Robust Amphiphobic Few-Layer Black Phosphorus Nanosheet with Improved Stability.

Few-layer black phosphorus (FL-BP) has been intensively studied due to its attractive properties and great potential in electronic and optoelectronic applications. However, the intrinsic instability of FL-BP greatly limits its practical application. In this study, the amphiphobic FL-BP is achieved by functionalization of 1 H ,1 H ,2 H ,2 H -perfluorooctyltrichlorosilane (PFDTS) on the surface of FL-BP. The obtained PFDTS coated FL-BP (FL-BP/PFDTS) demonstrates enhanced stability, which is not observed during significant degradation for 2 months in high moisture content environment (95% humidity). Particularly, attributing to the surface amphiphobicity, FL-BP/PFDTS exhibits strong surface water repellency in the presence of oleic acid (as the contaminant), while other passivation coating layers (such as hydrophilic or hydrophobic coating) become hydrophilicity under such conditions. Owing to this advantage, the obtained FL-BP/PFDTS demonstrates enhanced stability in high moisture content environment for 2 months, even though the surface is contaminated by oil liquid or other organic solvents (such as oleic acid, CH2Cl2, and N -methyl-2-pyrrolidone). The passivation of FL-BP by amphiphobic coating provides an effective approach for FL-BP stabilization toward future applications

A leaf vein-like hierarchical silver grids transparent electrode towards high-performance flexible electrochromic smart windows

Abstract(#br)As essential components of numerous flexible and wearable optoelectronic devices, the flexible transparent conducting electrodes (TCEs) with sufficient optical transmittance and electric conductivity become more and more important. In this work, we fabricated a large-area flexible TCE based on leaf vein-like hierarchical metal grids (HMG) comprising of mesoscale “trunk” and microscale “branches”. The self-formed branched grids made the conducting paths distributing uniformly while the laser-etching trunk grids enabled to transport the collected electrons across long-distance. The Ag HMG exhibited high optical transmittance (~81%) with low sheet resistance (1.36 Ω sq –1 ), which could be simply optimized through adjusting the grids’ widths, spaces, and the sizes of the TiO 2 colloidal crackle patterns. In addition, on the basis of such advanced HMG electrode, flexible electrochromic devices (ECDs) with remarkable cyclic performance were fabricated. The HMG with high transparency, conductivity, and flexibility provides a promising TCE for the next-generation flexible and wearable optoelectronic devices

A hint from phosphine complex: The π back-bonding in cobalt-phosphorene composite enables enhanced electrocatalytic performance

Regulating the electronic structure of the metal electrocatalyst is fundamental for its performance optimizing. The electronic states of the active metal centers are highly dependent on their coordination environment, especially when bonding is formed. The π back-bonding can induce great electron density redistribution around metals, yet it is barely applied in electrocatalyst design. Herein we electrodeposited metallic cobalt on black phosphorus (BP) nanosheets, forming BP-Co with a unique π back-bonding on the interfaces. The BP-Co exhibited high electrocatalytic activity and stability for hydrogen evolution reaction in alkaline electrolyte. The electrochemical and spectroscopic characterizations demonstrated that the BP acted as σ donor and π acceptor to coordinate with electron-rich metallic Co, similar to the phosphine complex. The directional σ bond strengthen the relationship between BP and Co, while the non-directional π bond accelerated the in-plane electron transfer. The π back donation also decreased the oxophilicity of Co to make BP-Co resist the poison from oxygen species. This study can intrigue new thinking prospective for the electrocatalyst design

Engineering of Amorphous PtOx Interface on Pt/WO3 Nanosheets for Ethanol Oxidation Electrocatalysis

Direct and complete electro-oxidation of ethanol to CO2 is highly desirable for the commercialization of the direct ethanol fuel cells but is challenging. Current electrocatalysts (mainly Pt, Pd) for ethanol oxidation reaction (EOR), unfortunately, still suffer from low CO2 selectivity and rapid performance deterioration. In this study, a new Pt/α-PtOx/WO3 electrocatalyst containing amorphous PtOx structures is successfully synthesized via a facile hydrothermal reaction following Ar atmosphere annealing. The migration of lattice oxygens in the WO3 during the annealing process is confirmed as the mechanism for the formation and manipulation of amorphous interfaces containing PtOx species in the Pt/α-PtOx/WO3 electrocatalyst. The obtained Pt/α-PtOx/WO3 with tunable amorphous PtOx interfaces favors the desorption of poisoning EOR intermediates (such as CO) and high CO2 selectivity. Therefore, the state-of-art of the Pt/α-PtOx/WO3 exhibits excellent EOR activity (2.76 A mg–1), stability (47.99% of the initial activity preserved after 3600 s), and particularly high CO2 selectivity (reached 21.9%, higher than most reported values for Pt or other noble metals based EOR catalysts). This study may provide a new strategy to improve the EOR performance of metal-based catalysts and to rationally design and prepare other high-performing electrocatalysts via engineering the amorphous interfaces.</p

