Ammonium Folate-Reinforced Self-Assembly of Gelatin into N/B/O-Enriched Hierarchical Porous Carbons with Loosely Layered Structure for Anti-Freezing Flexible Supercapacitors.

Heteroatom-doped layered porous carbons are recently regarded as promising electrode materials for high energy density supercapacitors because they can integrate high-level heteroatom-doping and layered nano-space together to provide huge pseudocapacitive reaction areas and accelerate ion diffusion/transport. Herein, an innovative strategy is reported to prepare N/B/O co-doped layered porous carbons via ammonium folate-reinforced self-assembly of gelatin and boric acid followed by carbonization. Biomass-derived ammonium folate not only acts as an N-riched precursor but also can fasten in the process of self-assembly via boric acid-assisted electrostatic adsorption and hydrogen bonding to promote the formation of stable 3D cross-linked networks, resulting in the obtained N/B/O co-doped layered porous carbon (BNLC-850) has a large specific surface area (1822 m2 g-1 ), hierarchical porous structure and super-high heteroatom contents (N, 12.65; B, 5.67; and O, 13.84 at.%). The BNLC-850 achieves an ultrahigh specific capacitance of 525.2 F g-1 in the alkaline electrolyte at 0.5 A g-1 , meanwhile, DFT calculations reveal that the high-level N/B/O-doping can effectively weaken the adsorption barriers of K-ions. Moreover, the BNLC-850 assembles anti-freezing flexible solid-state supercapacitors in MPEI-TF-IL gel polymer electrolyte deliver a high energy density of 41.2 Wh kg-1 , excellent flexibility, and long cycle-life at -20 °C.

Rechargeable Zn-Air Batteries with Outstanding Cycling Stability Enabled by Ultrafine FeNi Nanoparticles-Encapsulated N-Doped Carbon Nanosheets as a Bifunctional Electrocatalyst.

Despite grand advances in Zn-air batteries in recently years, their commercialization remains challenging due largely to the lack of efficient bifunctional oxygen catalysts. Herein, we report the crafting of a bifunctional electrocatalyst comprising ultrafine alloyed FeNi nanoparticles encapsulated within N-doped layered carbon nanosheets (denoted FeNi/N-LCN) for high-efficiency Zn-air batteries. The FeNi/N-LCN electrocatalyst is yielded via the coordination of triphenylimidazole-containing polyaniline (TPANI) oligomer with Fe- and Ni-containing precursors, followed by hydrogen binding with melamine and subsequent pyrolysis. The as-constructed FeNi/N-LCN manifests outstanding activity and stability toward both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The primary Zn-air battery assembled with FeNi/N-LCN delivers both high specific capacity and peak power density. Remarkably, the rechargeable Zn-air battery can be repeatedly charged and discharged for 1100 h at 5 mA cm-2 and for 600 h at 10 mA cm-2, representing the highest cycling stability among various reported Zn-air batteries.

Triple-Responsive Pickering Emulsion Stabilized by Core Cross-linked Supramolecular Polymer Particles.

It is significant to explore multiresponsive Pickering emulsions because of their flexibility in terms of demulsification in comparison with the single stimuli-responsive systems. In this study, we described a triple-responsive oil-in-water Pickering emulsion that was stabilized by amphiphilic core cross-linked supramolecular polymer particles (CCSPs). For this purpose, ß-cyclodextrin-terminated poly(N-isopropylacrylamide) (PNIPAM-ß-CD) and azobenzene-capped poly(4-vinylpyridine) (P4VP-azo) were separately synthesized by reversible addition-fragmentation chain transfer polymerization. By virtue of the inclusion interaction between the ß-CD host and the azobenzene guest in dimethyl sulfoxide, the amphiphilic supramolecular block copolymer, poly(4-vinylpyridine)-b-poly(N-isopropylacrylamide) (P4VP-b-PNIPAM), was formed. CCSPs were prepared through the combination of the self-assembly of P4VP-b-PNIPAM in the selective solvent, water, and the cross-linking of the P4VP core with 1,4-dibromobutane. Due to thermoresponsiveness of PNIPAM shells and the supramolecular linkages between the cross-linked hydrophobic P4VP core and hydrophilic PNIPAM shells, the as-prepared CCSPs exhibited temperature-, light-, and amantadine hydrochloride guest-triggered morphological transitions. Such triple-responsive morphological transitions gifted CCSPs stabilized oil-in-water Pickering emulsion with flexible demulsification in response to various factors, such as thermo, light, and amantadine hydrochloride or their combinations. Such triple-responsive oil-in-water Pickering emulsion also provided an ideal platform for heterogeneous reactions conducted at the oil-water interface. A large interfacial area and responsive demulsification allowed the reaction to be performed with an efficient and sustainable pattern.

