Strengthening Mechanism of a Single Precipitate in a Metallic Nanocube.

Nanoprecipitates play a significant role in the strength, ductility, and damage tolerance of metallic alloys through their interaction with crystalline defects, especially dislocations. However, the difficulty of observing the action of individual precipitates during plastic deformation has made it challenging to conclusively determine the mechanisms of the precipitate-defect interaction for a given alloy system and presents a major bottleneck in the rational design of nanostructured alloys. Here, we demonstrate the in situ compression of core-shell nanocubes as a promising platform to determine the precise role of individual precipitates. Each nanocube with a dimension of ∼85 nm contains a single spherical precipitate of ∼25 nm diameter. The Au-core/Ag-shell nanocubes show a yield strength of 495 MPa with no strain hardening. The deformation mechanism is determined to be surface nucleation of dislocations which easily traverses through the coherent Au-Ag interface. On the other hand, the Au-core/Cu-shell nanocubes show a yield strength of 829 MPa with a pronounced strain hardening rate. Molecular dynamics and dislocation dynamics simulations, in conjunction with TEM analysis, have demonstrated the yield mechanism to be the motion of threading dislocations extending from the semicoherent Au-Cu interface to the surface, and strain hardening to be caused by a single-armed Orowan looping mechanism. Nanocube compression offers an exciting opportunity to directly compare computational models of defect dynamics with in situ deformation measurements to elucidate the precise mechanisms of precipitate hardening.

Interfacial Engineering of Semicoherent Interface at Purified CsPbBr3 Quantum Dots/2D-PbSe for Optimal CO2 Photoreduction Performance.

Heterogeneous photocatalysts are extensively used to achieve interfacial electric fields for acceleration of oriented charge carrier transport and further promotion of photocatalytic redox reactions. Unfortunately, the incoherent interfaces are almost present in the heterostructures owing to large lattice mismatch accompanied by the interfacial defects and high density of gap states, acting as high energy barriers for charge migration. In this work, we report the atomic engineering of CsPbBr3/PbSe heterogeneous interfaces and conversion from incoherent features to semicoherent characters via methyl acetate (MeOAc) purification of CsPbBr3 quantum dots (QDs) before composited with two-dimensional (2D)-PbSe, which is confirmed by high-resolution transmission electron microscopy. The photocatalytic performances and theoretical calculations indicate that semicoherent interfaces are favorable for improving the activity and reactivity of the heterostructure, triggering 3 times enhanced photocatalytic CO2 reduction rate with 91% selectivity and satisfactory stability. This study proposes a facile method for photocatalytic heterojunctions to transform incoherent interfaces to photocatalytically beneficial semicoherent boundaries, accompanying with a systematic analysis of the consequent chemical dynamics to demonstrate the mechanism of the semicoherent interface for supporting photocatalysis. The understandings gained from this work are valuable for rational interfacial lattice engineering of heterogeneous photocatalysts for efficient solar fuel production.

Direct Z-Scheme Heterojunction of Semicoherent FAPbBr3/Bi2WO6 Interface for Photoredox Reaction with Large Driving Force.

Metal halide perovskites with direct band gap and strong light absorption are promising materials for harvesting solar energy; however, their relatively narrow band gap limits their redox ability when used as a photocatalyst. Adding a second semiconductor component with the appropriate band structure offsets can generate a Z-scheme photocatalytic system, taking full advantage of the perovskite's intrinsic properties. In this work, we develop a direct Z-scheme photocatalyst based on formamidinium lead bromide and bismuth tungstate (FAPbBr3/Bi2WO6) with strong redox ability for artificial solar-to-chemical energy conversion. With desirable band offsets and strong joint redox potential, the dual photocatalyst is shown to form a semicoherent heterointerface. Ultrafast transient infrared absorption studies employing selective excitation reveal synergetic photocarrier dynamics and demonstrate Z-scheme charge transfer mechanisms. Under simulated solar irradiation, a large driving force photoredox reaction (∼2.57 eV) of CO2 reduction coupled with benzyl alcohol oxidation to benzaldehyde is achieved on the Z-scheme FAPbBr3/Bi2WO6 photocatalyst, harnessing the full synergetic potential of the combined system.