Jiawei Lv

Self‐Assembly of Chiral Gold Clusters into Crystalline Nanocubes of Exceptional Optical Activity

Self-assembly of inorganic nanoparticles into ordered structures is of interest in both science and technology because it is expected to generate new properties through collective behavior; however, such nanoparticle assemblies with characteristics distinct from those of individual building blocks are rare. Herein we use atomically precise Au clusters to make ordered assemblies with emerging optical activity. Chiral Au clusters with strong circular dichroism (CD) but free of circularly polarized luminescence (CPL) are synthesized and organized into uniform body-centered cubic (BCC) packing nanocubes. Once the ordered structure is formed, the CD intensity is significantly enhanced and a remarkable CPL response appears. Both experiment and theory calculation disclose that the CPL originates from restricted intramolecular rotation and the ordered stacking of the chiral stabilizers, which are fastened in the crystalline lattices.

Boosting Hot Electrons in Hetero-superstructures for Plasmon-Enhanced Catalysis

Hetero-nanostructures featured with both strong plasmon absorption and high catalytic activity are believed to be ideal platforms to realize efficient light-driven catalysis. However, in reality, it remains a great challenge to acquire high-performance catalysis in such hetero-nanostructures due to poor generation and transfer of plamson-induced hot electrons. In this report, we demonstrate that Au nanorod@Pd superstructures (Au@Pd SSs), where the ordered Pd nanoarrays are precisely grown on Au nanorod surfaces via solution-based seed-mediated approach, would be an excellent solution for this challenge. Both experiment and theory disclose that the ordered arrangement of Pd on Au nanorod surfaces largely promotes hot electron generation and transfer via amplified local electromagnetic field and decreased electron-phonon coupling, respectively. Each effect is separately highlighted in experiments by the significant plasmon-enhanced catalytic activity of Au@Pd SSs in two types of important reactions with a distinct time scale of bond-dissociation event: molecular oxygen activation and carbon-carbon coupling reaction. This work opens the door to design and application of new generation photocatalysts.

Excitonic Circular Dichroism of Chiral Quantum Rods

As an emerging type of optically active materials, chiral molecules-stabilized semiconductor quantum dots (QDs) have achieved extensive attention. Unfortunately, understanding of the optical characteristics of chiral QDs observed by circular dichroism (CD) spectroscopy remains a great challenge due to their rather weak signals. Herein, we successfully achieve much enhanced CD responses from l- or d-cysteine-stabilized wurtzite CdSe quantum rods (QRs) thanks to their unique optical anisotropy. Furthermore, the optical activity of CdSe QRs is explored to be improved and subsequently become stable with the geometrical aspect ratio (AR) increasing, and such change matches well with alternation of the polarization factor of CdSe QRs. A non-degenerate coupled-oscillator (NDCO) model is established to elucidate the optical activity of chiral QRs, and the positive and negative natures of the CD peaks appearing at the first exciton band are clearly assigned to different transition polarization along 4pz,Se → 5sCd and 4p(x,y),Se → 5sCd, respectively. This work opens the door toward comprehension and design of optically active semiconductor nanomaterials.

Gold Nanowire Chiral Ultrathin Films with Ultrastrong and Broadband Optical Activity

An ultrastrong and broadband chiroptical response is key but remains challenging for many device applications. A simple and cost-effective bottom-up method is introduced to fabricate large-area long-range ordered chiral ultrathin films with the Langmuir-Schaeffer technique using gold nanowires as building blocks. Significantly, as-prepared ultrathin films display giant optical activity across a broad wavelength range covering visible and near infrared regions with an anisotropic factor of up to 0.285, which is the record value for bottom-up techniques. Detailed experimental result and theoretical analysis disclose that such remarkable optical activity originates from birefringence and dichroism of the well-aligned Au nanowire layers in the ultrathin films. The universality of this facile strategy for constructing chiral ultrathin films is further demonstrated with many other one-dimensional nanomaterials.

Interface Engineering in Solution-Processed Nanocrystal Thin Films for Improved Thermoelectric Performance

Solution-processed PbTe nanocrystal (NC) thin films are ligand exchanged by ethylenediamine and then annealed at 400 °C for enhancement of NC coupling. To further improve the performance, heterostructures are introduced into the PbTe/PbS films. Significantly, an optimized ZT of ≈0.30 is successfully achieved at 405 K. This method opens an avenue toward thermoelectric thin film devices with high performance.