Dual responsive Pickering emulsions stabilized by constructed core crosslinked polymer nanoparticles via reversible covalent bonds.

In this study, pH- and glucose-responsive Pickering emulsions stabilized by core crosslinked polymer nanoparticles, which were constructed via reversible covalent bonds, were presented for the first time. Firstly, well-defined PDMA-b-PAPBA (poly(N,N-dimethylacrylamide)-b-poly(3-acrylamidophenylboronic acid)) diblock copolymers were synthesized via sequential reversible addition-fragmentation chain transfer (RAFT) polymerization reactions. By means of complexation of PBA units of PDMA-b-PAPBA with PVA in basic water, core crosslinked polymer nanoparticles (CCPNs) with a core-shell structure were formed. The PAPBA/PVA crosslinked network and PDMA acted as the core and shell, respectively. Because of the reversible B-O chemical bonds in the core, the as-produced CCPNs showed structural transitions in response to the external stimuli involving pH and glucose. Investigation of the interfacial activities revealed that CCPNs exhibited high emulsifying performances, and oil in water (o/w) Pickering emulsions could be formed at a low particle content. The formed Pickering emulsions showed high stability at room temperature without any disturbances, whereas de-emulsification was observed upon improving the pH or adding glucose at a given pH. This is the first report on a responsive Pickering emulsion whose stability can be manipulated by glucose, and this type of fabricated manipulative Pickering emulsions are expected to provide useful guidance in the fields of oil recovery, interfacial reactions, etc.

A highly sensitive and reversible chemosensor for Hg(2+) detection based on porphyrin-thymine conjugates.

In this study, we demonstrated a highly sensitive, selective, and reversible chemosensor for Hg(2+) determination. This chemosensor was synthesized by direct condensation of thymin-1-ylacetic acid with zinc tetraaminoporphyrin, which has a porphyrin core as the fluorophore and four thymine (T) moieties as the specific interaction sites for Hg(2+) . The probe (4T-ZnP) exhibited split Soret bands with a small peak at 408 nm and a strong band at 429 nm in a dimethylformamide/H2 O (7/3, v/v) mixed solvent as well as a strong emission band at 614 nm. Upon the addition of Hg(2+) , the probe displayed strong fluorescence quenching due to the formation of T-Hg(2+) -T complexes. With the aid of the fluorescence spectrometer, the chemosensor in the dimethylformamide/H2 O (7/3, v/v) mixed solvent (0.3 µM) exhibited a detection limit of 6.7 nM. Interferences from other common cations, such as Co(2+) , K(+) , Sn(2+) , Zn(2+) , Cu(2+) , Ni(2+) , Mn(2+) , Na(+) , Ca(2+) , Mg(2+) , Pb(2+) , and Cd(2+) , associated with Hg(2+) analysis were effectively inhibited.

Porous N-Doped Carbon Prepared from Triazine-Based Polypyrrole Network: A Highly Efficient Metal-Free Catalyst for Oxygen Reduction Reaction in Alkaline Electrolytes.

Metal-free N-doped carbon (NC) materials have been regarded as one of the most promising catalysts for the oxygen reduction reaction (ORR) in alkaline media because of their outstanding ORR catalytic activity, high stability, and good methanol tolerance. Up to now, only a small minority of such catalysts have been synthesized from triazine-based polymeric networks. Herein, we report the synthesis of such NC catalyst by directly pyrolyzing a nitrogen-rich, triazine-based polypyrrole network (TPN). The TPN is fabricated by oxidative polymerization of 2,4,6-tripyrrol-1,3,5-triazine monomer using TfOH as the protonating agent and benzoyl peroxide as the oxidizing agent. The obtained NC-900 (pyrolyzed at 900 °C) catalyst exhibits excellent ORR activity in alkaline media with a high ORR onset potential (0.972 V vs RHE), a large kinetic-limiting current density (15.66 mA cm-2 at 0.60 V), and good MeOH tolerance and durability. The as-synthesized NC-900 material is a potential candidate as a highly active, stable, and low-cost ORR catalyst for alkaline fuel cells.

