Direct measurement of built-in electric field inside a 2D cavity.

The on-demand assembly of 2D heterostructures has brought about both novel interfacial physical chemistry and optoelectronic applications; however, existing studies rarely focus on the complementary part-the 2D cavity, which is a new-born area with unprecedented opportunities. In this study, we have investigated the electric field inside a spacer-free 2D cavity consisting of a monolayer semiconductor and a gold film substrate. We have directly captured the built-in electric field crossing a blinking 2D cavity using a Kelvin probe force microscopy-Raman system. The simultaneously recorded morphology (M), electric field (E), and optical spectroscopy (O) mapping profile unambiguously reveals dynamical fluctuations of the interfacial electric field under a constant cavity height. Moreover, we have also prepared non-blinking 2D cavities and analyzed the gap-dependent electric field evolution with a gradual heating procedure, which further enhances the maximum electric field exceeding 109 V/m. Our work has revealed substantial insights into the built-in electric field within a 2D cavity, which will benefit adventures in electric-field-dependent interfacial sciences and future applications of 2D chemical nanoreactors.

Zygote structure enables pluripotent shape-transforming deployable structure.

We propose an algorithmic framework of a pluripotent structure evolving from a simple compact structure into diverse complex 3D structures for designing the shape-transformable, reconfigurable, and deployable structures and robots. Our algorithmic approach suggests a way of transforming a compact structure consisting of uniform building blocks into a large, desired 3D shape. Analogous to a fertilized egg cell that can grow into a preprogrammed shape according to coded information, compactly stacked panels named the zygote structure can evolve into arbitrary 3D structures by programming their connection path. Our stacking algorithm obtains this coded sequence by inversely stacking the voxelized surface of the desired structure into a tree. Applying the connection path obtained by the stacking algorithm, the compactly stacked panels named the zygote structure can be deployed into diverse large 3D structures. We conceptually demonstrated our pluripotent evolving structure by energy-releasing commercial spring hinges and thermally actuated shape memory alloy hinges, respectively. We also show that the proposed concept enables the fabrication of large structures in a significantly smaller workspace.

Influence of the Epoxy/Acid Stoichiometry on the Cure Behavior and Mechanical Properties of Epoxy Vitrimers.

Bisphenol A epoxy resin cured with a mixture of dimerized and trimerized fatty acids is the first epoxy vitrimer and has been extensively studied. However, the cure behavior and thermal and mechanical properties of this epoxy vitrimer depend on the epoxy/acid stoichiometry. To address these issues, epoxy vitrimers with three epoxy/acid stoichiometries (9:11, 1:1 and 11:9) were prepared and recycled four times. Differential scanning calorimetry (DSC) was used to study the cure behavior of the original epoxy vitrimers. The dynamic mechanical properties and mechanical performance of the original and recycled epoxy vitrimers were investigated by using dynamic mechanical analysis (DMA) and a universal testing machine. Furthermore, the reaction mechanism of epoxy vitrimer with different epoxy/acid stoichiometry was interpreted. With an increase in the epoxy/acid ratio, the reaction rate, swelling ratio, glass transition temperature and mechanical properties of the original epoxy vitrimers decreased, whereas the gel content increased. The recycling decreased the swelling ratio and elongation at break of the original epoxy vitrimers. Moreover, the elongation at break of the recycled epoxy vitrimers decreased with the epoxy/acid ratio at the same recycling time. However, the gel content, tensile strength and toughness of the original epoxy vitrimers increased after the recycling. The mechanical properties of epoxy vitrimers can be tuned with the variation in the epoxy/acid stoichiometry.

Fabrication of environmentally-friendly composited sponges for efficient removal of fluoroquinolones antibiotics from water.

