Blocking Metal Nanocluster Growth through Ligand Coordination and Subsequent Polymerization: The Case of Ruthenium Nanoclusters as Robust Hydrogen Evolution Electrocatalysts.

Metal nanoclusters providing maximized atomic surface exposure offer outstanding hydrogen evolution activities but their stability is compromised as they are prone to grow and agglomerate. Herein, a possibility of blocking metal ion diffusion at the core of cluster growth and aggregation to produce highly active Ru nanoclusters supported on an N, S co-doped carbon matrix (Ru/NSC) is demonstrated. To stabilize the nanocluster dispersion, Ru species are initially coordinated through multiple Ru─N bonds with N-rich 4'-(4-aminophenyl)-2,2:6',2''-terpyridine (TPY-NH2) ligands that are subsequently polymerized using a Schiff base. After the pyrolysis of the hybrid composite, highly dispersed ultrafine Ru nanoclusters with an average size of 1.55 nm are obtained. The optimized Ru/NSC displays minimal overpotentials and high turnover frequencies, as well as robust durability both in alkaline and acidic electrolytes. Besides, outstanding mass activities of 3.85 A mg-1 Ru at 50 mV, i.e., 16 fold higher than 20 wt.% Pt/C are reached. Density functional theory calculations rationalize the outstanding performance by revealing that the low d-band center of Ru/NSC allows the desorption of *H intermediates, thereby enhancing the alkaline HER activity. Overall, this work provides a feasible approach to engineering cost-effective and robust electrocatalysts based on carbon-supported transition metal nanoclusters for future energy technologies.

A Novel Anderson-Type POMs-Based Hybrids Flame Retardant for Reducing Smoke Release and Toxicity of Epoxy Resins.

Smoke emission and smoke toxicity have drawn more attention to improving the fire safety of polymers. In this work, a polyoxometalates (POMs)-based hybrids flame retardant (P-AlMo6 ) epoxy resin (EP) is prepared with toxicity-reduction and smoke-suppression properties via a peptide coupling reaction between POMs and organic molecules with double DOPO (bisDOPA). It combines the good compatibility of the organic molecule and the superior catalytic performance of POMs. Compared to pure EP, the glass transition temperature and flexural modulus of EP composite with 5 wt.% P-AlMo6 (EP/P-AlMo6 -5) are raised by 12.3 °C and 57.75%, respectively. Notably, at low flame-retardant addition, the average CO to CO2 ratio (Av-COY/Av-CO2 Y) is reduced by 33.75%. Total heat release (THR) and total smoke production (TSP) are lowered by 44.4% and 53.7%, respectively. The Limited Oxygen Index (LOI) value achieved 31.7% and obtained UL-94 V-0 rating. SEM, Raman, X-ray photoelectron spectroscopy, and TG-FTIR are applied to analyze the flame-retardant mechanism in condensed and gas phase. Outstanding flame retardant, low smoke toxicity properties are attained due to the catalytic carbonization ability of metal oxides Al2 O3 and MoO3 produced from the breakdown of POMs. This work advances the development of POMs-based hybrids flame retardants with low smoke toxicity properties.

Metallopolymer Particle Engineering via Etching of Boronate Polymers toward High-Performance Overall Water Splitting Catalysts.

Metallopolymers combine the property features of both metallic compounds and organic polymers, representing a typical direction for the design of high-performance hybrid materials. Here, a highly adaptive etching method to create pores and cavities in the metallopolymer particles is established. Starting from boronate polymer (BP) and inorganic@BP core-shell particles, porous, hollow, and yolk-shell metallopolymer particles can be fabricated, respectively. By taking advantage of the easy control over composition and pore/cavity structure, these metallopolymer particles provide a universal platform for the fabrication of nitrogen, boron co-doped carbon nanocomposites loaded with metals (M-NBCs). The as-prepared M-NBCs exhibit remarkable catalytic activities toward oxygen evolution reaction and hydrogen evolution reaction. An alkaline overall water splitting cell assembled by using M-NBCs as the anode and cathode can be driven by a single AAA battery. The proposed strategy for the construction of metallopolymer composites may enlighten for the design of complex hybrid nanomaterials.

