Electroplated Electrodes for Continuous and Mass-Efficient Electrochemical Hydrogenation.

Electrocatalytic hydrogenations (ECH) enable the reduction of organic substrates upon usage of electric current and present a sustainable alternative to conventional processes if green electricity is used. Opposed to most current protocols for electrode preparation, this work presents a one-step binder- and additive-free production of silver- and copper-electroplated electrodes. Controlled adjustment of the preparation parameters allows for the tuning of catalyst morphology and its electrochemical properties. Upon optimization of the deposition protocol and carbon support, high faradaic efficiencies of 93 % for the ECH of the Vitamin A- and E-synthon 2-methyl-3-butyn-2-ol (MBY) are achieved that can be maintained at current densities of 240 mA cm-2 and minimal catalyst loadings of 0.2 mg cm-2, corresponding to an unmatched production rate of 1.47 kgMBE gcat -1 h-1. For a continuous hydrogenation process, the protocol can be directly transferred into a single-pass operation mode giving a production rate of 1.38 kgMBE gcat -1 h-1. Subsequently, the substrate spectrum was extended to a total of 17 different C-C-, C-O- and N-O-unsaturated compounds revealing the general applicability of the reported process. Our results lay an important groundwork for the development of electrochemical reactors and electrodes able to directly compete with the palladium-based thermocatalytic state of the art.

Optimizing Active Layer Morphology of Organic Solar Cells by Constructing Random Copolymers with Simple Third Units.

The molecular structure of the polymer PM6 is elaborately modified through random copolymerization by incorporating simple units of either difluoro-substituted thiophene (2FT) or dicyano-substituted thiophene (2CNT). The incorporation of the 2FT unit significantly enhanced the coplanarity of the random copolymers, leading to improved molecular crystallinity, whereas the introduction of the 2CNT unit featured the opposite effect. Thanks to the optimized morphology resembling a fiber-like interpenetrating network structure, the organic solar cells based on PM6-10%2FT:IT4F showed higher and more balanced charge mobilities, achieving a power conversion efficiency (PCE) of 12.65%, which is comparable to that of PM6-based devices. For comparison, the 2CN-series random copolymers-based devices exhibited lower PCEs of ˂12%. Interestingly, a superior PCE close to 19.0% is achieved in PM6:L8-BO:PM6-20%2CN based ternary device due to the significant improvement in open-circuit voltage. This work demonstrates that the crystallinity of donor polymers can be enhanced by introducing simple structural units to strengthen the coplanarity of the backbone, thereby achieving an optimized morphology that promotes favorable charge transport.

Processing the Interlayer and Optimizing the Active Layer by One-Step Dissolution Compensation in Organic Solar Cells.

Optimized morphology of the active layer and electrode interface is critical for obtaining high-performance organic solar cells. However, achieving this typically involves a multifaceted, sequential process that renders outcomes unpredictable. Here, by exploiting the dissolution compensation, we propose a one-step method that integrates interlayer fabrication and a controllable morphology optimization. Taking an "out of the box" approach, we incorporate the good solvent of the active layer into the interlayer solution to act as dissolution compensation, breaking the orthogonal solvent principles to allow the morphology of the active layer to evolve to an optimized state while the interface layer is being processed. Using two commercially available material systems, D18:Y6 and D18:L8-BO, as examples, it was found that the JSC and fill factor (FF) device can be improved by using an appropriate ratio of the compensation solvent chloroform in the interlayer solution. As a result, the power conversion efficiency of the device based on the two state-of-the-art systems can be increased by about 7.5% (D18:Y6, from 17.04 to 18.31%; D18:L8-BO, from 17.97 to 19.31%). This one-step strategy has been shown to be universally applicable to other diverse systems and provides a simple yet reliable method for accurately depositing high-quality interlayers with an optimized active layer morphology in high-performance organic solar cells and other solution-processable organic electronics.

Crossbreeding Effect of Chalcogenation and Iodination on Benzene Additives Enables Optimized Morphology and 19.68% Efficiency of Organic Solar Cells.

