Oxygen-rich poly-bisvanillonitrile embedded amorphous zirconium oxide nanoparticles as reusable and porous adsorbent for removal of arsenic species from water.

A new oxygen-rich porous polymer based on bisvanillonitrile was synthesized and characterized. This polymer was employed as support for the anchoring of 14.5 w% amorphous zirconium oxide nanoparticles. The formation of homogeneously dispersed nanoparticles in the poly-bisvanillonitrile (PBVN) host material was confirmed using N2-sorption, XRPD, XPS and electron microscopy. The combination of zirconium oxide nanoparticles having active adsorption sites with the porous supporting material showed excellent adsorption of arsenic species. The resulting adsorption capacities of the hybrid material extend to 245 mg g-1 for arsenite (AsIII) and 115 mg g-1 for arsenate (AsV). Moreover, adsorption kinetics showed a fast removal of both arsenic species with initial adsorption rate h of 0.0646 mg g-1 min-1 for arsenite and 0.0746 mg g-1 min-1 for arsenate. The immobilization was not interfered by the presence of other compounds in solution, indicating the applicability in real working environments. The material could be regenerated in a continuous mode using a 0.1 mol L-1 sodium hydroxide solution at 70 °C to desorb arsenic.

Sustainable Battery Materials from Biomass.

Sustainable sources of energy have been identified as a possible way out of today's oil dependency and are being rapidly developed. In contrast, storage of energy to a large extent still relies on heavy metals in batteries. Especially when built from biomass-derived organics, organic batteries are promising alternatives and pave the way towards truly sustainable energy storage. First described in 2008, research on biomass-derived electrodes has been taken up by a multitude of researchers worldwide. Nowadays, in principle, electrodes in batteries could be composed of all kinds of carbonized and noncarbonized biomass: On one hand, all kinds of (waste) biomass may be carbonized and used in anodes of lithium- or sodium-ion batteries, cathodes in metal-sulfur or metal-oxygen batteries, or as conductive additives. On the other hand, a plethora of biomolecules, such as quinones, flavins, or carboxylates, contain redox-active groups that can be used as redox-active components in electrodes with very little chemical modification. Biomass-based binders can replace toxic halogenated commercial binders to enable a truly sustainable future of energy storage devices. Besides the electrodes, electrolytes and separators may also be synthesized from biomass. In this Review, recent research progress in this rapidly emerging field is summarized with a focus on potentially fully biowaste-derived batteries.

Interplay of Porosity, Wettability, and Redox Activity as Determining Factors for Lithium-Organic Electrochemical Energy Storage Using Biomolecules.

Although several recent publications describe cathodes for electrochemical energy storage materials made from regrown biomass in aqueous electrolytes, their transfer to lithium-organic batteries is challenging. To gain a deeper understanding, we investigate the influences on charge storage in model systems based on biomass-derived, redox-active compounds and comparable structures. Hybrid materials from these model polymers and porous carbon are compared to determine precisely the causes of exceptional capacity in lithium-organic systems. Besides redox activity, particularly, wettability influences capacity of the composites greatly. Furthermore, in addition to biomass-derived molecules with catechol functionalities, which are described commonly as redox-active species in lithium-bio-organic systems, we further describe guaiacol groups as a promising alternative for the first time and compare the performance of the respective compounds.

Dynamics of ionic liquids in the presence of polymer-grafted nanoparticles.

We incorporated polymer-grafted nanoparticles into ionic and zwitterionic liquids to explore the solvation and confinement effects on their heterogeneous dynamics using quasi-elastic neutron scattering (QENS). 1-Hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) mixed with deuterated poly(methyl methacrylate) (d-PMMA)-grafted nanoparticles is studied to unravel how dynamic coupling between PMMA and HMIM-TFSI influence the fast and slow diffusion characteristics of the HMIM+ cations. The zwitterionic liquid, 1-butyl-3-methyl imidazole-2-ylidene borane (BMIM-BH3) is critically selected and mixed with PMMA-grafted nanoparticles for comparison in this work as its ions do not self-dissociate and it does not couple with PMMA through ion-dipole interactions as HMIM-TFSI does. We find that long-range unrestricted diffusion of HMIM+ cations is higher in well-dispersed particles than in aggregated particle systems, whereas the localized diffusion of HMIM+ is measured to be higher in close-packed particles. Translational diffusion dynamics of BMIM-BH3 is not influenced by any particle structures suggesting that zwitterions do not interact with PMMA. This difference between two ionic liquid types enables us to decouple polymer effects from the diffusion of ionic liquids, which is integral to understand the ionic transport mechanism in ionic liquids confined in polymer-grafted nanoparticle electrolytes.

Vanillin decorated chitosan as electrode material for sustainable energy storage.

Energy storage materials made from bioresources are crucial to fulfil the need for truly sustainable energy storage. In this work, vanillin, being a lignin-derived molecule, is coupled to chitosan, a biobased polymer backbone, and used as a redox active electrode material. The structure of those electrodes is highly defined, leading to better product security than in lignin based electrodes, which have been presented as sustainable electrodes in the past. With over 60% of saccharide units in chitosan functionalised by vanillin, the concentration of redox functionalities in the copolymer is significantly higher than in lignin materials. Composites with carbon black require no further binders or additives to be used as electrode material and show reversible charge storage up to 80 mA h g-1 (respective to the total electrode material) and good stability. Consequently, these electrodes are amongst the best performing electrodes made from regrown organic matter.

Stability of the zwitterionic liquid butyl-methyl-imidazol-2-ylidene borane.

