Nanostructures and multi-scale aggregation of high ion exchange capacity short-side-chain perfluorosulfonic acid dispersion.

Short-side-chain perfluorosulfonic acid (SSC-PFSA) ionomers with high ion-exchange-capacity are promising candidates for high-temperature proton exchange membranes (PEMs) and catalyst layer (CL) binders. The solution-casting method determines the importance of SSC-PFSA dispersion characteristics in shaping the morphology of PEMs and CLs. Therefore, a thorough understanding of the chain behavior of SSC-PFSA in dispersions is essential for fabricating high-quality PEMs and CLs. In this study, we have employed multiple characterization techniques, including dynamic light scatting (DLS), small-angle X-ray scattering (SAXS), and cryo-transmission electron microscope (Cryo-TEM), to fully study the chain aggregation behaviors of SSC-PFSA in water-ethanol solvents and elucidate the concentration-dependent self-assembly process. In dilute dispersions (2 mg/mL), SSC-PFSA assembles into mono-disperse rod-like aggregates, featuring a twisted fluorocarbon backbone that forms a hydrophobic stem, and the sulfonic acid side chains extending outward to suit the hydrophilic environment. As the concentration increases, the radius of rod particles increases from 1.47 to 1.81 nm, and the mono-disperse rod particles first form a "end-to-end" configuration that doubles length (10 mg/mL), and then transform into a swollen network structure in semi-dilute dispersion (20 mg/mL). This work provides a well-established structure model for SSC-PFSA dispersions, which is the key nanostructure to be inherited by PEMs.

Rational Materials and Structure Design for Improving the Performance and Durability of High Temperature Proton Exchange Membranes (HT-PEMs).

Hydrogen energy as the next-generation clean energy carrier has attracted the attention of both academic and industrial fields. A key limit in the current stage is the operation temperature of hydrogen fuel cells, which lies in the slow development of high-temperature and high-efficiency proton exchange membranes. Currently, much research effort has been devoted to this field, and very innovative material systems have been developed. The authors think it is the right time to make a short summary of the high-temperature proton exchange membranes (HT-PEMs), the fundamentals, and developments, which can help the researchers to clearly and efficiently gain the key information. In this paper, the development of key materials and optimization strategies, the degradation mechanism and possible solutions, and the most common morphology characterization techniques as well as correlations between morphology and overall properties have been systematically summarized.

All-polymer organic solar cells with nano-to-micron hierarchical morphology and large light receiving angle.

Distributed photovoltaics in living environment harvest the sunlight in different incident angles throughout the day. The development of planer solar cells with large light-receiving angle can reduce the requirements in installation form factor and is therefore urgently required. Here, thin film organic photovoltaics with nano-sized phase separation integrated in micro-sized surface topology is demonstrated as an ideal solution to proposed applications. All-polymer solar cells, by means of a newly developed sequential processing, show large magnitude hierarchical morphology with facilitated exciton-to-carrier conversion. The nano fibrilar donor-acceptor network and micron-scale optical field trapping structure in combination contributes to an efficiency of 19.06% (certified 18.59%), which is the highest value to date for all-polymer solar cells. Furthermore, the micron-sized surface topology also contributes to a large light-receiving angle. A 30% improvement of power gain is achieved for the hierarchical morphology comparing to the flat-morphology devices. These inspiring results show that all-polymer solar cell with hierarchical features are particularly suitable for the commercial applications of distributed photovoltaics due to its low installation requirement.

Nanosized Proton Conductor Array with High Specific Surface Area Improves Fuel Cell Performance at Low Pt Loading.

The use of ordered catalyst layers, based on micro-/nanostructured arrays such as the ordered Nafion array, has demonstrated great potential in reducing catalyst loading and improving fuel cell performance. However, the size (diameter) of the basic unit of the most existing ordered Nafion arrays, such as Nafion pillar or cone, is typically limited to micron or submicron sizes. Such small sizes only provide a limited number of proton transfer channels and a small specific area for catalyst loading. In this work, the ordered Nafion array with a pillar diameter of only 40 nm (D40) was successfully prepared through optimization of the Nafion solvent, thermal annealing temperature, and stripping mode from the anode alumina oxide (AAO) template. The density of D40 is 2.7 × 1010 pillars/cm2, providing an abundance of proton transfer channels. Additionally, D40 has a specific area of up to 51.5 cm2/cm2, which offers a large area for catalyst loading. This, in turn, results in the interface between the catalyst layer and gas diffusion layer becoming closer. Consequently, the peak power densities of the fuel cells are 1.47 (array as anode) and 1.29 W/cm2 (array as cathode), which are 3.3 and 2.9 times of that without array, respectively. The catalyst loading is significantly reduced to 17.6 (array as anode) and 61.0 µg/cm2 (array as cathode). Thus, the nanosized Nafion array has been proven to have high fuel cell performance with low Pt catalyst loading. Moreover, this study also provides guidance for the design of a catalyst layer for water electrolysis and electrosynthesis.

