Poly(ethylene oxide)- and Polyzwitterion-Based Thermoplastic Elastomers for Solid Electrolytes.

In this article, ABA triblock copolymer (tri-BCP) thermoplastic elastomers with poly(ethylene oxide) (PEO) middle block and polyzwitterionic poly(4-vinylpyridine) propane-1-sulfonate (PVPS) outer blocks were synthesized. The PVPS-b-PEO-b-PVPS tri-BCPs were doped with lithium bis-(trifluoromethane-sulfonyl) imide (LiTFSI) and used as solid polyelectrolytes (SPEs). The thermal properties and microphase separation behavior of the tri-BCP/LiTFSI hybrids were studied. Small-angle X-ray scattering (SAXS) results revealed that all tri-BCPs formed asymmetric lamellar structures in the range of PVPS volume fractions from 12.9% to 26.1%. The microphase separation strength was enhanced with increasing the PVPS fraction (fPVPS) but was weakened as the doping ratio increased, which affected the thermal properties of the hybrids, such as melting temperature and glass transition temperature, to some extent. As compared with the PEO/LiTFSI hybrids, the PVPS-b-PEO-b-PVPS/LiTFSI hybrids could achieve both higher modulus and higher ionic conductivity, which were attributed to the physical crosslinking and the assistance in dissociation of Li+ ions by the PVPS blocks, respectively. On the basis of excellent electrical and mechanical performances, the PVPS-b-PEO-b-PVPS/LiTFSI hybrids can potentially be used as solid electrolytes in lithium-ion batteries.

Microphase Separation with Sub-3 nm Microdomains in Comb-Like Poly(n-alkyl acrylate) Homopolymers Facilitated by Charged Junction Groups between the Main Chains and Side Chains.

The phase structure with a small domain size in polymers is expected to provide a template for lithography to fabricate electronic devices, while the uniformity and thermal stability of the phase structure are vital in lithography. In this work, we report an accurately microphase-separated system of comb-like poly(ionic liquid) (PIL)-based homopolymers containing imidazolium cation junctions between the main chain parts and the long alkyl side chains, poly(1-((2-acryloyloxy)ethyl)-3-alkylimidazolium bromide) (P(AOEAmI-Br)). The ordered hexagonally packed cylinder (HEX) and lamellar (LAM) structures with small domain sizes (sub-3 nm) were successfully achieved. Since the microphase separation was induced by the incompatibility between the main chain parts and the hydrophobic alkyl chains, the microdomain spacing of the ordered structure was independent of the molecular weight and molecular weight distribution of P(AOEAmI-Br) homopolymers and could be precisely regulated by changing the length of the alkyl side chains. Importantly, the microphase separation was promoted by the charged junction groups; thus, the phase structure and domain size of P(AOEAmI-Br) exhibited excellent thermal stability.

Improved activity and significant SO2 tolerance of Sb-Pd-V oxides on N-doped TiO2 for CB/NOx synergistic degradation.

The synergistic degradation of VOCs and NOx that were emitted from the incineration of municipal and medical wastes by a single catalyst is challenging, due to the poor activity at low temperatures, and the SO2 poisoning on the active sites. Herein, N-doped TiO2 (N-TiO2) was used as the support for designing a highly efficient and stable catalyst system for CB/NOx synergistic degradation even in the presence of SO2. The prepared SbPdV/N-TiO2 catalyst, which presented excellent activity and tolerance to SO2 in the CBCO + SCR process, was investigated by a series of characterizations (such as XRD, TPD, XPS, H2-TPR and so on) as well as DFT calculations. The electronic structure of the catalyst was effectively modulated after N doping, resulting in effective charge flow between the catalyst surface and gas molecules. More importantly, the adsorption and deposition of sulfur species and reaction transient intermediates on active centers were restrained, while a new N adsorption center for NOx was provided. Abundant adsorption centers and superior redox properties ensured smooth CB/NOx synergistic degradation. The removal of CB mainly follows the L-H mechanism, while NOx elimination follows both E-R and L-H mechanisms. As a result, N doping provides a new approach to develop more advanced anti-SO2 poisoning CB/NOx synergistic catalytic removal systems for extensive applications.

Electrostatic crosslinking-enabled highly asymmetric lamellar nanostructures of polyzwitterionic block copolymers for lithography.

