Direct Construction of Isomeric Benzobisoxazole-Vinylene-Linked Covalent Organic Frameworks with Distinct Photocatalytic Properties.

Vinylene/olefin-linked two-dimensional covalent organic frameworks (v-2D-COFs) have emerged as advanced semiconducting materials with excellent in-plane conjugation, high chemical stabilities, and precisely tunable electronic structures. Exploring new linkage chemistry for the reticular construction of v-2D-COFs remains in infancy and challenging. Herein, we present a solid-state benzobisoxazole-mediated aldol polycondensation reaction for the construction of two novel isomeric benzobisoxazole-bridged v-2D-COFs (v-2D-COF-NO1 and v-2D-COF-NO2) with trans and cis configurations of benzobisoxazole. Interestingly, the isomeric benzobisoxazole linkers endow the two v-2D-COFs with distinct optoelectronic and electrochemical properties, ranging from light absorption and emission to charge-transfer properties. When employed as the photocathode, v-2D-COF-NO1 exhibits a photocurrent of up to ∼18 µA/cm2 under AM 1.5G irradiation at -0.3 V vs reversible hydrogen electrode (RHE), which is twice the value of v-2D-COF-NO2 (∼9.1 µA/cm2). With Pt as a cocatalyst, v-2D-COF-NO1 demonstrates a photocatalytic hydrogen evolution rate of ∼1.97 mmol h-1 g-1, also in clear contrast to that of v-2D-COF-NO2 (∼0.86 mmol h-1 g-1) under identical conditions. This work demonstrates the synthesis of v-2D-COFs via benzobisoxazole-mediated aldol polycondensation with isomeric structures and distinct photocatalytic properties.

Polaron and Exciton Delocalization in Oligomers of High-Performance Polymer PTB7.

A key characteristic of organic photovoltaic cells is the efficient charge separation in the active layer. Sufficient delocalization of the positive polaron in organic photovoltaics is considered essential for the effective separation of the opposite charges and the suppression of recombination. We use light-induced EPR and ENDOR spectroscopy combined with DFT calculations to determine the electronic structure of the positive polaron in PTB7-type oligomers. Utilizing the superior spectral resolution of high-frequency (130 GHz) D-band EPR, the principal components of the g tensors were determined. Pulsed ENDOR spectroscopy at X-band allowed the measurement of 1H hyperfine coupling constants. A comparison of g tensors and 1H hyperfine coupling constants of the PTB7-type oligomers with the high-performance PTB7 polymer revealed a delocalization of the positive polaron in the polymer over about four monomeric units, corresponding to about 45 Å in length. Our current study thus not only determines the polaron delocalization length in PTB7 but also validates the approach combining EPR/ENDOR spectroscopy with DFT-calculated magnetic resonance parameters. This is of importance in those cases where oligomers of defined length are not easily obtained. In addition, the delocalization of the neutral triplet exciton was also determined in the oligomers and compared with polymer PTB7. The analysis revealed that the neutral triplet exciton is substantially more delocalized than the positive polaron, exceeding 10 monomeric units.

Effects of Intra- and Interchain Interactions on Exciton Dynamics of PTB7 Revealed by Model Oligomers.

Recent studies have shown that molecular aggregation structures in precursor solutions of organic photovoltaic (OPV) polymers have substantial influence on polymer film morphology, exciton and charge carrier transport dynamics, and hence, the resultant device performance. To distinguish photophysical impacts due to increasing π-conjugation from chain lengthening and π-π stacking from single/multi chain aggregation in solution and film, we used oligomers of a well-studied charge transfer polymer PTB7 with different lengths as models to reveal intrinsic photophysical properties of a conjugated segment in the absence of inter-segment aggregation. In comparison with previously studied photophysical properties in polymeric PTB7, we found that oligomer dynamics are dominated by a process of planarization of the conjugated backbone into a quinoidal structure that resembles the self-folded polymer and that, when its emission is isolated, this quinoidal excited state resembling the planar polymer chain exhibits substantial charge transfer character via solvent-dependent emission shifts. Furthermore, the oligomers distinctly lack the long-lived charge separated species characteristic of PTB7, suggesting that the progression from charge transfer character in isolated chains to exciton splitting in neat polymer solution is modulated by the interchain interactions enabled by self-folding.

