Boosting Photocatalytic Hydrogen Evolution Reaction Using Dual Plasmonic Antennas

Abstract

Plasmon-mediated photocatalytic water splitting has attracted extensive attention due to its bright future in using visible light, but the enhancement mechanism is still unclear, and the efficiency remains low. Herein, a dual-plasmonic-antenna strategy that allows efficient generation of energetic hot electrons and strong electromagnetic fields simultaneously has been developed to boost the photocatalytic hydrogen evolution reaction (HER). Au@CdS core–shell nanoparticles are assembled on Ag@SiO2 shell-isolated nanoparticles, forming dual-plasmonic-antenna nanocomposites. Transient absorption spectroscopic experiments and electromagnetic field simulations demonstrate that both hot-electron transfer and plasmon-induced resonance energy transfer exist in this system. The Au@CdS antenna can generate energetic hot electrons to trigger the HER, while the Ag@SiO2 antenna produces strong electromagnetic fields to promote the generation and separation of hot carriers, thus significantly improving the HER performance under visible light irradiation. Such a dual-plasmonic-antenna concept overcomes the intrinsic limitation of traditional plasmonic photocatalytic materials and offers unique opportunities to develop efficient photocatalysts.

Hybrid Plasmonic Nanomaterials for Hydrogen Generation and Carbon Dioxide Reduction

“…Yang et al synthesized hybrid dual plasmonic antenna consisting of partially CdS-coated Au satellites assembled on SiO 2 -coated Ag nanoparticles (Ag@SiO 2 /Au@CdS with pinholes). 132 Panels i and ii of Figure 3 c show the spatial arrangement of the metals. When tested for the HER, this structure yielded one of the highest performances for this type of PNP–SC hybrids (191 × 10 3 μmol g –1 h –1 , Figure 3 c).…”

Plasma-Wind-Assisted In2S3 Preparation with an Amorphous Surface Structure for Enhanced Photocatalytic Hydrogen Production

“…However, a significant obstacle to the industrialization of photocatalytic hydrogen production is low conversion efficiency. Many strategies have been therefore proposed to enhance the optical, electrical, and catalytic properties of photocatalysts to improve their efficiency, including heterojunction structural design [ 6 , 7 ], the introduction of plasmonic materials [ 8 , 9 , 10 ], defect engineering (e.g., oxygen or sulfur vacancy) [ 11 , 12 ], phase transition [ 13 , 14 ], and single-atom catalysis [ 15 , 16 , 17 ]. It is worth noting that catalysis is a surface redox reaction on the photocatalyst, where the water molecules split into hydrogen and oxygen [ 18 ].…”

Au-Cu2–xTe Plasmonic Heteronanostructure Photoelectrocatalysts

“…Therefore, the better activity of the Au-Cu 2−x Te heterostructure toward HER was mainly due to the more electron-abundant Au, which is attributed to the additional reductive sites for hydrogen ion reduction, thereby facilitating the spontaneous charge transfer between metal and semiconductors and resulting in their intrinsic catalytic activity. 4 The corresponding Tafel plots of the pure Cu 2−x Te and Au-Cu 2−x Te heterostructures are presented in Figure 3b, to reveal the hydrogen evolution kinetics of the catalysts loaded working electrode. From the data, it was observed that the Tafel slope for heterostructure materials was about 154 mV/dec, smaller than that for pure Cu 2−x Te (183 mV/dec).…”

“…Plasmonic heteronanostructures are widely established as the leading optical material for photochemical and photoelectrochemical (PEC) reactions. − The exciton–plasmon coupling remained a key feature for boosting the charge carrier transfer and enhancing the catalytic activity of these materials. − To overcome the global energy crisis and environmental issues, production of a clean energy source like hydrogen using these heterostructured catalysts as one of the renewable methods has also been widely explored. − Among these, dual plasmonic nanostructures remained in a special category for their higher absorption ability and efficient photogenerated charge carrier transportation. ,, Au-Cu 2– x S and Au-Cu 2– x Se are the most common Au coupled copper based chalcogenide heterostructures, and these were also explored for catalysis in HER, OER, and CO 2 RR. ,,− The importance of such materials with Cu­(I) is due to their stoichiometry, where some percentage of Cu­(I) either remains vacant or is transformed to Cu­(II), which induces localized surface plasmon resonance (LSPR) in these materials. − Hence, adding plasmonic Au to these copper compounds invariably boosts the dual plasmonic character, ideal for electrocatalytic (EC) and PEC reactions.…”

“…From the figure, it is evident that, to reach the same current density of 10 mA/cm 2 , Au-Cu 2– x Te required lowest overpotential of 282 mV compared to that of 454 mV for pure Cu 2– x Te. Therefore, the better activity of the Au-Cu 2– x Te heterostructure toward HER was mainly due to the more electron-abundant Au, which is attributed to the additional reductive sites for hydrogen ion reduction, thereby facilitating the spontaneous charge transfer between metal and semiconductors and resulting in their intrinsic catalytic activity . The corresponding Tafel plots of the pure Cu 2– x Te and Au-Cu 2– x Te heterostructures are presented in Figure b, to reveal the hydrogen evolution kinetics of the catalysts loaded working electrode.…”