In this study, two environmentally-friendly macroscopically formal (PVF) composited sponges (PL and PLS) functionalized with lignin and lignosulfonate, respectively, were fabricated by a one-step mechanical foaming method. PLS, obtained with the fed mass ratio of 0.3:1 lignosulfonate to PVF in the preparation process, possessed a large specific surface area of approximately 22.396 m2/g, a three-dimensional skeleton structure with a skeletal density of 3.236 g/cm3, and 0.338 mmol/g of acidic oxygen-containing groups. Thus, it showed a high adsorption capacity of 0.16-0.24 mmol/g in removing seven antibiotics, of the popular fluoroquinolones (FQs) family from water. The contributions of hydrogen bonding, electrostatic attraction (EA) and π-π electron donor-acceptor interaction to the adsorption of FQs onto the PL and PLS sponges were analyzed systematically by investigating the pH dependence of the adsorption capacity, and the changes in adsorption of two sub structural analogs of FQs as molecular probes, and by performing theoretical calculations. The EA between the acidic oxygen-containing groups on the sponges and the amino groups of FQs played a dominant role in adsorption in near neutral conditions, leading to a superior adsorption performance for PLS. Overall, the composited sponges have the advantages of simple production, environmental-friendliness, convenient recycle, and low cost, which renders them potentially viable in treating real wastewater containing FQs.

Near-Infrared-Responsive Photo-Driven Nitrogen Fixation Enabled by Oxygen Vacancies and Sulfur Doping in Black TiO2-xSy Nanoplatelets.

Solar-driven nitrogen fixation is a promising clean and mild approach for ammonia synthesis beyond the conventional energy-intensive Haber-Bosch process. However, it is still challenging to design highly active, stable, and low-cost photocatalysts for activating inert N2 molecules. Herein, we report the synthesis of anatase-phase black TiO2-xSy nanoplatelets enriched with abundant oxygen vacancies and sulfur anion dopants (VO-S-rich TiO2-xSy) by ion exchange method at gentle conditions. The VO-S-rich TiO2-xSy nanoplatelets display a narrowed bandgap of 1.18 eV and much stronger light absorption that extends to the near-infrared (NIR) region. The co-presence of oxygen vacancies and sulfur dopants facilitates the adsorption of N2 molecules, promoting the reaction rate of N2 photofixation. Theoretical calculations reveal the synergistic effect of oxygen vacancies and sulfur dopants on visible-NIR light adsorption and photoexcited carrier transfer/separation. The VO-S-rich TiO2-xSy exhibits improved ammonia yield rates of 114.1 µmol g-1 h-1 under full-spectrum irradiation and 86.2 µmol g-1 h-1 under visible-NIR irradiation, respectively. Notably, even under only NIR irradiation (800-1100 nm), the VO-S-rich TiO2-xSy can still deliver an ammonia yield rate of 14.1 µmol g-1 h-1. This study presents the great potential to regulate the activity of photocatalysts by rationally engineering the defect sites and dopant species for room-temperature N2 reduction.

Removal of fluoroquinolone antibiotics using actinia-shaped lignin-based adsorbents: Role of the length and distribution of branched-chains.

A series of actinia-shaped lignin-based adsorbents (LNAEs) featuring lignin(LN) as the core and grafted poly(acrylic acid) (PAA) as the tentacle were designed and fabricated. LNAEs were applied to remove ofloxacin and ciprofloxacin from water, and their maximum adsorption capacities were 0.835 and 0.965 mmol/g at pH 6.0, respectively. However, their adsorption capacities were up to about 20 % and 31 % reductions in the present of NaCl and humic acid, respectively. Electrostatic attraction (EA) and hydrogen bonding (HB), including ordinary HB and negative charged auxiliary HB, were mainly involved in adsorption. Experimental and calculation results indicated HB contributes more than EA. The effects of two structural factors of LNAEs, namely, PAA branched-chain length(L) and distribution density(D), on the adsorption performance associated with HB and EA, were quantitatively discussed using a binary nonlinear model based on phenomenological theory. The fitting results were completely consistent with the experimental findings. D was more efficient than L in promoting HB and EA in adsorption due to the cooperative effects of adjacent branched-chains and enhanced activity of terminal groups. This study provides a better understanding of the structure-activity relationship of surface grafting-modified adsorbents and fundamental guidance for the exploitation and design of novel and efficient adsorbents.

