Design Principles for Maximizing Hole Utilization of Semiconductor Quantum Wires toward Efficient Photocatalysis.

Maximizing hole-transfer kinetics-usually a rate-determining step in semiconductor-based artificial photosynthesis-is pivotal for simultaneously enabling high-efficiency solar hydrogen production and hole utilization. However, this remains elusive yet as efforts are largely focused on optimizing the electron-involved half-reactions only by empirically employing sacrificial electron donors (SEDs) to consume the wasted holes. Using high-quality ZnSe quantum wires as models, we show that how hole-transfer processes in different SEDs affect their photocatalytic performances. We found that larger driving forces of SEDs monotonically enhance hole-transfer rates and photocatalytic performances by almost three orders of magnitude, a result conforming well with the Auger-assisted hole-transfer model in quantum-confined systems. Intriguingly, further loading Pt cocatalyts can yield either an Auger-assisted model or a Marcus inverted region for electron transfer, depending on the competing hole-transfer kinetics in SEDs.

On-demand synthesis of high-quality, blue-light-active ZnSe colloidal quantum wires.

Beyond the state-of-the-art Cd-containing quantum wires (QWs), heavy-metal-free semiconductor QWs, such as ZnSe, are of great interest for next-generation environmental-benign applications. Unfortunately, simultaneous, on-demand manipulation of their radial and axial sizes-that allows strong quantum confinement in the blue-light region-has so far been challenging. Here we present a two-step catalyzed growth strategy that enables independent, high-precision and wide-range controls over the diameter and length of ZnSe QWs. We find that a new epitaxial orientation between the cubic-phase Ag2Se solid catalyst and wurtzite ZnSe QWs kinetically favors the formation of defect-free ultrathin QWs. Thanks to their high uniformity, the resulting blue-light-active, phase-pure ZnSe QWs exhibit well-defined excitonic absorption with the 1Se-1Sh transition linewidth as narrow as sub-13 nm. Combining the transient absorption spectroscopy, we further show that surface electron traps in these ZnSe QWs can be eliminated by thiol passivation, which results in long-lived charge carriers and high-efficiency solar-to-hydrogen conversion.

Catalyzed Growth for Atomic-Precision Colloidal Chalcogenide Nanowires and Heterostructures: Progress and Perspective.

One-dimensional colloidal semiconductor nanowires are of wide interest in nanoscale electronics and photonics. As compared to the zero-dimensional counterparts, their geometrical anisotropy offers an additional degree of freedom to tailor the electronic and optical properties and enables customized heterostructures with increased complexity. The colloidal synthetic chemistry developed over past decades has fueled the emergence of diverse one-dimensional nanocrystals and heterostructures, whereas the synthetic pursuit for compositionally and structurally defining them at the atomic-level precision remains yet a giant challenge. Catalyzed growth, wherein nanowires grow at the catalyst-nanowire interfaces in a layer-by-layer manner, offers a promising path toward such an ultimate goal. In this Perspective, we will take a close look at how catalyzed growth would enable the on-demand, atomic-precision control of colloidal nanowires and their heterostructures. We then further highlight their potentials for constructing higher-order heteroarchitectures with new and/or enhanced performances. Finally, we conclude with a forward-looking perspective on future challenges.