe导带周围电子与金属域费米能级之间的穿梭是高效光催化剂混合系统的主要决定因素。

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