Regulating the reactivity of black phosphorus via protective chemistry

Rationally regulating the reactivity of molecules or functional groups is common in organic chemistry, both in laboratory and industry synthesis. This concept can be applied to inorganic nanomaterials, particularly two-dimensional black phosphorus (BP) nanosheets. The high reactivity of few-layer (even monolayer) BP is expected to be "shut down" when not required and to be resumed upon application. Here, we demonstrate a protective chemistry-based methodology for regulating BP reactivity. The protective step initiates from binding Al3+ with lone pair electrons from P to decrease the electron density on the BP surface, and ends with an oxygen/water-resistant layer through the self-assembly of hydrophobic 1,2-benzenedithiol (BDT) on BP/Al3+ This protective step yields a stabilized BP with low reactivity. Deprotection of the obtained BP/Al3+/BDT is achieved by chelator treatment, which removes Al3+ and BDT from the BP surface. The deprotective process recovers the electron density of BP and thus restores the reactivity of BP.National Research Foundation (NRF)Published versionThis study was financially supported by the National Natural Science Foundation of China (21771154), the Shenzhen Fundamental Research Programs (JCYJ20190809161013453), the Natural Science Foundation of Fujian Province of China (2018J01019 and 2018J05025), and the Fundamental Research Funds for the Central Universities (20720180019 and 20720180016). This research was also supported by the Singapore National Research Foundation Investigatorship (NRF-NRFI2018-03)

Robust Amphiphobic Few‐Layer Black Phosphorus Nanosheet with Improved Stability

Few-layer black phosphorus (FL-BP) has been intensively studied due to its attractive properties and great potential in electronic and optoelectronic applications. However, the intrinsic instability of FL-BP greatly limits its practical application. In this study, the amphiphobic FL-BP is achieved by functionalization of 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFDTS) on the surface of FL-BP. The obtained PFDTS coated FL-BP (FL-BP/PFDTS) demonstrates enhanced stability, which is not observed during significant degradation for 2 months in high moisture content environment (95% humidity). Particularly, attributing to the surface amphiphobicity, FL-BP/PFDTS exhibits strong surface water repellency in the presence of oleic acid (as the contaminant), while other passivation coating layers (such as hydrophilic or hydrophobic coating) become hydrophilicity under such conditions. Owing to this advantage, the obtained FL-BP/PFDTS demonstrates enhanced stability in high moisture content environment for 2 months, even though the surface is contaminated by oil liquid or other organic solvents (such as oleic acid, CH2Cl2, and N-methyl-2-pyrrolidone). The passivation of FL-BP by amphiphobic coating provides an effective approach for FL-BP stabilization toward future applications.Ministry of Education (MOE)Published versio

Assembly of Ultrathin Gold Nanowires into Honeycomb Macroporous Pattern Films with High Transparency and Conductivity

Because of its promising properties, honeycomb macroporous pattern (HMP) film has attracted increasing attention. It has been realized in many artificial nanomaterials, but the formation of these HMPs was attributed to templates or polymer/supermolecule/surfactant assistant assembly. Pure metal HMP film has been difficult to produce using a convenient colloidal template-free method. In this report, a unique template-free approach for preparation of Au HMP film with high transparency and conductivity is presented. Ultrathin Au nanowires, considered a linear polymer analogue, are directly assembled into HMP film on various substrates using a traditional static breath figure method. Subsequent chemical cross-linking and oxygen plasma treatment greatly enhance the stability and conductivity of the HMP film. The resulting HMP film exhibits great potential as an ideal candidate for transparent flexible conductive nanodevices

Colorimetric Biosensor for Detection of Cancer Biomarker by Au Nanoparticle-Decorated Bi₂Se₃ Nanosheets

The colorimetric biosensors have attracted intensive interest; however, their relatively low sensitivity limits their applications in clinic detection. Herein, we develop an effective colorimetric biosensor based on highly catalytic active Au nanoparticle-decorated Bi₂Se₃ (Au/Bi₂Se₃) nanosheets. Au/Bi₂Se₃ nanosheets are facilely synthesized by simply sonicating Au precursor with the as-synthesized Bi₂Se₃ nanosheets in aqueous solution. Because of the low redox potential and typical topological insulating properties, Bi₂Se₃ nanosheets is capable of providing and accumulating electrons on its surface. Such unique properties of Bi₂Se₃ nanosheets contribute to strong synergistic catalytic effects with Au nanoparticles, particularly when Au/Bi₂Se₃ nanosheets are utilized for catalyzing the reduction of 4-nitrophenol (4-NP) by NaBH₄ (<i>K</i> = 386.67 s^–1g^–1). The excellent catalytic activity of Au/Bi₂Se₃ nanosheets can be “switched off” upon treatment of antibody of cancer biomarker such as anticarcinoembryonic antibody (anti-CEA). Addition of the corresponding antigen such as cancer biomarker carcinoembryonic antibody (CEA) can successively help “switch on” the catalytic activity of Au/Bi₂Se₃ nanosheets, where the resuming degree however depends on the antigen concentration. This cancer biomarker depended catalytic behavior therefore allows Au/Bi₂Se₃ nanosheets to be employed as a colorimetric sensor for detection of a particular cancer biomarker, for the reduction of 4-nitrophenol (4-NP) by NaBH₄ itself involves apparent color change. The sensor shows high sensitivity and selectivity for the cancer biomarker, even for a concentration as low as 160 pg/mL for CEA, which fully satisfies the requirement for real clinical applications. The developed colorimetric sensor shows good generality for detection of different types of cancer biomarkers, such as α-fetoprotein (AFP) and prostate-specific antigen (PSA). Furthermore, real clinic sample analyzing result shows that the prepared biosensor is efficient for detection of CEA, providing an alternative method in cancer diagnosis