Volatile solid additives have attracted increasing attention in optimizing the morphology and improving the performance of currently dominated non-fullerene acceptor-based organic solar cells (OSCs). However, the underlying principles governing the rational design of volatile solid additives remain elusive. Herein, a series of efficient volatile solid additives are successfully developed by the crossbreeding effect of chalcogenation and iodination for optimizing the morphology and improving the photovoltaic performances of OSCs. Five benzene derivatives of 1,4-dimethoxybenzene (DOB), 1-iodo-4-methoxybenzene (OIB), 1-iodo-4-methylthiobenzene (SIB), 1,4-dimethylthiobenzene (DSB) and 1,4-diiodobenzene (DIB) are systematically studied, where the widely used DIB is used as the reference. The effect of chalcogenation and iodination on the overall property is comprehensively investigated, which indicates that the versatile functional groups provided various types of noncovalent interactions with the host materials for modulating the morphology. Among them, SIB with the combination of sulphuration and iodination enabled more appropriate interactions with the host blend, giving rise to a highly ordered molecular packing and more favorable morphology. As a result, the binary OSCs based on PM6:L8-BO and PBTz-F:L8-BO as well as the ternary OSCs based on PBTz-F:PM6:L8-BO achieved impressive high PCEs of 18.87%, 18.81% and 19.68%, respectively, which are among the highest values for OSCs.

Optimization of the Morphology of the Removal Function for Rotating Abrasive Water Jet Polishing.

Abrasive water jet polishing has significant advantages in the manufacturing of complex optical components (such as high-slope optical component cavities) that require high-precision manufacturing. This is due to its processing process, in which the polishing tool does not make direct contact with the surface of the workpiece, and instead maintains a considerable distance. However, the removal functions of most existing abrasive water-jet polishing technologies do not possess strict symmetry, which significantly impacts the ability to correct surface figure errors. Therefore, this study implements rotating abrasive water-jet polishing based on traditional abrasive water jet processing to optimize the removal function, which turns it into a Gaussian form; thus, obtaining a type of removal function more suitable for CCOS polishing. This paper derives an empirical formula between the distance s' from the peak removal point of the removal function to the stagnation point and the nozzle tilt angle α, based on geometric relationships and experimental results, analyzes the relationship between material removal efficiency, nozzle tilt angle, and standoff distance. Finally, this paper verifies through experiments the validity of this empirical formula under different process parameters. Therefore, this study obtains the process conditions that allow rotating abrasive water-jet polishing technology to achieve a stable Gaussian form removal function, and the appropriate process parameters to be selected in conjunction with polishing efficiency; thereby, effectively improving the removal function's corrective ability and manufacturing efficiency. It provides theoretical support for the processing capability and process parameter selection of abrasive water-jet polishing technology, solves the problem of limited shaping capability of existing abrasive water jet tools, and significantly improves the manufacturing capability of high-end optical components.

Cyano-Functionalized Fused Bithiophene Imide Dimer-Based n-Type Polymers for High-Performance Organic Thermoelectrics.

Doped n-type polymers usually exhibit low electrical conductivities and thermoelectric power factors (PFs), restricting the development of high-performance p-n-junction-based organic thermoelectrics (OTEs). Herein, the design and synthesis of a new cyano-functionalized fused bithiophene imide dimer (f-BTI2), CNI2, is reported, which synergistically combines the advantages of both cyano and imide functionalities, thus leading to substantially higher electron deficiency than the parent f-BTI2. On the basis of this novel building block, a series of n-type donor-acceptor and acceptor-acceptor polymers are successfully synthesized, all of which show good solubility, deep-lying frontier molecular orbital levels, and favorable polymer chain orientation. Among them, the acceptor-acceptor polymer PCNI2-BTI delivers an excellent electrical conductivity up to 150.2 S cm-1 and a highest PF of 110.3 µW m-1  K-2 in n-type OTEs, attributed to the optimized polymer electronic properties and film morphology with improved molecular packing and higher crystallinity assisted by solution-shearing technology. The PF value is the record of n-type polymers for OTEs to date. This work demonstrates a facile approach to designing high-performance n-type polymers and fabricating high-quality films for OTE applications.

