Amorphous Mn3 O4 Nanocages with High-Efficiency Charge Transfer for Enhancing Electro-Optic Properties of Liquid Crystals.

Improving electro-optic properties is essential for fabricating high-quality liquid crystal displays. Herein, by doping amorphous Mn3 O4 octahedral nanocages (a-Mn3 O4 ONCs) into a nematic liquid crystal (NLC) matrix E7, outstanding electro-optic properties of the blend are successfully obtained. At a doping concentration of 0.03 wt%, the maximum decreases of threshold voltage (Vth ) and saturation voltage (Vsat ) are 34% and 31%, respectively, and the increase of contrast (Con ) is 160%. This remarkable electro-optic activity can be attributed to high-efficiency charge transfer within the a-Mn3 O4 ONCs NLC system, caused by metastable electronic states of a-Mn3 O4 ONCs. To the best of our knowledge, such remarkable decreased electro-optic activity is observed for the first time from doping amorphous semiconductors, which could provide a new pathway to develop excellent energy-saving amorphous materials and improve their potential applications in electro-optical devices.

Direct Experimental Observation of Facet-Dependent SERS of Cu2 O Polyhedra.

Semiconductor-based surface enhanced Raman scattering (SERS) has attracted great attention due to its excellent spectral reproducibility, high uniformity, and good anti-interference ability. However, its relatively low SERS sensitivity still hinders its further developments in both performance and applications. Since the SERS is a peculiar surface effect, investigating the facet-dependent SERS activity of semiconductor nanostructures is crucial to boost their SERS signals. Although the semiconductor facet-dependent SERS effect is predicted via numerical calculations, convincing experimental evidence is scarce due to complicated and undefined surface conditions. In this work, three facet-defined ({100}, {110}, and {111} facets) Cu2 O microcrystals (MCs) with clear surface atomic configuration are utilized to investigate the facet-dependent SERS effect. The results from the Kelvin probe force microscopy measurements on single Cu2 O polyhedron, demonstrate that the facet-dependent work function plays a crucial role in the interfacial charge transfer process. Comparing with the {110} and {111} facets, the {100} facet possesses the lowest electronic work function, which enables more efficient interfacial charge transfer. The simulation results further confirm that the {100}-facets can transfer the most electrons from Cu2 O MCs to molecules due to its lowest facet work function, resulting in the largest increment of the molecular polarization.

The Flexibility of an Amorphous Cobalt Hydroxide Nanomaterial Promotes the Electrocatalysis of Oxygen Evolution Reaction.

Structural flexibility can be a desirable trait of an operating catalyst because it adapts itself to a given catalytic process for enhanced activity. Here, amorphous cobalt hydroxide nanocages are demonstrated to be a promising electrocatalyst with an overpotential of 0.28 V at 10 mA cm-2 , far outperforming the crystalline counterparts and being in the top rank of the catalysts of their kind, under the condition of electrocatalytic oxygen evolution reaction. From the direct experimental in situ and ex situ results, this enhanced activity is attributed to its high structural flexibility in terms of 1) facile and holistic transformation into catalytic active phase; 2) hosting oxygen vacancies; and 3) structure self-regulation in a real-time process. Significantly, based on plausible catalytic mechanism and computational simulation results, it is disclosed how this structural flexibility facilitates the kinetics of oxygen evolution reaction. This work deepens the understanding of the structure-activity relationship of the Co-based catalysts in electrochemical catalysis, and it inspires more applications that require flexible structures enabled by such amorphous nanomaterials.

Nickel nanoparticle-stabilized room-temperature blue-phase liquid crystals.

Blue-phase liquid crystals (BPLCs) are regarded as a potential candidate for the next generation of optical devices, but they appear in a narrow temperature range, which restricts their applicability. The nanoparticle (NP) stabilization of BPLCs, is usually about either simple-cubic BP (BPII) or body-centered-cubic BP (BPI). Hence, NP-stabilized BPIIs and BPIs possessing wide temperature ranges have been scarcely reported. Here, nickel nanoparticles (Ni NPs) were synthesized and introduced into a BPLC. The concentration-dependent temperature range effects of Ni NPs on the BPLC were investigated. A trace amount of Ni NPs could stabilize the BPLC and increase the temperature ranges of BPII and BPI; this is attributable to the Ni NPs tending to be trapped at the joints of the disclination lines, as a result of the elastic interaction, stabilizing the overall lattice structure of the BPLC. When doped with 0.05 wt% Ni NPs, the mixture shows a wider range with 7.7 °C than the range with 5.9 °C of the BPLC without Ni NPs. Meanwhile, the phase sequence and range of the aforementioned phases are reproducible upon heating and cooling, which shows that the BPLCs doped with Ni NPs are thermodynamically stable.

Remarkable SERS Activity Observed from Amorphous ZnO Nanocages.