Exceptional Single-Molecule Transport Properties of Ladder-Type Heteroacene Molecular Wires.

A series of ladder-type fused heteroacenes consisting of thiophenes and benzothiophenes were synthesized and functionalized with thiol groups for single-molecule electrical measurements via a scanning tunneling microscopy break-junction method. It was found that this molecular wire system possesses exceptional charge transport properties with weak length dependence. The tunneling decay constant ß was estimated to be 0.088 and 0.047 Å(-1) under 0.1 and 0.5 bias, respectively, which is one of the lowest ß values among other non-metal-containing molecular wires, indicating that a planar ladder structure favors charge transport. Transition voltage spectroscopy showed that the energy barrier decreases as the length of the molecule increases. The general trend of the energy offsets derived from the transition voltage via the Newns-Anderson model agrees well with that of the Fermi/HOMO energy level difference. Nonequilibrium Green's function/density functional theory was used to further investigate the transport process in these molecular wires.

Synthesis of Ladder-Type Thienoacenes and Their Electronic and Optical Properties.

A series of ladder-type thienoacenes based on benzo[1,2-b:4,5-b']dithiophene (BDT) have been synthesized and characterized. They were shown to be p-type semiconductors with wide band gaps and able to support multiple stable cationic states. As the conjugation lengthens, these oligomers become more emissive, showing high quantum yields. They were shown to be good two-photon absorbers, exhibiting high two-photon absorption coefficients.

Bamboo-like nitrogen-doped carbon nanotubes directly grown from commercial carbon black for encapsulating FeCo nanoparticles as efficient oxygen reduction electrocatalysts.

Efficient methods for preparing carbon nanotube (CNT)-confined metal catalysts are of great significance for electrocatalysis. Hence, in this study, Fe and Co promoters were added to the precursors of commercial carbon black and melamine to form N-doped CNTs confined bimetallic catalysts (FeCo@N-CNTs) via in situ pyrolysis. The FeCo@N-CNT catalysts exhibited a bamboo-like morphology with FeCo alloy nanoparticles encapsulated in the CNTs and high activity toward the oxygen reduction reaction, with a half-wave potential of 0.864 mV, higher than that of commercial Pt/C (0.827 mV) in alkaline solutions. The catalytic performance is attributable to the synergistic effects between the FeCo alloy and N-doped CNT structure. Moreover, the confinement of the FeCo nanoparticles inside the CNTs imparted the prepared catalysts with resistance to methanol poisoning and long-term stability. This versatile method of synthesizing CNTs directly from carbon black provides a new strategy for preparing high-performance non-precious-metal-based N-doped CNT catalysts for practical fuel cell applications.

Seawater-Boosting Surface-Initiated Atom Transfer Radical Polymerization for Functional Polymer Brush Engineering.

Iron-mediated surface-initiated reversible deactivation radical polymerization (Fe0 SI-RDRP) is an appealing approach to produce robust polymer surfaces with low toxicity and biocompatibility, while its application has been limited so far due to the poor activity of iron-based catalysts. Herein, we show that the iron(0)-mediated surface-initiated atom transfer radical polymerization (Fe0 SI-ATRP) could be significantly enhanced by simply using seawater as reaction media. In comparison, there was no polymer brush formation in deionized water. This method could convert a range of monomers to well-defined polymer brushes with unparalleled speed (up to 31.5 nm min-1) and a minor amount of monomer consumption (µL). Moreover, the resultant polymer brush shows chain-end fidelity which could be exemplified by repetitive Fe0 SI-ATRP to obtain tetrablock brushes. Finally, we show the preparation of polymer-brush-gated ion-selective membranes by Fe0 SI-ATRP for osmotic energy conversion, which gives excellent power densities of 5.93 W m-2, outperforming the most reported as well as commercialized benchmark (5 W m-2).

Galvanic-Replacement-Assisted Surface-Initiated Atom Transfer Radical Polymerization for Functional Polymer Brush Engineering.