Volatile Solid Additive-Assisted Sequential Deposition Enables 18.42% Efficiency in Organic Solar Cells.

Morphology optimization of active layer plays a critical role in improving the performance of organic solar cells (OSCs). In this work, a volatile solid additive-assisted sequential deposition (SD) strategy is reported to regulate the molecular order and phase separation in solid state. The OSC adopts polymer donor D18-Cl and acceptor N3 as active layer, as well as 1,4-diiodobenzene (DIB) as volatile additive. Compared to the D18-Cl:N3 (one-time deposition of mixture) and D18-Cl/N3 (SD) platforms, the D18-Cl/N3(DIB) device based on DIB-assisted SD method exhibits a finer phase separation with greatly enhanced molecular crystallinity. The optimal morphology delivers superior charge transport and extraction, offering a champion power conversion efficiency of 18.42% with significantly enhanced short-circuit current density (Jsc ) of 27.18 mA cm-2 and fill factor of 78.8%. This is one of the best performances in binary SD OSCs to date. Angle-dependent grazing-incidence wide-angle X-ray scattering technique effectively reveals the vertical phase separation and molecular crystallinity of the active layer. This work demonstrates the combination of volatile solid additive and sequential deposition is an effective method to develop high-performance OSCs.

Synergistic Effects of Chlorination and Branched Alkyl Side Chain on the Photovoltaic Properties of Simple Non-Fullerene Acceptors with Quinoxaline as the Core.

To date, the fused-ring electron acceptors show the best photovoltaic performances, and the development of simple non-fullerene acceptors via intramolecular noncovalent interactions can reduce synthetic costs. In this work, four simple non-fullerene acceptors with an A-D-A'-D-A configuration (QCIC1, QCIC2, QCIC3, and QCIC4) were synthesized. They contained the same conjugated backbone (A': quinoxaline; D: cyclopentadithiophene; A: dicyano-indanone) but different halogen atoms and alkyl side chains. Due to the chlorination on the end-groups and the most and/or longest branched alkyl side chains on the backbone, the blended film composed of QCIC3 and donor poly{[2,6'-4,8-di(5-ethylhexylthienyl)benzo [1,2-b : 4,5-b']dithiophene]-alt-[5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c : 4',5'-c']dithiophene-4,8-dione)]} (PBDB-T) exhibited the strongest π-π stacking and the most suitable phase-separation domains among the four blended films. Therefore, the QCIC3-based organic solar cells yielded the highest power conversion efficiency of 10.55 %. This work provides a pathway to optimize the molecular arrangements and enhance the photovoltaic property of simple electron acceptors through subtle chemical modifications.

Compatibility between Solubility and Enhanced Crystallinity of Benzotriazole-Based Small Molecular Acceptors with Less Bulky Alkyl Chains for Organic Solar Cells.

Optimizing the molecular structures of organic solar cell (OSC) materials and boosting the power conversion efficiencies are the eternal theme in the solar energy region. A series of fused benzotriazole (BTA)-based A-DA'D-A structures of nonfullerene acceptors (such as Y18) were developed for application in efficient OSCs, in which high quantum efficiencies and low voltage losses could be achieved because of the optimized electron-deficient core and specific molecular geometry. Here, based on the BTA core, the bulky alkyl chain on the BTA unit was further tailored to minimize the lateral alkyl chains and enhance the crystallinity while maintaining an adequate solubility. The resulting NFAs of BTA-C1, BTA-C5, and BTA-C6 are synthesized. Compared with the well-designed molecular Y18 (BTA-C8), we found that simply replacing the 2-ethylhexyl chain with a single methyl (BTA-C1) can easily improve the fill factor up to 77%, but its poor light absorption capacity and large domain size impeded further efficiency improvement. In particular, the BTA-C5, with a shortened branch alkyl chain of 2-methylbutyl, achieves suitable solubility and enhanced crystallinity. Significantly, owing to the balanced charge carrier mobility and suitable phase separation, the BTA-C5-based binary single-junction OSCs achieve a high efficiency of 17.11%, which is one of the top values in BTA-based OSCs.

Improved Efficiency of Perovskite Solar Cells by the Interfacial Modification of the Active Layer.