Self-activatable carbon nanotube@ruthenium-catechol coordination complex for hydrogen evolution reaction.

We report a simple metal ion-catechol coordination strategy to coat ruthenium-catechol polymer complex (TAC-Ru) on the surface of carbon nanotubes (CNT) to form a core-shell structure (abbreviated as CNT@TAC-Ru). This is achieved by firstly polymerizing catechol and boronic acid monomers on the surface of CNT to form a boronate ester polymer (BP) shell. Then, Ru3+is used to etch the BP shell, and cleave the dynamic boronate ester bond, leading to the formation of a CNT@ruthenium-catechol coordination complex based on the coordinative efficiency of the catechol group. The electrocatalytic property of the CNT@TAC-Ru composite can be activated through electrochemical cycling treatment. The as-activated CNT@TAC-Ru exhibits evidently improved hydrogen evolution reaction (HER) performance with an overpotential of 10 mV in 1.0 M KOH at a current density of 10 mA cm-2, which is better than that of commercial Pt/C (32 mV). And the long-term stability is also desirable. This work provides a pyrolysis-free method to form metal-polymer-carbon composite with high HER performance under the alkaline condition.

Predictable Particle Engineering: Programming the Energy Level, Carrier Generation, and Conductivity of Core-Shell Particles.

Core-shell structures are of particular interest in the development of advanced composite materials as they can efficiently bring different components together at nanoscale. The advantage of this structure greatly relies on the crucial design of both core and shell, thus achieving an intercomponent synergistic effect. In this report, we show that decorating semiconductor nanocrystals with a boronate polymer shell can easily achieve programmable core-shell interactions. Taking ZnO and anatase TiO2 nanocrystals as inner core examples, the effective core-shell interactions can narrow the band gap of semiconductor nanocrystals, change the HOMO and LUMO levels of boronate polymer shell, and significantly improve the carrier density of core-shell particles. The hole mobility of core-shell particles can be improved by almost 9 orders of magnitude in comparison with net boronate polymer, while the conductivity of core-shell particles is at most 30-fold of nanocrystals. The particle engineering strategy is based on two driving forces: catechol-surface binding and B-N dative bonding and having a high ability to control and predict the shell thickness. Also, this approach is applicable to various inorganic nanoparticles with different components, sizes, and shapes.

Composite polymer nanoarchitectures from a one-pot hydrothermal route.

Exploitation of facile and versatile synthetic approaches to polymeric nanoarchitectures is of great interest in polymer science and engineering. Herein, we show that a simple hydrothermal route using double-solvents as reaction media has the ability to generate polymer nanospheres with tunable morphologies and components. In this one-pot approach, condensation polymerization of a resol precursor and radical polymerization of styrene are allowed to occur simultaneously under hydrothermal treatment. The synergistic self-organization of phenol-formaldehyde crosslinked networks and polystyrene chains leads to the formation of well-defined hollow nanospheres with adjustable shell thickness or even Janus particles comprising a solid hemisphere and a hollow hemisphere. Furthermore, control over the composition of the hollow polymer nanospheres can be easily achieved by introducing a third monomer into the hydrothermal system.

Fluorescent polymeric assemblies as stimuli-responsive vehicles for drug controlled release and cell/tissue imaging.

Polymer assemblies with good biocompatibility, stimuli-responsive properties and clinical imaging capability are desirable carriers for future biomedical applications. Herein, we report on the synthesis of a novel anthracenecarboxaldehyde-decorated poly(N-(4-aminophenyl) methacryl amide-oligoethyleneglycolmonomethylether methacrylate) (P(MAAPAC-MAAP-MAPEG)) copolymer, comprising fluorescent chromophore and acid-labile moiety. This copolymer can assemble into micelles in aqueous solution and shows a spherical shape with well-defined particle size and narrow particle size distribution. The pH-responsive property of the micelles has been evaluated by the change of particle size and the controlled release of guest molecules. The intrinsic fluorescence property endows the micelles with excellent cell/tissue imaging capability. Cell viability evaluation with human hepatocellular carcinoma BEL-7402 cells demonstrates that the micelles are nontoxic. The cellular uptake of the micelles indicates a time-dependent behavior. The H22-tumor bearing mice treated with the micelles clearly exhibits the tumor accumulation. These multi-functional nanocarriers may be of great interest in the application of drug delivery.