For the bulk self-assembly of traditional diblock copolymers (di-BCPs), lamellar structures only occur when two constituents have similar volume fractions (f) and two alternating layers tend to have similar thicknesses. Highly asymmetric lamellar (A-LAM) structures, in which the thickness of one layer is several times higher than the other, are hardly formed in di-BCPs, while they have potential applications in nanolithography. In this work, A-LAM structures with different dimensions were constructed using a type of simple linear di-BCP, polystyrene-b-poly(4-vinylpyridine)propane-1-sulfonate (PS-b-PVPS) with the polyzwitterionic block PVPS in minority. The origin of the A-LAM structure was ascribed to the electrostatic crosslinking and confirmed by doping PS-b-PVPS block copolymers (BCPs) with N-butyl pyridinium methane sulfonate (BPMS). The morphology of compositionally asymmetric PS-b-PVPS BCPs changed from A-LAM to cylindrical structures upon salt-doping, i.e. the phase behavior of common BCPs was recovered. In addition, the morphologies of PS-b-PVPS BCPs with similar molecular weights but varied compositions were also studied, and only two kinds of structures (lamellar or ill-defined spherical structure) were observed when the volume fraction of PVPS (fPVPS) was less than 0.5, and the composition range for the formation of the lamellar structure was found to be fPVPS ≥ 0.188.

Approaching Molecular Definition on Oxide-Supported Single-Atom Catalysts.

ConspectusSingle-atom catalysts (SACs) offer unique advantages such as high (noble) metal utilization through maximum possible dispersion, large metal-support contact areas, and oxidation states usually unattainable in classic nanoparticle catalysis. In addition, SACs can serve as models for determining active sites, a simultaneously desired as well as elusive target in the field of heterogeneous catalysis. Due to the complexity of heterogeneous catalysts bearing a variety of different sites on metal particles and the respective support as well as at their interface, studies of intrinsic activities and selectivities remain largely inconclusive. While SACs could close this gap, many supported SACs remain intrinsically ill-defined due to complexities arising from the variety of different adsorption sites for atomically dispersed metals, hampering the establishment of meaningful structure-activity correlations. In addition to overcoming this limitation, well-defined SACs could even be utilized to shed light on fundamental phenomena in catalysis that remain ambiguous when studies are obscured by the complexity of heterogeneous catalysts.In this Account, we describe approaches to break down the complexity of supported single-atom catalysts through the careful choice of oxide supports with specific binding motives as well as the adsorption of well-defined ligands such as ionic liquids on single metal sites. An example of molecularly defined oxide supports is polyoxometalates (POMs), which are metal oxo clusters with precisely known composition and structure. POMs exhibit a limited number of sites to anchor atomically dispersed metals such as Pt, Pd, and Rh. Polyoxometalate-supported single-atom catalysts (POM-SACs) thus represent ideal systems for the in situ spectroscopic study of single atom sites during reactions as, in principle, all sites are identical and thus equally active in catalytic reactions. We have utilized this benefit in studies of the mechanism of CO and alcohol oxidation reactions as well as the hydro(deoxy)genation of various biomass-derived compounds. More so, the redox properties of polyoxometalates can be finely tuned by changing the composition of the support while keeping the geometry of the single-atom active site largely constant. We further developed soluble analogues of heterogeneous POM-SACs, opening the door to advanced liquid-phase nuclear magnetic resonance (NMR) and UV-vis techniques but, in particular, to electrospray ionization mass spectrometry (ESI-MS) which proves powerful in determining catalytic intermediates as well as their gas-phase reactivity. Employing this technique, we were able to resolve some of the long-standing questions about hydrogen spillover, demonstrating the broad utility of studies on defined model catalysts.

PEO-Based Block Copolymer Electrolytes Containing Double Conductive Phases with Improved Mechanical and Electrochemical Properties.

In this work, the advanced all solid-state block copolymer electrolytes (SBCPEs) for lithium-ion batteries with double conductive phases, poly(ethylene oxide)-b-poly(trimethyl-N-((2-(dimethylamino)ethyl methacrylate)-7-propyl)-ammonium bis(trifluoromethanesulfonyl) imide) (PEO-b-PDM-dTFSI)/LiTFSI, were fabricated, in which the charged PDM-dTFSI block contained double quaternary ammonium cations and the PEO block was doped with LiTFSI. The disordered (DIS) and ordered lamellae (LAM) phase structures were achieved by adjusting the composition of the block copolymer and the doping ratio r. In addition, the presence of the hard PDM-dTFSI block and the formation of the LAM phase structure resulted in a good mechanical strength of the solid PEO-b-PDM-dTFSI/LiTFSI electrolyte, and it could maintain a high level of 104 Pa at 100 °C, which was around 10,000 times stronger than that of the PEO/LiTFSI electrolyte. Based on the good mechanical and electrochemical properties, the PEO-b-PDM-dTFSI/LiTFSI SBCPE exhibited excellent long-term galvanostatic cycle performance, indicating the strong ability to suppress lithium dendrites.

Fabrication of High χ-Low N Block Copolymers with Thermally Stable Sub-5 nm Microdomains Using Polyzwitterion as a Constituent Block.