As the most promising material for thin-film solar cells nowadays, perovskite shine for its unique optical and electronic properties. Perovskite-based solar cells have already been demonstrated with high efficiencies. However, it is still very challenging to optimize the morphology of perovskite film. In this paper we proposed a smooth and continuous perovskite active layer by treating the poly (3, 4-ethylenedioxythiophene): poly (styrenesulphonate) (PEDOT:PSS) with pre-perovskite deposition and dimethylsulfoxide (DMSO) rinse. The scanning electron microscope (SEM) and atomic force microscope (AFM) images confirmed a perovskite active layer consisting of large crystal grains with less grain boundary area and enhanced crystallinity. The perovskite devices fabricated by this method feature a high power conversion efficiency (PCE) of 11.36% and a short-circuit current (Jsc) of 21.9 mAcm-2.

Fracture Strength and Osseointegration of an Ultrafine-Grained Titanium Mini Dental Implant after Macromorphology Optimization.

The aim of this in vitro and in vivo study was to evaluate the fracture strength and osseointegration of an ultrafine-grained pure titanium (UFG-Ti) mini dental implant, prepared by equal channel angular pressing (ECAP) after macro-morphology optimization. UFG-Ti was prepared by ECAP using four passes in route Bc with the internal channel angle of 120° at room temperature. Furthermore, its microstructure and mechanical properties were studied. In optimization, a three-dimensional finite element model (FEM) composed of an UFG-Ti mini implant and alveolar bone was established to improve the implant surface area and decrease the stress distribution. Then, optimized mini implants were fabricated using UFG-Ti, and a fracture strength test was performed. For the in vivo study, UFG-Ti mini implants were inserted into rabbit femurs. A histological assessment and a pull-out test were performed to evaluate its osseointegration ability. The results show that the ultimate tensile strength of UFG-Ti (685 ± 35 MPa) was significantly higher than that of commercial pure titanium (CP-Ti grade 4, 454 ± 27 MPa). After optimization, the surface area of the 2.5 mm diameter mini implant was 19% higher than that of the standard-thread mini implant, and the maximum equivalent stress (Max EQV stress) decreased by 28% in cortical bone and by 33.1% in cancellous bone, when the thread height was 0.3 mm and the pitch was 0.67 mm. The fracture strength of the UFG-Ti mini implants (328 ± 21 N) was significantly higher than that of CP-Ti grade 4 mini implants (197 ± 11 N). The in vivo study showed favorable osseointegration in both the UFG-Ti and CP-Ti groups, but the osseointegration strength of the optimized mini implants was higher than that of the standard-thread mini implants. In conclusion, the fracture and osseointegration strength had been significantly improved for UFG-Ti mini dental implant after optimization. The excellent mechanical properties and osseointegration of the UFG-Ti mini implant suggest its feasibility for clinical application.

Rhombicuboctahedron unit cell based scaffolds for bone regeneration: geometry optimization with a mechanobiology - driven algorithm.

In a context more and more oriented towards customized medical solutions, we propose a mechanobiology-driven algorithm to determine the optimal geometry of scaffolds for bone regeneration that is the most suited to specific boundary and loading conditions. In spite of the huge number of articles investigating different unit cells for porous biomaterials, no studies are reported in the literature that optimize the geometric parameters of such unit cells based on mechanobiological criteria. Parametric finite element models of scaffolds with rhombicuboctahedron unit cell were developed and incorporated into an optimization algorithm that combines them with a computational mechanobiological model. The algorithm perturbs iteratively the geometry of the unit cell until the best scaffold geometry is identified, i.e. the geometry that allows to maximize the formation of bone. Performances of scaffolds with rhombicuboctahedron unit cell were compared with those of other scaffolds with hexahedron unit cells. We found that scaffolds with rhombicuboctahedron unit cell are particularly suited for supporting medium-low loads, while, for higher loads, scaffolds with hexahedron unit cells are preferable. The proposed algorithm can guide the orthopaedic/surgeon in the choice of the best scaffold to be implanted in a patient-specific anatomic region.