Polymer crystallization dynamics investigated by synchronous scanning spectrum.

There is a cosine function between the reflected light intensity of a solid surface and its refractive index. And the mean squared fluctuation of refractive index is related to fluctuation of density and concentration. So some internal structures changes of materials can be reflected by changes in reflected light. Based on this theory, the synchronous scanning spectrum (SSS) technique was successfully applied to monitor melting and nonisothermal melt-crystallization of poly(ε-caprolactone) (PCL) film on a copper substrate. SSS can be implemented on a spectrofluorimeter by simultaneously scanning the excitation and emission monochromators (i. e, Δλ = λex-λem = 0 nm). In SSS of PCL films, two dominant peaks correlated to the light source spectrum of the spectrofluorimeter (at 467 and 473 nm) were used to characterize the macromolecular structure evolution during the melting and nonisothermal melt-crystallization processes. Detailed thermodynamic and crystallization kinetics parameters obtained by SSS method. The Avrami exponent n obtained by SSS method is in the range of 2.8-3.2 with an average of 3.13, illustrating a heterogeneous nucleation process followed by a three-dimensional spherulitic crystal growth mechanism. The crystallization activation energy is -158.2 kJ · mol(-1). These results are in agreement with values determined from differential scanning calorimetry (DSC) method. It indicates that SSS technique is a simple, effective in situ method for measuring the dynamic melting and crystallization process of polymers. Moreover, the SSS method is a universal spectroscopic technique based on a spectrofluorimeter for monitoring both luminescent and non-luminous solid polymers.

Carboxymethylcellulose hydrogels with stable carbon quantum dots: Enabling dynamic fluorescence modulation, automatic erasure, and secure information encryption.

Inspired by "disappear after reading", a time-modulated encryption hydrogel was synthesized by carboxymethyl cellulose with carbon quantum dots. Carboxymethyl cellulose in this system stabilized carbon quantum dots, which ensured the whole hydrogel worked well. The encryption/decryption of information depended on pH adjustment, application of EDTA and Cr (VI). Furthermore, an in-depth analysis of the fluorescence change mechanism uncovered that fluorescence quenching was potentially influenced by internal filtering effects and static quenching, which involved the amino, carboxyl, and hydroxyl groups present within the hydrogel.

Heterogeneous silver-polyaniline nanocomposites with tunable morphology and controllable catalytic properties.

This paper introduces not only a simple hydrothermal route to silver-polyaniline (Ag-PANI) nanocomposites with controllable morphology, but also a type of catalyst possessing tunable and switchable catalytic capability. Ag-PANI Janus nanoparticles (NPs) and Ag@PANI core-shell NPs have been constructed successfully at different hydrothermal temperatures. The diameter of both Ag and PANI hemispheres of Janus NPs, as well as the PANI shell thickness of core-shell NPs, was finely tuned via adjustment of the feed ratio. We also gained a deeper insight into the functionalities of PANI components in the catalytic capability of the heterogeneous catalysts, choosing catalytic reductions of nitrobenzene (NB) and 4-nitrophenol (4-NP) as model reactions. Our results showed that the catalytic capability of the nanocomposites was dependent on the PANI morphology and hydrophobicity. The PANI shell coating on Ag NPs can concentrate the lipophilic NB, thus leading to an enhanced catalytic capability of Ag@PANI core-shell NPs. However, this enhanced catalytic capability was not observed for Ag-PANI Janus NPs when catalytically reducing NB. More importantly, the catalytic capability of the core-shell NPs in the reduction of hydrophilic 4-NP is switchable by varying the PANI shell from an undoped to a doped state.