Enhancement of the semiconductor-molecule interaction, in particular, promoting the interfacial charge transfer process (ICTP), is key to improving the sensitivity of semiconductor-based surface enhanced Raman scattering (SERS). Herein, by developing amorphous ZnO nanocages (a-ZnO NCs), we successfully obtained an ultrahigh enhancement factor of up to 6.62×105 . This remarkable SERS sensitivity can be attributed to high-efficiency ICTP within a-ZnO NC molecule system, which is caused by metastable electronic states of a-ZnO NCs. First-principles density functional theory (DFT) simulations further confirmed a stronger ICTP in a-ZnO NCs than in their crystalline counterparts. The efficient ICTP can even generate π bonding in Zn-S bonds peculiar to the mercapto molecule adsorbed a-ZnO NCs, which has been verified through the X-ray absorption near-edge structure (XANES) characterization. To the best of our knowledge, this is the first time such remarkable SERS activity has been observed within amorphous semiconductor nanomaterials, which could open a new frontier for developing highly sensitive and stable SERS technology.

High-Yield Synthesis of Hollow Octahedral Silver Nanocages with Controllable Pack Density and Their High-Performance Sers Application.

Nanoparticle-assembled octahedral Ag nanocages with sharp edges have been successfully synthesized through a Cu2 O-based template-assisted strategy. In the reaction system, Ag nanoparticles can be self-assembled on the surface of Cu2 O octahedrons, which is accomplished by the reduction of Ag+ by NaBH4 in the presence of sodium citrate as a capping agent. The hollow octahedral Ag nanocages are obtained after removing the inner Cu2 O cores with acetic acid. According to the scanning electron microscopy (SEM) and transmission electron microscopy characterization, the Ag nanocages are weaved by small nanoparticles, the rough surfaces are bestrewed with pores and sharp edges. It is found that the pack density of Ag nanoparticles strongly affects the surface enhanced Raman scattering (SERS) activities. The as-prepared 1.05-Ag cages with optimal pack density have suitable interparticle distance and suitable size of pores, which significantly enhance SERS signals. The SERS signals of rhodamine 6G (R6G) molecules can be detected at an ultralow concentration of 10-14 m when 1.05-Ag cages are used as substrates. In addition to sensitivity, 1.05-Ag cages also exhibit good reproducibility. It is expected that the ultrahigh sensitivity will endow the Ag nanocages to become a promising candidate as high-performance SERS-based chemical sensor.

Enhanced Long-Term Corrosion Resistance of 316L Stainless Steel by Multilayer Amorphous Carbon Coatings.

Diamond-like carbon (DLC) coatings are effective in protecting the key components of marine equipment and can greatly improve their short-term performance (1.5~4.5 h). However, the lack of investigation into their long-term (more than 200 h) performance cannot meet the service life requirements of marine equipment. Here, three multilayered DLC coatings, namely Ti/DLC, TiCx/DLC, and Ti-TiCx/DLC, were prepared, and their long-term corrosion resistance was investigated. Results showed that the corrosion current density of all DLC coatings was reduced by 1-2 orders of magnitude compared with bare 316L stainless steel (316Lss). Moreover, under long-term (63 days) immersion in a 3.5 wt.% NaCl solution, all DLC coatings could provide excellent long-term corrosion protection for 316Lss, and Ti-TiCx/DLC depicted the best corrosion resistance; the polarization resistances remained at ~3.0 × 107 Ω·cm2 after immersion for 63 days, with more interfaces to hinder the penetration of the corrosive media. Meanwhile, during neutral salt spray (3000 h), the corrosion resistance of Ti/DLC and TiCx/DLC coatings showed a certain degree of improvement because the insoluble corrosion products at the defects blocked the subsequent corrosion. This study can provide a route to designing amorphous carbon protective coatings for long-term marine applications in different environments.

Composition-adjustable Ag-Au substitutional alloy microcages enabling tunable plasmon resonance for ultrasensitive SERS.

Engineering the surface plasmon resonance (SPR) properties is a critical issue for improving device performance in the fields of plasmonics, nanophotonics, optoelectronics, and electrochemistry. Here, we demonstrated a programmable manipulation of the surface plasmon resonance (SPR) effect using composition-adjustable Ag-Au substitutional alloy microcages (SAMCs) through a facile NaBH4-cooperative galvanic replacement reaction. The SPR frequency of the Ag-Au SAMCs can be continuously and exquisitely manipulated without resonance damping or broadening via accurate adjustment of the elemental composition distribution at the perfect homogeneity on the atomic-level. Significantly, both the tunable SPR frequency and excellent chemical stability synergistically endow the hollow Ag-Au SAMCs with excellent SERS sensitivity and reproducibility, which lays a foundation for the realization of trace detection of thiram at an ultralow concentration of 1 × 10-12 M. This strategy is a promising candidate for efficient promotion of the SERS activity for metal-based substrates.