A Near-Infrared Photoactive Morphology Modifier Leads to Significant Current Improvement and Energy Loss Mitigation for Ternary Organic Solar Cells.

Herein, efficient organic solar cells (OSCs) are realized with the ternary blend of a medium band gap donor (poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione)] (PBDB-T)) with a low band gap acceptor (2,2'-((2Z,2'Z)-(((2,5-difluoro-1,4-phenylene)bis(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene-6,2-diyl))bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (HF-PCIC)) and a near-infrared acceptor (2,2'-((2Z,2'Z)-(((4,4,9,9-tetrakis(4-hexylphenyl)-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(4-((2-ethylhexyl)oxy)thiophene-5,2-diyl))bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (IEICO-4F)). It is shown that the introduction of IEICO-4F third component into PBDB-T:HF-PCIC blend increases the short-circuit current density (Jsc) of the ternary OSC to 23.46 mA cm-2, with a 44% increment over those of binary devices. The significant current improvement originates from the broadened absorption range and the active layer morphology optimization through the introduction of IEICO-4F component. Furthermore, the energy loss of the ternary cells (0.59 eV) is much decreased over that of the binary cells (0.80 eV) due to the reduction of both radiative recombination from the absorption below the band gap and nonradiative recombination upon the addition of IEICO-4F. Therefore, the power conversion efficiency increases dramatically from 8.82% for the binary cells to 11.20% for the ternary cells. This work provides good examples for simultaneously achieving both significant current enhancement and energy loss mitigation in OSCs, which would lead to the further construction of highly efficient ternary OSCs.

Highly Efficient Nonfullerene Polymer Solar Cells Enabled by a Copper(I) Coordination Strategy Employing a 1,3,4-Oxadiazole-Containing Wide-Bandgap Copolymer Donor.

A novel wide-bandgap copolymer of PBDT-ODZ based on benzo[1,2-b:4,5-b' ]dithiophene (BDT) and 1,3,4-oxadiazole (ODZ) blocks is developed for efficient nonfullerene polymer solar cells (NF-PSCs). PBDT-ODZ exhibits a wide bandgap of 2.12 eV and a low-lying highest occupied molecular orbital (HOMO) level of -5.68 eV, which could match well with the low-bandgap acceptor of 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylthienyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene (ITIC-Th), inducing a good complementary absorption from 300 to 800 nm and a minimal HOMO level offset (0.1 eV). The PBDT-ODZ:ITIC-Th devices exhibit a large open-circuit voltage (Voc ) of 1.08 eV and a low energy loss (Eloss ) of 0.50 eV, delivering a high power conversion efficiency (PCE) of 10.12%. By adding a small amount of copper(I) iodide (CuI) as an additive to form coordination complexes in the active blends, much higher device performances are achieved due to the improved absorption and crystallinity. After incorporating 4% of CuI, the PCE is elevated to 12.34%, with a Voc of 1.06 V, a Jsc of 17.1 mA cm-2 and a fill factor of 68.1%. This work not only provides a novel oxadiazole-containing wide-bandgap polymeric donor candidate for high-performance NF-PSCs but also presents an efficient morphology-optimization approach to elevate the PCE of NF-PSCs for future practical applications.

High-Efficiency Nonfullerene Polymer Solar Cell Enabling by Integration of Film-Morphology Optimization, Donor Selection, and Interfacial Engineering.

Carrier mobility is a vital factor determining the electrical performance of organic solar cells. In this paper we report that a high-efficiency nonfullerene organic solar cell (NF-OSC) with a power conversion efficiency of 6.94 ± 0.27% was obtained by optimizing the hole and electron transportations via following judicious selection of polymer donor and engineering of film-morphology and cathode interlayers: (1) a combination of solvent annealing and solvent vapor annealing optimizes the film morphology and hence both hole and electron mobilities, leading to a trade-off of fill factor and short-circuit current density (Jsc); (2) the judicious selection of polymer donor affords a higher hole and electron mobility, giving a higher Jsc; and (3) engineering the cathode interlayer affords a higher electron mobility, which leads to a significant increase in electrical current generation and ultimately the power conversion efficiency (PCE).