A Novel P/N/Si-Containing Vanillin-Based Compound for a Flame-Retardant, Tough Yet Strong Epoxy Thermoset.

It is still extremely challenging to endow epoxy resins (EPs) with excellent flame retardancy and high toughness. In this work, we propose a facile strategy of combining rigid-flexible groups, promoting groups and polar phosphorus groups with the vanillin compound, which implements a dual functional modification for EPs. With only 0.22% phosphorus loading, the modified EPs obtain a limiting oxygen index (LOI) value of 31.5% and reach V-0 grade in UL-94 vertical burning tests. Particularly, the introduction of P/N/Si-containing vanillin-based flame retardant (DPBSi) improves the mechanical properties of EPs, including toughness and strength. Compared with EPs, the storage modulus and impact strength of EP composites can increase by 61.1% and 240%, respectively. Therefore, this work introduces a novel molecular design strategy for constructing an epoxy system with high-efficiency fire safety and excellent mechanical properties, giving it immense potential for broadening the application fields of EPs.

Multifunctional Organohydrogels for pH-Responsive Fluorescent and Electrostimulus Writing.

Hydrogels have attracted widespread attention in anticounterfeiting due to their unique physical/chemical properties and designability. However, hydrogels' poor mechanical properties and sluggish response to chemical stimuli pose challenges for their wide application. A fluorescent tough organohydrogel capable of freeform writing of information is reported in this work. By incorporation of the fluorescent monomer 7-methylacryloxy-4-methylcoumarin into the polyacrylamide network in a covalently cross-linked manner while intertwining with the carboxymethyl cellulose sodium network, a fluorescent tough organohydrogel with a dual-network structure is prepared. The organohydrogel shows acid-base-mediated adjustable fluorescence through the transformation of fluorescent monomers. Ion printing and electrical stimulation design achieved free information storage and encryption. In addition, the prepared organohydrogel has good antifreezing properties and can be encrypted and decrypted at subzero temperatures. The encrypted information in the organohydrogel can be read only after UV-light irradiation. These patterned fluorescent organohydrogels should find applications in protected message displays for improved information security.

Platinum-nanoparticle-supported core--shell polymer nanospheres with unexpected water stability and facile further modification.

Core-shell nanospheres (CSNSs) with hydrophobic cores and hydrophilic shells were fabricated via a simple mini-emulsion polymerization for the stabilization of platinum nanoparticles (Pt-NPs). The CSNSs showed extremely high loading capacity of Pt-NPs (the largest loading amount of the Pt-NPs was about 49.2 wt%). Importantly, the Pt-NPs/CSNSs nanocomposites had unexpected stability in aqueous solution. DLS results revealed that the CSNSs loaded with Pt-NPs exhibited almost no aggregation after standing for a long time . However, the Pt-NPs immobilized on the CSNSs were not straitlaced: they could transport and redistribute between CSNSs freely when the environmental temperature was higher than the melting point of the CSNS shell. Owing to their excellent stability in aqueous solution, the surface of the Pt-NPs/CSNSs nanocomposites could be further decorated easily. For example, polyaniline (PANI)-coated Pt-NPs/CSNSs, nickel (Ni)-coated Pt-NPs/CSNSs and PANI/Pt-NPs dual-layer hollow nanospheres were facilely fabricated from the Pt-NPs/CSNS nanocomposites.

In Situ Generation of Ultrathin MoS2 Nanosheets in Carbon Matrix for High Energy Density Photo-Responsive Supercapacitors.