High-temperature low-humidity proton exchange membrane with "stream-reservoir" ionic channels for high-power-density fuel cells.

The perfluorosulfonic acid (PFSA) proton exchange membrane (PEM) is the key component for hydrogen fuel cells (FCs). We used in situ synchrotron scattering to investigate the PEM morphology evolution and found a "stream-reservoir" morphology, which enables efficient proton transport. The short-side-chain (SSC) PFSA PEM is fabricated under the guidance of morphology optimization, which delivered a proton conductivity of 193 milliSiemens per centimeter [95% relativity humidity (RH)] and 40 milliSiemens per centimeter (40% RH) at 80°C. The improved glass transition temperature, water permeability, and mechanical strength enable high-temperature low-humidity FC applications. Performance improvement by 82.3% at 110°C and 25% RH is obtained for SSC-PFSA PEM FCs compared to Nafion polymer PEM devices. The insights in chain conformation, packing mechanism, crystallization, and phase separation of PFSAs build up the structure-property relationship. In addition, SSC-PFSA PEM is ideal for high-temperature low-humidity FCs that are needed urgently for high-power-density and heavy-duty applications.

Enhanced ammonia sensing response based on Pt-decorated Ti3C2Tx/TiO2composite at room temperature.

Herein, we report a Pt-decorated Ti3C2Tx/TiO2gas sensor for the enhanced NH3sensing response at room temperature. Firstly, the TiO2nanosheets (NSs) arein situgrown onto the two-dimensional (2D) Ti3C2Txby hydrothermal treatment. Similar to Ti3C2Txsensor, the Ti3C2Tx/TiO2sensor has a positive resistance variation upon exposure to NH3, but with slight enhancement in response. However, after the loading of Pt nanoparticles (NPs), the Pt-Ti3C2Tx/TiO2sensor shows a negative response with significantly improved NH3sensing performance. The shift in response direction indicates that the dominant sensing mechanism has changed under the sensitization effect of Pt NPs. At room temperature, the response of Pt-Ti3C2Tx/TiO2gas sensor to 100 ppm NH3is about 45.5%, which is 13.8- and 10.8- times higher than those of Ti3C2Txand Ti3C2Tx/TiO2gas sensors, respectively. The experimental detection limit of the Pt-Ti3C2Tx/TiO2gas sensor to detect NH3is 10 ppm, and the corresponding response is 10.0%. In addition, the Pt-Ti3C2Tx/TiO2gas sensor shows the fast response/recovery speed (23/34 s to 100 ppm NH3), high selectivity and good stability. Considering both the response value and the response direction, the corresponding gas-sensing mechanism is also deeply discussed. This work is expected to shed a new light on the development of noble metals decorated MXene-metal oxide gas sensors.

Bionic Construction of Helical Bi2 O3 Microfibers for Highly Efficient CO2 Electroreduction.

Helical Bi2 O3 microfibers (HBM) were prepared with the assistance of cotton template through a simple heating treatment in air. This twisted structure induced the lattice strains, enriched the oxygen vacancies of Bi2 O3 , and promoted the sufficient exposure of active sites simultaneously, thus performing outstanding activity and selectivity as catalyst for CO2 electroreduction to formate. The faradaic efficiency (FE) of formate reached 100.4±1.9 % at -0.90 V vs. reversible hydrogen electrode (RHE) in an H-cell, and the partial current density was boosted to 226 mA cm-2 with FEformate of 96 % at -1.08 V vs. RHE in a flow cell. This work may open a new era for construction of metal oxide fibers by bionic strategy as high-performance electrocatalysts.

Single-junction organic solar cells with over 19% efficiency enabled by a refined double-fibril network morphology.

In organic photovoltaics, morphological control of donor and acceptor domains on the nanoscale is the key for enabling efficient exciton diffusion and dissociation, carrier transport and suppression of recombination losses. To realize this, here, we demonstrated a double-fibril network based on a ternary donor-acceptor morphology with multi-length scales constructed by combining ancillary conjugated polymer crystallizers and a non-fullerene acceptor filament assembly. Using this approach, we achieved an average power conversion efficiency of 19.3% (certified 19.2%). The success lies in the good match between the photoelectric parameters and the morphological characteristic lengths, which utilizes the excitons and free charges efficiently. This strategy leads to an enhanced exciton diffusion length and a reduced recombination rate, hence minimizing photon-to-electron losses in the ternary devices as compared to their binary counterparts. The double-fibril network morphology strategy minimizes losses and maximizes the power output, offering the possibility of 20% power conversion efficiencies in single-junction organic photovoltaics.

The Molecular Ordering and Double-Channel Carrier Generation of Nonfullerene Photovoltaics within Multi-Length-Scale Morphology.

