Project description:Molybdenum sulfides are very attractive noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) from water. The atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx), which exhibits significantly higher HER activity compared to its crystalline counterpart. Here we show that HER-active a-MoSx, prepared either as nanoparticles or as films, is a molecular-based coordination polymer consisting of discrete [Mo3S13](2-) building blocks. Of the three terminal disulfide (S2(2-)) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimization of this HER electrocatalyst as an alternative to platinum.
Project description:Hydrothermal reaction of 4,4-trimethylenedipyridine (tmdp) with ZnI2 under 175 degrees C yields a novel compound, {[Zn2I4(tmdp)2]n.[Zn2I4(tmdp)2]n}, which has a chiral infinite double-stranded helical structure consisting of two single-stranded helices of the same handedness.
Project description:Herein, we report the synthesis of DNA-functionalized infinite-coordination-polymer (ICP) nanoparticles as biocompatible gene-regulation agents. ICP nanoparticles were synthesized from ferric nitrate and a ditopic 3-hydroxy-4-pyridinone (HOPO) ligand bearing a pendant azide. Addition of Fe(III) to a solution of the ligand produced nanoparticles, which were colloidally unstable in the presence of salts. Conjugation of DNA to the Fe(III)-HOPO ICP particles by copper-free click chemistry afforded colloidally stable nucleic-acid nanoconstructs. The DNA-ICP particles, when cross-linked through sequence-specific hybridization, exhibited narrow, highly cooperative melting transitions consistent with dense DNA surface loading. The ability of the DNA-ICP particles to enter cells and alter protein expression was also evaluated. Our results indicate that these novel particles carry nucleic acids into mammalian cells without the need for transfection agents and are capable of efficient gene knockdown.
Project description:Amorphous perfluoroalkenyl vinyl ether polymer devices can store a remarkably powerful electric charge because their surface contains nanometre-sized cavities that are sensitive to the so-called quantum-size effect. With a work function of approximately 10 eV, the devices show a near-vertical line in the Nyquist diagram and a horizontal line near the -90° phase angle in the Bode diagram. Moreover, they have an integrated effect on the surface area for constant current discharging. This effect can be explained by the distributed constant electric circuit with a parallel assembly of nanometre-sized capacitors on a highly insulating polymer. The device can illuminate a red LED light for 3 ms after charging it with 1 mA at 10 V. Further gains might be attained by integrating polymer sheets with a micro-electro mechanical system.
Project description:The push to advance efficient, renewable, and clean energy sources has brought with it an effort to generate materials that are capable of storing hydrogen. Metal-organic framework materials (MOFs) have been the focus of many such studies as they are categorized for their large internal surface areas. We have addressed one of the major shortcomings of MOFs (their processibility) by creating and 3D printing a composite of acrylonitrile butadiene styrene (ABS) and MOF-5, a prototypical MOF, which is often used to benchmark H2 uptake capacity of other MOFs. The ABS-MOF-5 composites can be printed at MOF-5 compositions of 10% and below. Other physical and mechanical properties of the polymer (glass transition temperature, stress and strain at the breaking point, and Young's modulus) either remain unchanged or show some degree of hardening due to the interaction between the polymer and the MOF. We do observe some MOF-5 degradation through the blending process, likely due to the ambient humidity through the purification and solvent casting steps. Even with this degradation, the MOF still retains some of its ability to uptake H2, seen in the ability of the composite to uptake more H2 than the pure polymer. The experiments and results described here represent a significant first step toward 3D printing MOF-5-based materials for H2 storage.
Project description:The title compound catena-poly[aqua-sodium-μ(2)-aqua-μ(3)-2-nitro-cinnamato], [Na(C(9)H(6)NO(4))(H(2)O)(2)](n), the sodium salt of trans-2-nitro-cinnamic acid, is a one-dimensional coordination polymer based on six-coordinate octa-hedral NaO(6) centres, comprising three facially related monodentate carboxyl-ate O-atom donors from separate ligands (all bridging) [Na-O = 2.4370 (13)-2.5046 (13) Å], and three water mol-ecules (two bridging and one monodentate) [Na-O = 2.3782 (13)-2.4404 (17) Å]. The structure is also stabilized by intra-chain water-carboxyl-ate and water-nitro O-H⋯O hydrogen bonds.
Project description:Polymer composite materials with hierarchical porous structure have been advancing in many different application fields due to excellent physico-chemical properties. However, their synthesis continues to be a highly energy-demanding and environmentally unfriendly process. This work reports a unique water based synthesis of monolithic 3D reduced graphene oxide (rGO) composite structures reinforced with poly(methyl methacrylate) polymer nanoparticles functionalized with epoxy functional groups. The method is based on reduction-induced self-assembly process performed at mild conditions. The textural properties and the surface chemistry of the monoliths were varied by changing the reaction conditions and quantity of added polymer to the structure. Moreover, the incorporation of the polymer into the structures improves the solvent resistance of the composites due to the formation of crosslinks between the polymer and the rGO. The monolithic composites were evaluated for selective capture of CO2. A balance between the specific surface area and the level of functionalization was found to be critical for obtaining high CO2 capacity and CO2/N2 selectivity. The polymer quantity affects the textural properties, thus lowering its amount the specific surface area and the amount of functional groups are higher. This affects positively the capacity for CO2 capture, thus, the maximum achieved was in the range 3.56-3.85 mmol/g at 1 atm and 25 °C.
Project description:Recently, coordination polymers (CPs) have been frequently reported in the field of energy storage as electrode materials for lithium-ion batteries (LIBs) due to their highly adjustable architectures, which have a variety of active sites and obviously defined lithium transport routes. A well-designed redox-active organic linker with potential active sites for storing lithium ions, pyrazine-2,3-dicarboxylate (H2PDA), was applied for generating CPs by a simple hydrothermal method. When employed as anode materials in LIBs, those two one-dimensional (1D) CPs with an isomorphic composition, [M(PDA)(H2O)2]n (M = Co for Co-PDA and Ni for Ni-PDA), produced outstanding reversible capacities and stable cycling performance. The Co-PDA displays a substantial reversible capacity of 936 mAh g-1 at 200 mA g-1 after 200 cycles, as well as an excellent cycling life at high currents. According to the ex situ characterizations, the high reversible specific capacity of the post-cycled electrodes was found to be a result of both the transition metal ions and the organic ligands, and Co-PDA and Ni-PDA electrode materials show reversible insertion/extraction processes that are accompanied by crystallization to an amorphous state.