Stimuli-responsive supercapacitors have attracted broad interest in constructing self-powered smart devices. However, due to the demand for high cyclic stability, supercapacitors usually utilize stable or inert electrode materials, which are difficult to exhibit dynamic or stimuli-responsive behavior. Herein, this issue is addressed by designing a MoS2 @carbon core-shell structure with ultrathin MoS2 nanosheets incorporated in the carbon matrix. In the three-electrode system, MoS2 @carbon delivers a specific capacitance of 1302 F g-1 at a current density of 1.0 A g-1 and shows a 90% capacitance retention after 10 000 charging-discharging cycles. The MoS2 @carbon-based asymmetric supercapacitor displays an energy density of 75.1 Wh kg-1 at the power density of 900 W kg-1 . Because the photo-generated electrons can efficiently migrate from MoS2 nanosheets to the carbon matrix, the assembled photo-responsive supercapacitor can answer the stimulation of ultraviolet-visible-near infrared illumination by increasing the capacitance. Particularly, under the stimulation of UV light (365 nm, 0.08 W cm-2 ), the device exhibits a ≈4.50% (≈13.9 F g-1 ) increase in capacitance after each charging-discharging cycle. The study provides a guideline for designing multi-functional supercapacitors that serve as both the energy supplier and the photo-detector.

Electrically programmable adhesive hydrogels for climbing robots.

Although there have been notable advances in adhesive materials, the ability to program attaching and detaching behavior in these materials remains a challenge. Here, we report a borate ester polymer hydrogel that can rapidly switch between adhesive and nonadhesive states in response to a mild electrical stimulus (voltages between 3.0 and 4.5 V). This behavior is achieved by controlling the exposure and shielding of the catechol group through water electrolysis-induced reversible cleavage and reformation of the borate ester moiety. By switching the electric field direction, the hydrogel can repeatedly attach to and detach from various surfaces with a response time as low as 1 s. This programmable attaching/detaching strategy provides an alternative approach for robot climbing. The hydrogel is simply pasted onto the moving parts of climbing robots without complicated engineering and morphological designs. Using our hydrogel as feet and wheels, the tethered walking robots and wheeled robots can climb on both vertical and inverted conductive substrates (i.e., moving upside down) such as stainless steel and copper. Our study establishes an effective route for the design of smart polymer adhesives that are applicable in intelligent devices and an electrochemical strategy to regulate the adhesion.

Evolution of density fluctuation to a lamellar crystal in a poly(trimethylene terephthalate) film revealed by the resonance light scattering technique.

The dynamic process of cold crystallization of amorphous poly(trimethylene terephthalate) (PTT) was investigated with resonance light scattering (RLS). By using an enhanced scattering peak at 329 nm, which was in close proximity to the absorption band of PTT film, density fluctuation due to gradual transition from amorphous to crystalline with increasing temperature was monitored. Accordingly, molecular chains movement and structure evolution in PTT during cold crystallization, in particular, the information about each phase of crystallization, including induction, nucleation, nucleus growth and secondary crystallization, were thoroughly revealed. The experimental results indicated that the kinetics parameters measured by the RLS method were in good agreement with those obtained by differential scanning calorimetry (DSC) and fluorescence spectroscopy. In addition, the RLS method can tell more details of the movement and variation in fine structures than DSC and fluorescence techniques as a result of its significantly enhanced scattering signals, like the orientation fluctuations of rigid segments in the course of glass transition and crystallization induction.

Kinetics of phase separation in polymer blends revealed by resonance light scattering spectroscopy.

In this work, kinetics of phase separation in the blends of polystyrene (PS) and poly(vinyl methyl ether) (PVME) was investigated by a simple and sensitive method, i.e., resonance light scattering (RLS) spectroscopy. Owing to the aggregation of chromophores (phenyl rings) in the systems when phase separation occurred, RLS intensities were drastically enhanced and hence acted as a characteristic indicator. At the early stage of phase separation, two different RLS behaviors corresponding to spinodal decomposition (SD) and nucleation and growth (NG) were observed. The Cahn-Hilliard (C-H) linearization theory was found not applicable for kinetics analysis of the scattering data at lambda < 346 nm due to RLS effect near the absorption band. Based on a decomposition reaction model, the apparent activation energy of SD phase separation was estimated by the Arrhenius equation. In view of its simplicity and sensitivity of measurement, affordability and availability of instrument, and wide application range of polymer blends, RLS proved to be an effective means for characterization of microstructural variation in polymer blends.

Design of Slidable Polymer Networks: A Rational Strategy to Stretchable, Rapid Self-Healing Hydrogel Electrolytes for Flexible Supercapacitors.