The success of nonfullerene acceptor (NFA) solar cells lies in their unique physical properties beyond the extended absorption and suitable energy levels. The current study investigates the morphology and photophysical behavior of PBDB-T donor blending with ITIC, 4TIC, and 6TIC acceptors. Single-crystal study shows that the π-π stacking and side-chain interaction dictate molecular assembly, which can be carried to blended films, forming a multi-length-scale morphology. Spontaneous carrier generation is seen in ITIC, 4TIC, and 6TIC neat films and their blended thin films using the PBDB-T donor, providing a new avenue of zero-energy-loss carrier formation. The molecular packing associated with specific contacts and geometry is key in influencing the photophysics, as demonstrated by the charge transfer and carrier lifetime results. The 2D layer of 6TIC facilitates the exciton-to-polaron conversion, and the largest photogenerated polaron yield is obtained. The new mechanism, together with the highly efficient blending region carrier generation, has the prospect of the fundamental advantage for NFA solar cells, from molecular assembly to thin-film morphology.

Improved Thermo-Mechanical Properties and Reduced Hydrogen Permeation of Short Side-Chain Perfluorosulfonic Acid Membranes Doped with Ti3C2Tx.

Benefiting from its large specific surface with functional -OH/-F groups, Ti3C2Tx, a typical two-dimensional (2D) material in the recently developed MXene family, was synthesized and used as a filler to improve the properties of the short side-chain (SSC) perfluorosulfonic acid (PFSA) proton exchange membrane. It is found that the proton conductivity is enhanced by 15% while the hydrogen permeation is reduced by 45% after the addition of 1.5 wt% Ti3C2Tx filler into the SSC PFSA membrane. The improved proton conductivity of the composite membrane could be associated with the improved proton transport environment in the presence of the hydrophilic functional groups (such as -OH) of the Ti3C2Tx filler. The significantly reduced hydrogen permeation could be attributed to the incorporation of the impermeable Ti3C2Tx 2D fillers and the decreased hydrophilic ionic domain spacing examined by the small angle X-ray scattering (SAXS) for the composite membrane. Furthermore, improved thermo-mechanical properties of the SSC/Ti3C2Tx composite membrane were measured by dynamic mechanical analyzer (DMA) and tensile strength testing. The demonstrated higher proton conductivity, lower hydrogen permeation, and improved thermo-mechanical stability indicate that the SSC/Ti3C2Tx composite membranes could be a potential membrane material for PEM fuel cells operating above the water boiling temperature.

Capture the high-efficiency non-fullerene ternary organic solar cells formula by machine-learning-assisted energy-level alignment optimization.

Appropriate energy-level alignment in non-fullerene ternary organic solar cells (OSCs) can enhance the power conversion efficiencies (PCEs), due to the simultaneous improvement in charge generation/transportation and reduction in voltage loss. Seven machine-learning (ML) algorithms were used to build the regression and classification models based on energy-level parameters to predict PCE and capture high-performance material combinations, and random forest showed the best predictive capability. Furthermore, two sets of verification experiments were designed to compare the experimental and predicted results. The outcome elucidated that a deep lowest unoccupied molecular orbital (LUMO) of the non-fullerene acceptors can slightly reduce the open-circuit voltage (V OC) but significantly improve short-circuit current density (J SC), and, to a certain extent, the V OC could be optimized by the slightly up-shifted LUMO of the third component in non-fullerene ternary OSCs. Consequently, random forest can provide an effective global optimization scheme and capture multi-component combinations for high-efficiency ternary OSCs.

High-Efficiency Organic Photovoltaics using Eutectic Acceptor Fibrils to Achieve Current Amplification.

The intrinsic electronic properties of donor (D) and acceptor (A) materials in coupling with morphological features dictate the output in organic solar cells (OSCs). New physical properties of intimate eutectic mixing are used in nonfullerene-acceptor-based D-A1 -A2 ternary blends to fine-tune the bulk heterojunction thin film morphology as well as their electronic properties. With enhanced thin film crystallinity and improved carrier transport, a significant JSC amplification is achieved due to the formation of eutectic fibrillar lamellae and reduced defects state density. Material wise, aligned cascading energy levels with much larger driving force, and suppressed recombination channels confirm efficient charge transfer and transport, enabling an improved power conversion efficiency (PCE) of 17.84%. These results reveal the importance of utilizing specific material interactions to control the crystalline habit in blended films to form a well-suited morphology in guiding superior performances, which is of high demand in the next episode of OSC fabrication toward 20% PCE.

3-(4,6-Dichloro-1,3,5-triazin-2-yl)-2,2-dimethyl-1,3-oxazolidine.

In the title compound, C(8)H(10)Cl(2)N(4)O, the dichloro-substituted triazine ring and the quasi-plane of the five-membered dimethyl-substituted oxazolidine unit, in which the O atom lies 0.228 (1) Šout of the least-squares plane, are close to being coplanar [dihedral angle = 4.99 (10)°]. In the crystal, mol-ecules are linked by inter-molecular C-H⋯Cl inter-actions, forming chains extend along the a axis. Also present are weak π-π inter-actions between triazine rings [minimum ring centroid separation = 3.7427 (11) Å].