Filling the Gap: Atomically Precise Metal Nanoclusters‐Induced Z‐Scheme Photosystem toward Robust and Stable Solar Hydrogen Generation

Abstract

Atomically precise metal nanoclusters (NCs) represent a promising generation of metal nanomaterial because of characteristic atomic stacking mode, abundant catalytic active sites, and molecular‐like discrete energy band structure. However, crafting metal NCs‐dominated photocatalytic systems with mediated charge transport pathways for photoredox catalysis is in the infant stage and their photocatalytic mechanisms remain elusive, which is largely hampered by the ultra‐short charge lifetime, generic instability, and complicated electronic structure of metal NCs. In this study, the smart construction of all‐solid‐state metal NCs‐transition metal chalcogenides quantum dots (TMCs QDs) Z‐scheme artificial photosystems for robust and stable solar‐to‐hydrogen conversion is demonstrated. The concurrent favorable photosensitization efficiency of metal NCs and TMCs QDs synergistically stimulate the unexpected Z‐scheme charge transport pathway, which significantly boosts the anisotropic spatial vectorial charge transport/separation, giving rise to considerably enhanced visible‐light‐responsive photocatalytic hydrogen generation performances along with favorable stability. This study would push forward the prosperity of exploring metal NCs‐based photosystems for solar‐to‐hydrogen conversion.

Crafting Insulating Polymer Mediated and Atomically Precise Metal Nanoclusters Photosensitized Photosystems Towards Solar Water Oxidization

“…In the context of energy crisis, the photoelectrochemical (PEC) water-splitting technology provides a sustainable method for achieving solar energy conversion, − which is as important as polluted water purification. − In the past few years, atomically precise metal nanoclusters (NCs) have received great attention by virtue of their distinct atomic packing pattern from conventional metal nanocrystals, quantum confinement effect, and a multitude of active sites, featuring promising photosensitiveness and catalytic centers for photoredox catalysis. − Metal NCs feature a characteristic highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap, which endows them with favorable light absorption and a long excited state of charge transfer over a wide range of the solar spectrum. , Among various metal NCs, gold (Au x ) NCs have been frequently utilized as photosensitizers in photoelectrochemical (PEC) systems. Compared with Au x NCs, atomically precise silver NCs exhibit a larger UV–visible absorption extinction coefficient, a lower density state, and no Landau damping. , Moreover, the price of silver is lower than that of gold, and thus, Ag NCs demonstrate a broad prospect as a new type of solar collector .…”

“…7−10 Metal NCs feature a characteristic highest occupied molecular orbital (HOMO)−lowest unoccupied molecular orbital (LUMO) gap, which endows them with favorable light absorption and a long excited state of charge transfer over a wide range of the solar spectrum. 11,12 Among various metal NCs, gold (Au x ) NCs have been frequently utilized as photosensitizers in photoelectrochemical (PEC) systems. Compared with Au x NCs, atomically precise silver NCs exhibit a larger UV−visible absorption extinction coefficient, a lower density state, and no Landau damping.…”

Ag Nanoparticle-Decorated GaN/β-Ga2O3 Core–Shell Nanowires as Catalysts for Highly Efficient CO2-to-CO Photocatalytic Conversion

“…Multicomposite catalysts have been extensively studied to enhance the catalytic activity. − Herein, a GaN@β-Ga 2 O 3 core–shell nanowire (NW) array photocatalyst was obtained through the thermal oxidation of GaN NWs, inspired by previous reports on single GaN and Ga 2 O 3 . The design of this material improves the charge separation rate, facilitating efficient photoreduction of CO 2 under simulated sunlight.…”

Surfactant-free 2D/2D Pd/g-C3N4 for enhanced photocatalytic CO2 reduction

“…Photocatalysis, which converts solar energy into chemical energy, is an appealing strategy to overcome energy crisis and environmental pollution. 1–3 Emerging two-dimensional (2D) semiconductors show unprecedented advantages in photocatalysis due to their ultrahigh surface area and short migration distance of carriers. 4,5 However, the quantum efficiency is still low due to the severe recombination of photogenerated electron–hole pairs.…”