Hydrogel electrolytes are of particular interest in the fabrication of flexible supercapacitors that are able to withstand deformation and physical damage. Nevertheless, there still exists a huge space in the design of hydrogel electrolytes with comprehensive performances including high processability, conductivity, mechanical strength, and self-healability. Herein, a slidable polymer network is constructed through the cross-linking reaction among commercially available polyethyleneimine (PEI), polyvinyl alcohol (PVA), and 4-formylphenylboronic acid (Bn) to generate PEI-PVA-Bn hydrogels, which have high adaptability to various electrolytes such as LiCl, NaCl, KCl, and ionic liquids. The as formed hydrogel electrolytes not only show excellent mechanical property (elongation at break up to 1223%, strength of 34.6 kPa) and self-healability (highest strain self-healing efficiency reaches 94.3% within 2 min) but also exhibit high conductivity (up to 21.49 mS cm-1). Flexible supercapacitors constructed by sandwiching the PEI-PVA-Bn-LiCl hydrogel electrolyte between two multiwalled carbon nanotube electrodes demonstrate a broadened operating potential window of 1.4 V, specific capacitance of 16.7 mF cm-2, high cycling stability up to 10 000 charge/discharge cycles, and excellent mechanical stability.

Anaerobic co-digestion of sewage sludge and food waste for hydrogen and VFA production with microbial community analysis.

In this study, the anaerobic co-digestion of food waste (FW) and sewage sludge (SS) was investigated for the production of hydrogen and volatile fatty acids (VFAs). The results showed that the anaerobic co-digestion of these materials enhanced the hydrogen content by 62.4% (v/v), 29.89% higher than that obtained by FW digestion alone, and the total VFA production reached at 281.84 mg/g volatile solid (VS), a 8.38% increase. This enhancement was primarily resulted from improvements in the multi-substrate characteristics, which were obtained by supplying a higher soluble chemical oxygen demand (23.78-32.14 g/L) and suitable a pH (6.12-6.51), decreasing total ammonia nitrogen by 18.67% and ensuring a proper carbon/nitrogen ratio (15.01-23.01). Furthermore, maximal hydrogen (62.39 mL/g VS) and total VFA production potential (294.63 mg/g VS) were estimated using response surface methodology optimization, which yielded FW percentages of 85.17% and 79.87%, respectively. Based on a pyrosequencing analysis, the dominant bacteria associated with VFA and hydrogen production were promoted under optimized condition, including members of genera Veillonella and Clostridium and the orders Bacteroidales and Lactobacillales.

Synthesis and application of aminophenyl-s-triazine derivatives as potential flame retardants in the modification of epoxy resins.

In order to develop new phosphorus-nitrogen-containing flame retardants, three novel compounds of DOPO-substituted aminophenyl-s-triazine (TAT-DOPO) with different P/N element ratios were synthesized by Kabachnik-Fields reaction. TAT-triDOPO possessing three DOPO units in one molecule exhibited the best thermal stability. Besides, TAT-triDOPO and TAT-hexaDOPO possessing active hydrogen displayed the characteristics of reactive-type retardant, while TAT-enneaDOPO without active hydrogen represented additive-type retardant. The influences of three TAT-DOPO compounds on the thermal stability, flame retardancy and mechanical properties of the cured EP composites were investigated. Compared with pure EP, the char yields of EP/TAT-DOPO were increased. The LOI value and the UL-94 ratings of EP/TAT-triDOPO with a 5% loading were improved to 34.0% and V-0 grade. The PHRR, THR and HRC of EP/TAT-triDOPO were decreased by 25.7%, 21.1% and 25.4%, respectively. Furthermore, the incorporation of TAT-triDOPO could also improve the flexural strength and elastic modulus of cured EP. It was explained that the existence of active hydrogen atoms within TAT-triDOPO molecule can act as effective chemical cross-linking points in EP network. Finally, based on the SEM and TGA-FTIR analysis of pyrolytic products of cured EP/TAT-DOPO, it was deduced that the prepared TAT-DOPO flame retardant could exhibit both condensed phase and gas phase flame-retardancy mechanism.