Here we present a facile and robust strategy, namely, galvanic-replacement-assisted surface-initiated Cu(0)-mediated atom transfer radical polymerization (gr-SI-Cu0ATRP, or gr-SI-Cu0CRP) for polymer brush engineering under ambient conditions. In gr-SI-Cu0ATRP, highly active and nanostructured Cu(0) surfaces are obtained by a simple galvanic replacement on zinc/aluminum surfaces in dilute Cu2+ solution. Polymer brush growth rate is extremely high (up to ∼904 nm in 30 min polymerization); meanwhile, both nano Cu(0) surfaces and Cu2+ solution can be reused multiple times without losing grafting efficiency. We also demonstrate that the gr-SI-Cu0ATRP is advantageous for polymer brush engineering on arbitrary substrates, including flexible (polyethylene terephthalate), curved (polycarbonate), and porous (anodic aluminum oxide), and endow the substrates with various functionalities, for example, anti-icing, antifogging, and ion selectivity.

Viscosity Analysis of Battery Electrode Slurry.

We report the effects of component ratios and mixing time on electrode slurry viscosity. Three component quantities were varied: active material (graphite), conductive material (carbon black), and polymer binder (carboxymethyl cellulose, CMC). The slurries demonstrated shear-thinning behavior, and suspension properties stabilized after a relatively short mixing duration. However, micrographs of the slurries suggested their internal structures did not stabilize after the same mixing time. Increasing the content of polymer binder CMC caused the greatest viscosity increase compared to that of carbon black and graphite.

Highly Graphitized Carbon Coating on SiO with a π⁻π Stacking Precursor Polymer for High Performance Lithium-Ion Batteries.

A highly graphitized carbon on a silicon monoxide (SiO) surface coating at low temperature, based on polymer precursor π⁻π stacking, was developed. A novel conductive and electrochemically stable carbon coating was rationally designed to modify the SiO anode materials by controlling the sintering of a conductive polymer, a pyrene-based homopolymer poly (1-pyrenemethyl methacrylate; PPy), which achieved high graphitization of the carbon layers at a low temperature and avoided silicon carbide formation and possible SiO material transformation. When evaluated as the anode of a lithium-ion battery (LIB), the carbon-coated SiO composite delivered a high discharge capacity of 2058.6 mAh/g at 0.05 C of the first formation cycle with an initial Coulombic efficiency (ICE) of 62.2%. After 50 cycles at 0.1 C, this electrode capacity was 1090.2 mAh/g (~82% capacity retention, relative to the capacity of the second cycle at 0.1 °C rate), and a specific capacity of 514.7 mAh/g was attained at 0.3 C after 500 cycles. Furthermore, the coin-type full cell composed of the carbon coated SiO composite anode and the Li[Ni0.5Co0.2Mn0.3O2] cathode attained excellent cycling performance. The results show the potential applications for using a π⁻π stacking polymer precursor to generate a highly graphitize coating for next-generation high-energy-density LIBs.

Molecular Spring Enabled High-Performance Anode for Lithium Ion Batteries.

Flexible butyl interconnection segments are synthetically incorporated into an electronically conductive poly(pyrene methacrylate) homopolymer and its copolymer. The insertion of butyl segment makes the pyrene polymer more flexible, and can better accommodate deformation. This new class of flexible and conductive polymers can be used as a polymer binder and adhesive to facilitate the electrochemical performance of a silicon/graphene composite anode material for lithium ion battery application. They act like a "spring" to maintain the electrode mechanical and electrical integrity. High mass loading and high areal capacity, which are critical design requirements of high energy batteries, have been achieved in the electrodes composed of the novel binders and silicon/graphene composite material. A remarkable area capacity of over 5 mAh/cm² and volumetric capacity of over 1700 Ah/L have been reached at a high current rate of 333 mA/g.

Wide bandgap OPV polymers based on pyridinonedithiophene unit with efficiency >5.

We report the properties of a new series of wide band gap photovoltaic polymers based on the N-alkyl 2-pyridone dithiophene (PDT) unit. These polymers are effective bulk heterojunction solar cell materials when blended with phenyl-C71-butyric acid methyl ester (PC71BM). They achieve power conversion efficiencies (up to 5.33%) high for polymers having such large bandgaps, ca. 2.0 eV (optical) and 2.5 eV (electrochemical). Grazing incidence wide-angle X-ray scattering (GIWAXS) reveals strong correlations between π-π stacking distance and regularity, polymer backbone planarity, optical absorption maximum energy, and photovoltaic efficiency.