Geometry-Modulated Magnetoplasmonic Optical Activity of Au Nanorod-Based Nanostructures

Comprehension and modulation of optical activity at nanoscale have attracted tremendous interest in the past decades due to its potential application in many fields including chemical/biological sensing, artificial metamaterials, asymmetric catalysis, and so forth. As for the conventional molecular materials, magnetic field is among the most effective routes in inducing and manipulating their optical activity; whereas the magnetic optical activity at nanoscale calls for deeper understanding, especially for anisotropic noble metal nanoparticles. In this work, distinctly different magnetic circular dichroism (MCD) responses are demonstrated in gold nanorods (GNRs) with a derivative-shaped MCD signal corresponding to the transverse surface plasmon resonance (TSPR) band and a Gaussian-shaped signal at the position of the longitudinal surface plasmon resonance (LSPR) band. Furthermore, changing the aspect ratio of GNRs easily regulates such magnetoplasmonic CD response. More interestingly, GNR assemblies with different geometric configuration (end-to-end and side-by-side) show structure-sensitive magnetoplasmonic CD response. Armed with theoretical calculation, we clearly elucidate the intrinsic relationship of the resultant magnetoplasmonic CD response with the optical symmetry and geometry factor inside one-dimensional GNRs. This work not only greatly benefits our understanding toward the nature of SPR mode in anisotropic plasmonic nanostructures but also opens the way to achieve tunable magnetoplasmonic response, which will significantly advance the design and application of optical nanodevices.

Coordination-responsive drug release inside gold nanorod@metal-organic framework core–shell nanostructures for near-infrared-induced synergistic chemo-photothermal therapy

Multifunctional core–shell nanostructures formed by integration of distinct components have received wide attention as promising biological platforms in recent years. In this work, crystalline zeolitic imidazolate framework-8 (ZIF-8), a typical metal-organic framework (MOF), is coated onto single gold nanorod(AuNR) core for successful realization of synergistic photothermal and chemotherapy triggered by near-infrared (NIR) light. Impressively, high doxorubicin hydrochloride (DOX) loading capacity followed by pH and NIR light dual stimuli-responsive DOX release can be easily implemented through formation and breakage of coordination bonds in the system. Moreover, under NIR laser irradiation at 808 nm, these novel AuNR@MOF core–shell nanostructures exhibit effective synergistic chemo-photothermal therapy both in vitro and in vivo, confirmed by cell treatment and tumor ablation via intravenous injection.

Ligand effects on electronic and optoelectronic properties of two-dimensional PbS necking percolative superlattices

The inter-nanocrystal (NC) distance, necking degree, ordering level, and NC surface ligands all affect the electronic and optoelectronic properties of NC solids. Herein, we introduce a unique PbS structure of necking percolative superlattices to exclude the morphological factors and study the effect of ligands on the NC properties. X-ray photoelectron spectroscopy data indicate that 1,2-ethanedithiol (EDT), oxalic acid, mercaptopropionic acid, and NH4SCN (SCN) ligands were attached to the surface of NCs by substrate-supported ligand exchange. Field-effect transistors were tested and photodetector measurements were performed to compare these NC solids. An SCN-treated film had the highest mobility and responsivity under high-power intensity irradiation owing to its high carrier density, whereas an EDT-treated film had the lowest mobility, photocurrent, and dark current. These findings introduce new avenues for choosing suitable ligands for NC applications.

Ultrathin Chiral Metal–Organic‐Framework Nanosheets for Efficient Enantioselective Separation

Chiral metal-organic framework (CMOF) nanosheets only a few layers thick remain a virgin land waiting for exploration. Herein, the first examples of ultrathin CMOF nanosheets are prepared by the confinement growth of two-dimensional (2D) chiral layers, which are assembled by helical metal-organic chains within microemulsion. This convenient and easily scaled up inverse microemulsion method gives a series of 2D CMOF nanosheets composed of variable metal nodes or chiral ligands. More significantly, thanks to the exceptionally large number of chiral sites exposed on surfaces, the as-obtained CMOF nanosheets exhibit much higher enantioselectivity in chiral separation compared with their bulk counterparts.

Distinct Excitonic Circular Dichroism between Wurtzite and Zincblende CdSe Nanoplatelets

Nanocrystals (NCs) with identical components and sizes but different crystal structures could not be distinguished by conventional absorption and emission spectra. Herein, we find that circular dichroism (CD) spectroscopy can easily distinguish the CdSe nanoplatelets (NPLs) with different crystal structures of wurtzite (WZ) and zincblende (ZB) with the help of chiral l- or d-cysteine ligands. In particular, the CD signs of the first excitonic transitions in WZ and ZB NPLs capped by the same chiral cysteine are opposite. Theoretic calculation supports the viewpoint of different crystal structures and surfaces arrangements between WZ and ZB NPLs contributing to this significant phenomenon. The CD peaks appearing at the first excitonic transition band of WZ or ZB CdSe NPLs are clearly assigned to the different transition polarizations along 4p( x,y,z),Se → 5sCd or 4p( x,y),Se → 5sCd. This work not only provides a deep insight into the origin of the optical activity inside chiral semiconductor nanomaterials but also proposes the design principle of chiral semiconductor nanocrystals with high optic activity.