Electrochemical sensing platform for L-CySH based on nearly uniform Au nanoparticles decorated graphene nanosheets.

In this study, Au nanoparticles decorated graphene nanosheets were prepared using poly(vinylpyrrolidone) (PVP) covalently functionalized graphene oxide and chloroauric acid as template and Au precursor, respectively. Both the density and the size of Au nanoparticles deposited on the surface of graphene could be adjusted by the PVP grafting density. The graphene-Au hybrid nanosheets were then applied to fabricate a highly sensitive l-cysteine (L-CySH) electrochemical sensing platform. The cyclic voltammetry results showed that the modified glassy carbon electrode with graphene-Au hybrid nanosheets exhibited strong catalytic activity toward the electrooxidation of L-CySH. The current exhibited a widely linear response ranging from 0.1 to 24 µM with a low detection limit under the optimized conditions. The detection limit of L-CySH could reach as low as 20.5 nM (S/N=3). The enhanced electrochemical performance of the fabricated sensor was attributed to the combination of the excellent conductivity of graphene and strong catalytic property of uniform Au nanoparticles.

Water in oil emulsion stabilized by tadpole-like single chain polymer nanoparticles and its application in biphase reaction.

In this study, tadpole-like single chain polymer nanoparticles (TSCPNs) were efficiently synthesized by intramolecularly cross-linking P4VP block of commercial block polymer of PMMA2250-b-P4VP286 in N,N-dimethylformamide using propargyl bromide as cross-linking agent. The intramolecular cross-linking reaction led to the production of TSCPNs with a linear tail and a cross-linked head. The as-prepared TSCPNs were then applied as emulsifier to stabilize water in chlorobenzene emulsion, and an extremely stabilized water in oil (W/O) emulsion was generated at a low TSCPNs concentration. The TSCPNs concentration was as low as 0.0075 wt % versus total weight of water and chlorobenzene for emulsion formation. The emulsifying performance of TSCPNs was better than that of low molecular surfactant, such as Span-80. The generated W/O emulsion provided an ideal medium for the reduction of oil-soluble p-nitroanisole by water-soluble sulfide to p-anisidine, an effective contact problem between the two reactants with different solubility was well solved through interfacial reaction.

Formation of gradient multiwalled carbon nanotube stripe patterns by using evaporation-induced self-assembly.

Gradient stripe patterns of multiwalled carbon nanotubes (MWCNTs) with remarkable regularity over large areas were fabricated by using evaporation-induced self-assembly technique. In this method, a glass coverslip was inclinedly immersed into a suspension of MWCNTs in dichloroethane. By controlling the solvent evaporation temperature, well-defined gradient stripes were formed at the air-solvent-substrate contact line. The effects of several experimental parameters, such as the substrate tilt angle, concentration of MWCNTs, and evaporation temperature, on the regularity of stripes were discussed. A possible stripe formation process was described as a negative feedback of MWCNT concentration caused by a concavely curved shape of the meniscus. Additionally, the strips of MWCNTs on Si/SiO(2) substrate were directly used to fabricate field-effect transistor (FET) devices. The electrical properties of the MWCNT-FET devices were also investigated.

Sensitivity and selectivity determination of bisphenol A using SWCNT-CD conjugate modified glassy carbon electrode.

In this study, we demonstrated a highly sensitive electrochemical sensor for the determination of bisphenol A (BPA) in aqueous solution by using single-walled carbon nanotubes (SWCNTs)/ß-cyclodextrin (ß-CD) conjugate (SWCNT-CD) modified glassy carbon electrode (GCE). The cyclic voltammetry results show that the modified GCE exhibits strong catalytic activity toward the oxidation of BPA with a well-defined cyclic voltammetric peak at 0.543 V. The response current exhibits a linear range between 10.8 nM and 18.5 µM with a high sensitivity (1256 µA mM(-1)). The detection limit of BPA is 1.0 nM (S/N=3). The enhanced performance of the fabricated sensor can be attributed to the combination of the excellent electrocatalytic properties of SWCNTs and the molecular recognition ability of ß-CD. The sensor was successfully applied to determine BPA leached from real plastic samples with good recovery, ranging from 95% to 103%.