ABSTRACT
Metal nanoparticles (NP) supported on TiO2 are known to be efficient photocatalysts for solar-to-chemical energy conversion. While TiO2 decorated with copper NPs has the potential to become an attractive system, the poor oxidative stability of Cu severely limits its applicability. In this work, we demonstrate that, when Cu NPs supported on TiO2 nanobelts (NBs) are engaged in the photocatalytic generation of H2 from water under light illumination, Cu is not only oxidized in CuO but also dissolved under the form of Cu+/Cu2+ ions, leading to a continuous reconstruction of nanoparticles via Ostwald ripening. By nanoencapsulating the CuOx (Cu/CuO/Cu2O) NPs by a few layers of carbon supported on TiO2 (TC@C), Ostwald ripening can be suppressed. Simultaneously, the resulting CuOx@C NPs are photoreduced under light illumination to generate Cu@C NPs. This photoswitching strategy allows the preparation of a Cu plasmonic photocatalyst with enhanced activity for H2 production. Remarkably, the photocatalyst is even active when illuminated with visible light, indicating a clear plasmonic enhancement of photocatalytic activity from the surface plasmonic resonance (SPR) effect of Cu NPs. Three-dimensional electromagnetic wave-frequency domain (3D-EWFD) simulations were conducted to confirm the SPR enhancement. This advance bodes for the development of scalable multifunctional Cu-based plasmonic photocatalysts for solar energy transfer.
ABSTRACT
High-performance oxygen electrocatalysts play a key role in the widespread application of rechargeable Zn-air batteries (ZABs). Single-atom catalysts (SACs) with maximum atom efficiency and well-defined active sites have been recognized as promising alternatives of the present noble-metal-based catalysts for oxygen reduction reaction and oxygen evolution reaction. To improve their oxygen electrocatalysis activities and reveal the structure-activity relationship, many advanced synthesis and characterization methods have been developed to study the effects of 1) coordination and electronic structure of the metal centers and 2) morphology and stability of the conductive substrates. Herein, a detailed review of the recent advances of SACs with strong electronic metal-support interaction (EMSI) for rechargeable ZABs is provided. Great emphasis was placed on the EMSI forms and design strategies. Moreover, the importance and the impact of the atomic coordinating structure and the substrates on the oxygen electrocatalytic activity and stability are highlighted. Finally, future directions and perspectives on the development of SACs are also presented.
ABSTRACT
Rechargeable zinc-air batteries (ZABs) are considered as one of the most promising electrochemical energy devices due to their various unique advantages. Oxygen electrocatalysis, involving the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), determines the overall performance of zinc-air batteries. Therefore, the development of highly efficient bifunctional ORR/OER catalysts is critical for the large-scale application of ZABs. Carbon-based nanomaterials have been widely reported to be efficient electrocatalysts toward both ORR and OER. The enhanced activity of these electrocatalysts are usually attributed to different doping defects, synergistic effects and even the intrinsic carbon defects. Herein, an overview of the defect engineering in carbon-based electrocatalysts for ORR and OER is provided. The different types of intrinsic carbon defects and strategies for the generation of other defects in carbon-based electrocatalysts are presented. The interaction of heteroatoms doped carbon and transition metals (TMs) is also explored. In the end, the existing challenges and future perspectives on defect engineering are discussed.