Modification of the C2 position of the standard 1-butyl-3-methyl imidazolium cation by a borohydride group leads to a zwitterionic liquid (ZIL). The resulting imidazol-2-ylidene borane ZIL is liquid at room temperature. Dynamic viscosity as well as thermal and electrochemical stability are investigated. Thermal decomposition follows a similar pathway as in comparable imidazolium ionic liquids. The surprisingly low viscosity and good reductive stability make it a promising candidate for electrochemical applications.

Halogen free 1,2,3- and 1,2,4-triazolide based ionic liquids: synthesis and properties.

Triazoles have been successfully used as building blocks to create "fully organic" ILs featuring on both sides organic ions, i.e., 1,2,3- or 1,2,4-triazolide anions and 1,2,4-triazolium or imidazolium cations. Glass transition temperatures, densities and viscosities of these ILs were determined. Their electrochemical and thermal stability, and also conductivity, are higher than those for known ILs.

Ultrafast Self-Assembly of Sub-10 nm Block Copolymer Nanostructures by Solvent-Free High-Temperature Laser Annealing.

Laser spike annealing was applied to PS-b-PDMS diblock copolymers to induce short-time (millisecond time scale), high-temperature (300 to 700 °C) microphase segregation and directed self-assembly of sub-10 nm features. Conditions were identified that enabled uniform microphase separation in the time frame of tens of milliseconds. Microphase ordering improved with increased temperature and annealing time, whereas phase separation contrast was lost for very short annealing times at high temperature. PMMA brush underlayers aided ordering under otherwise identical laser annealing conditions. Good long-range order for sub-10 nm cylinder morphology was achieved using graphoepitaxy coupled with a 20 ms dwell laser spike anneal above 440 °C.

Green Imidazolium Ionics-From Truly Sustainable Reagents to Highly Functional Ionic Liquids.

We report the synthesis of task-specific imidazolium ionic compounds and ionic liquids with key functionalities of organic molecules from electro-, polymer-, and coordination chemistry. Such products are highly functional and potentially suitable for technology applications even though they are formed without elaborate reactions and from cheap and potentially green reagents. We further demonstrate the versatility of the used synthetic approach by introducing different functional and green counterions to the formed ionic liquids directly during the synthesis or after metathesis reactions. The influence of different cation structures and different anions on the thermal and electrochemical properties of the resulting ionic liquids is discussed. Our goal is to make progress towards economically competitive and sustainable task-specific ionic liquids.

Reversible Switching of Block Copolymer Nanopatterns by Orthogonal Electric Fields.

It is demonstrated that the orientation of striped patterns can be reversibly switched between two perpendicular in-plane orientations upon exposure to electric fields. The results on thin films of symmetric polystyrene-block-poly(2-vinyl pyridine) polymer in the intermediate segregation regime disclose two types of reorientation mechanisms from perpendicular to parallel relative to the electric field orientation. Domains orient via grain rotation and via formation of defects such as stretched undulations and temporal phase transitions. The contribution of additional fields to the structural evolution is also addressed to elucidate the generality of the observed phenomena. In particular solvent effects are considered. This study reveals the stabilization of the meta-stable in-plane oriented lamella due to sequential swelling and quenching of the film. Further, the reorientation behavior of lamella domains blended with selective nanoparticles is addressed, which affect the interfacial tensions of the blocks and hence introduce another internal field to the studied system. Switching the orientation of aligned block copolymer patterns between two orthogonal directions may open new applications of nanomaterials as switchable electric nanowires or optical gratings.

Design, Synthesis, and Use of Y-Shaped ATRP/NMP Surface Tethered Initiator.

Heterogeneous polymer brushes on surfaces can be easily formed from a binary initiator on a silicon oxide substrate where two different types of polymers can be grown side-by-side. Herein, we designed a new Y-shaped binary initiator using straightforward chemistry for "grafting from" polymer brushes. This initiator synthesis takes advantage of the Passerini reaction, a multicomponent reaction combining two initiator sites and one surface linking site. This Y-shaped binary initiator can be synthesized in three steps with a higher yield than other similar initiators reported in the literature, and can be performed on a multigram scale. We were able to attach the initiator to a silicon oxide substrate and successfully grow polymer brushes from both initiators (separately and in combination), confirmed by NEXAFS, AFM, and contact angle.

Electric-field-induced alignment of block copolymer/nanoparticle blends.

External electric fields readily align birefringent block-copolymer mesophases. In this study the effect of gold nanoparticles on the electric-field-induced alignment of a lamellae-forming polystyrene-block-poly(2-vinylpyridine) copolymer is assessed. Nanoparticles are homogeneously dispersed in the styrenic phase and promote the quantitative alignment of lamellar domains by substantially lowering the critical field strength above which alignment proceeds. The results suggest that the electric-field-assisted alignment of nanostructured block copolymer/nanoparticle composites may offer a simple way to greatly mitigate structural and orientational defects of such films under benign experimental conditions.

Block Copolymer Nanocomposites in Electric Fields: Kinetics of Alignment.

We investigate the kinetics of block copolymer/nanoparticle composite alignment in an electric field using in situ transmission small-angle X-ray scattering. As a model system, we employ a lamellae forming polystyrene-block-poly(2-vinyl pyridine) block copolymer with different contents of gold nanoparticles in thick films under solvent vapor annealing. While the alignment improves with increasing nanoparticle fraction, the kinetics slows down. This is explained by changes in the degree of phase separation and viscosity. Our findings provide extended insights into the basics of nanocomposite alignment.