An enhanced coagulation using a starch-based coagulant assisted by polysilicic acid in treating simulated and real surface water.

In this work, a simple and environmentally-friendly enhanced coagulation, by using a cationic starch-based coagulant (starch-3-chloro-2-hydroxypropyl trimethyl ammonium chloride, St-CTA) coupled with an optimized polysilicic acid (PSA), has been tried to coagulate the kaolin suspensions and humic acid (HA) aqueous solutions, which are used as the simulated sources of inorganic colloidal particles and organic pollutant, respectively, in micro-polluted turbid surface water. Dosing of St-CTA and PSA at the same time is more efficient and more convenient than other two separated feeding methods in this enhanced coagulation process. The synergic coagulation process and mechanism were studied and discussed in detail based on the apparent coagulation performance, floc properties, and zeta potentials of supernatants. St-CTA caused an efficient charge neutralization, i.e. compression of electric double layer of kaolin particles and electrostatic adsorption of HA, followed by an effective netting-bridging effect of PSA, resulting in an improved purification performance. St-CTA with a higher charge density showed better purification performance due to enhanced charge neutralization effect. In addition to simulated water, the validation of this enhanced coagulation process was further confirmed by comparison with a conventional coagulant, polyaluminium chloride, in treating a real surface water. This work thus provides a simple and environmentally-friendly strategy to efficiently purify micro-polluted turbid surface water and further improve the water safety.

Computational wrapping: A universal method to wrap 3D-curved surfaces with nonstretchable materials for conformal devices.

This study starts from the counterintuitive question of how we can render conventional stiff, nonstretchable, and even brittle materials sufficiently conformable to fully wrap curved surfaces, such as spheres, without failure. Here, we extend the geometrical design method of computational origami to wrapping. Our computational wrapping approach provides a robust and reliable method for fabricating conformal devices for arbitrary curved surfaces with a computationally designed nonpolyhedral developable net. This computer-aided design transforms two-dimensional (2D)-based materials, such as Si wafers and steel sheets, into various targeted conformal structures that can fully wrap desired 3D structures without fracture or severe plastic deformation. We further demonstrate that our computational wrapping approach enables a design platform that can transform conventional nonstretchable 2D-based devices, such as electroluminescent lighting and flexible batteries, into conformal 3D curved devices.

Evaluation of the structural factors for the flocculation performance of a co-graft cationic starch-based flocculant.

Three series of co-graft cationic starch (St)-based flocculants with distinct structural characteristics, namely, charge density (CD), graft-chain length (L), and graft-chain distribution (N), were successfully synthesized through graft copolymerization of [(2-methacryloyloxyethyl) trimethyl ammonium chloride] and acrylamide. These St-based flocculants with different molecular structures were used to flocculate various kaolin suspensions with different initial turbidities and a sodium humate (NaHA) aqueous solution. The experimental results indicated that CD contributed to flocculation evidently, whereas average L and its N were insignificant in experimentally measured ranges. On the basis of phenomenological theory, a second-order polynomial equation was used to further quantitatively analyze the effects of the three structural factors on the flocculation performance of these St-based flocculants, which were fully consistent with the experimental results. Besides, the optimal dose and its corresponding removal rate could be predicted exactly, and the flocculation mechanisms were discussed in detail according to the established models. With the combination of floc properties and zeta potentials, the flocculation mechanisms of these St-based flocculants for flocculation of kaolin suspensions and NaHA aqueous solution were mainly ascribed to charge patching and simple charge neutralization, respectively. These results improve the understanding of the structure-activity relationship of these graft St-based flocculants, which is of significant guidance for the utilization and design of novel flocculants.