In this work, we used zwitterionic poly(4-vinylpyridine) propane-1-sulfonate (PVPS) as a constituent block to construct high χ-low N block copolymers (BCPs) with different neutral polymers as the other block, including polystyrene (PS), poly(ethylene oxide) (PEO), and poly(l-lactide) (PLLA). Lamellar structures with sub-5 nm microdomains were observed in all three types of BCPs. Due to the tendency of self-aggregation induced by electrostatic interaction in polyzwitterion, the Flory-Huggins parameters (χ) between PVPS and most neutral polymers are relatively high, which provides a facile and efficient way to fabricate high χ-low N BCPs. In addition, the dimension of the sub-5 nm structures formed in PVPS-containing BCPs showed high thermal stability with a small fluctuation (±0.1 nm) of domain spacings upon heating.

Atomically Dispersed Pt1-Polyoxometalate Catalysts: How Does Metal-Support Interaction Affect Stability and Hydrogenation Activity?

Unlike nanostructured metal catalysts, supported single-atom catalysts (SACs) contain only atomically dispersed metal atoms, hinting at much more pronounced metal-support effects. Herein, we take a series of polyoxometalate-supported Pt catalysts as examples to quantitatively investigate the stability of Pt atoms on oxide supports and how the Pt-support interaction influences the catalytic performance. For this entire series, we show that the Pt atoms prefer to stay at a 4-fold hollow site of one polyoxometalate molecule and that the least adsorption energy to obtain sintering-resistant Pt SACs is 5.50 eV, which exactly matches the cohesive energy of bulk Pt metal. Further, we compared their catalytic performance in several hydrogenation reactions and simulated the reaction pathways of propene hydrogenation by density functional theory (DFT) calculations. Both experimental and theoretical approaches suggest that despite the Pt1-support interactions being different, the reaction pathways of various Pt1-polyoxometalate catalysts are very similar and their effective reaction barriers are close to each other and as low as 24 kJ/mol, indicating the possibility of obtaining SACs with improved stability without compromising activity. DFT calculations show that all reaction elementary steps take place only on the Pt atom without involving neighboring O atoms and that hydrogenation proceeds from the molecularly adsorbed H2 species. Pt SACs give a weaker H2 adsorption energy than Pt clusters or surfaces, resulting in small adsorption equilibrium constants and small apparent activation barriers, which agree between experiment and theory.

Influence of the Anion on the Oxidation of 5-Hydroxymethylfurfural by Using Ionic-Polymer-Supported Platinum Nanoparticle Catalysts.

Platinum nanoparticles stabilized by an imidazolium-based cross-linked polymer (with chloride as the counteranion) efficiently catalyzed the oxidation of 5-hydroxymethylfurfural to form 2,5-furandicarboxylic acid in water under mild conditions with oxygen as the oxidant. This catalyst system is explored herein by varying the counteranion, that is, replacing chloride by BF4 - , PF6 - , bis(trifluoromethylsulfonyl)imide, hexanoate, or laurate anions, in the cationic polymer. The counteranion influences the structure of the obtained platinum nanoparticles, the surface electronic properties, and their catalytic activity. The highest reaction rates were obtained with the weakly nucleophilic bis(trifluoromethylsulfonyl)imide anion, which also favored platinum in the zero oxidation state, leading to complete conversion of the substrate and a high yield of 2,5-furandicarboxylic acid under mild conditions.

Influence of the Anion on the Oxidation of 5-Hydroxymethylfurfural by Using Ionic-Polymer-Supported Platinum Nanoparticle Catalysts.

Invited for this month's cover are the groups of Prof. Paul J. Dyson at Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland and Prof. Ning Yan at National University of Singapore, Singapore. The cover shows the catalytic conversion of 5-hydroxymethylfurfural (5-HMF) into 2,5-furandicarboxylic acid catalyzed by platinum nanoparticles stabilized by polymeric imidazolium salts. The catalyst is represented by a nanoparticle footprint. The background represents a potential source of biomass. Read the full text of the article at 10.1002/cplu.201700344.

Significant Promotion Effect of Mo Additive on a Novel Ce-Zr Mixed Oxide Catalyst for the Selective Catalytic Reduction of NO(x) with NH3.

A novel Mo-promoted Ce-Zr mixed oxide catalyst prepared by a homogeneous precipitation method was used for the selective catalytic reduction (SCR) of NO(x) with NH3. The optimal catalyst showed high NH3-SCR activity, SO2/H2O durability, and thermal stability under test conditions. The addition of Mo inhibited growth of the CeO2 particle size, improved the redox ability, and increased the amount of surface acidity, especially the Lewis acidity, all of which were favorable for the excellent NH3-SCR performance. It is believed that the catalyst is promising for the removal of NO(x) from diesel engine exhaust.