Abstract

Organic solar cells (OSCs) present a promising renewable energy technology due to their cost-effectiveness, adaptability, and lightweight nature. The advent of non-fullerene acceptors has further boosted their significance, allowing for power conversion efficiencies that surpass 19% even with an active layer thickness of about 100 nm. However, in order to achieve large scale production, it is necessary to fabricate OSCs with thicker active layers exceeding 300 nm that are compatible with large-area printing techniques. Nevertheless, OSCs with thick active layers have inferior performance compared to those with thin active layers. To expedite the transition of OSCs from laboratory to industrial high-throughput manufacturing, considerable efforts have been made to comprehend the performance limitations of thick active-layer OSCs, develop novel photoactive materials that are high-performance and tolerant towards the thickness of the active layer, and optimize the morphology of the photoactive layer and device structure. This review aims to provide a comprehensive summary of the mechanisms that lead to efficiency loss in thick active-layer OSCs, the representative works on molecular design, and the optimization strategies for high-performance thick active-layer OSCs, and the remaining challenges that must be addressed.

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Comprehensive Summary

All-Polymer solar cells (all-PSCs) have attracted considerable attention due to their inherent advantages over other types of organic solar cells, including superior optical and thermal stability, as well as exceptional mechanical durability. Recently, all-PSCs have experienced remarkable advancements in device performance thanks to the invention of polymerized small-molecule acceptors (PSMAs) since 2017. Among these PSMAs, PY-IT has garnered immense interest from the scientific community due to its exceptional performance in all-PSCs. In this review, we presented the design principles of PY-IT and discussed the various strategies employed in device engineering for PY-IT-based all-PSCs. These strategies include additive and interface engineering, layer-by-layer processing methods, meniscus-assisted coating methods, and ternary strategy. Furthermore, this review highlighted several novel polymeric donor materials that are paired with PY-IT to achieve efficient all-PSCs. Lastly, we summarized the inspiring strategies for further advancing all-PSCs based on PY-IT. These strategies aim to enhance the overall performance and stability of all-PSCs by exploring new materials, optimizing device architectures, and improving fabrication techniques. By leveraging these approaches, we anticipate significant progress in the development of all-PSCs and their potential as a viable renewable energy source.

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Comprehensive Summary

Hemostatic hydrogels are widely applied for wound management of damaged tissues, traumatic wounds, and surgical incisions. Some hydrogels composed of bioactive components, including fibrin and thrombin, showed great promise in the clinic due to their good pro-coagulation effect. Based on the expanding knowledge of cascade catalysis reaction of coagulation and emerging bioactive substances. Recently, massive bioactive hydrogels based on peptides, hemocoagulase, polyphosphate (polyP), etc., have been developed as hemostatic materials. Based on the coagulation process and mechanism, we summarize the role of reported bioactive hydrogels in hemostasis in this review. We conclude the key points in the coagulation process, including activation of coagulation factors, fibrinogen polymerization, etc., then discuss how to design bioactive hydrogels to accelerate coagulation targeted to these points. Finally, we conclude the progress and propose a perspective of bioactive hydrogels with a pro-coagulation effect for hemostasis.

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This review expects to give an overview on macroporous hydrogels prepared by the ice templating, namely, cryogels. Recent progresses on emerging cryo-porogenation methods are introduced. Future opportunities on the application of cryogels are prospected. More importantly, the fundamental understanding concerning the behavior of the polymer chains during the formation of ice is proposed.

Comprehensive Summary

Macroporous hydrogels are water-swollen polymer networks with porous structures beyond the mesh size. They provide high specific surface areas and hieratical mass transfer channels which are desired for emerging applications including cell culturing, bio-separation, and drug delivery. A variety of approaches have been developed to fabricate macroporous hydrogels, including gas foaming, porogen templating, phase separation, 3D printing, etc. Alternatively, ice templating utilizes the crystallization of water as the porogenation mechanism which doesn't need the leaching of porogens. The porous structures can be easily manipulated by controlling the morphology of ice (size, orientation, etc.) upon freezing. In addition, mechanical properties of obtained porous hydrogels are commonly better than those of other macroporous hydrogels since the pore walls are made up of concentrated polymers through the freezing step. These three characteristics, that is, the green process, the highly tunable morphology, and the enhanced mechanical strength make the ice templating a superior porogenation method. This review expects to give an overview on macroporous hydrogels prepared by the ice templating, namely, cryogels. Recent progresses on emerging cryo-porogenation methods are introduced. Fundamental understanding concerning the behavior of the polymer chains during the formation of ice is proposed. Future opportunities on the application of cryogels are prospected.

It's reported that a method using alkali metal bromide (NaBr, KBr, CsBr) as a modification layer was used to prepare a highly efficient and stable FA-based Sn-Pb PSC with NiO _x HTL and the device with CsBr buffer layer achieved an outstanding PCE of 19.48%.

Comprehensive Summary

Formamidinium (FA)-based Sn-Pb perovskite solar cells (FAPb_0.5Sn_0.5I₃ PSCs) with ideal bandgap and impressive thermal stability have caught enormous attention recently. However, it still suffers from the challenge of realizing high efficiency due to the surface imperfections of the transport materials and the energy-level mismatch between functional contacts. Herein, it is demonstrated that the modification on buried interface with alkali metal salts is a viable strategy to alleviate these issues. We systematically investigate the role of three alkali metal bromide salts (NaBr, KBr, CsBr) by burying them between the NiO _x hole transport layer (HTL) and the perovskite light-absorbing layer, which can effectively passivate interface defects, improve energy-level matching and release the internal residual strain in perovskite layers. The device with CsBr buffer layer exhibits the best power conversion efficiency (PCE) approaching 20%, which is one of the highest efficiencies for FA-based Sn-Pb PSCs employing NiO _x HTLs. Impressively, the long-term storage stability of the unencapsulated device is also greatly boosted. Our work provides an efficient strategy to prepare desired FA-based ideal-bandgap Sn-Pb PSCs which could be applied in tandem solar cells.

Pd/Cu-catalyzed denitrogenative self-carbonylation of arylhydrazine hydrochlorides to synthesize symmetrical biaryl ketones under CO/O₂ pressure has been developed. The arylhydrazine hydrochlorides are used as a green arylating agent which releases nitrogen and water as byproducts. This developed protocol significantly restricts the formation of aryl iodide and azobenzene products even under favorable conditions. Additionally, this protocol provides a series of symmetric carbonylative ketones with a wide variety of functional group tolerance under CO/O₂ pressure.

Comprehensive Summary

An efficient Pd/Cu-catalyzed oxidative self-carbonylation of arylhydrazine with CO and molecular oxygen as an oxidant to afford symmetrical biaryl ketones via C—N bond activation has been developed. In this approach, arylhydrazine hydrochlorides are used as a green arylating agent which releases nitrogen and water as byproducts. This developed protocol significantly restricts the formation of aryl iodide and homo-coupled azobenzene products even under favorable conditions. A library of symmetrical biaryl ketones with wide functionalities was synthesized in good yields under mild conditions.

Comprehensive Summary

Exploring the physiochemical properties and expanding the applications of actinide-containing materials is paramount to address the escalating challenge of radioactive waste accumulation. However, unlocking the full potential of these materials is largely crippled by the radiotoxicity of the actinides. We report here two porous and luminescent thorium-based metal-organic frameworks (Th-BITD-1 and Th-BITD-2) that serve as a bifunctional platform for sequencing and sensing of radioiodine, a much more radioactive fission product discharged during the nuclear fuel reprocessing. In particular, the resulting Th-BITD-1 displays better iodine uptake performance than Th-BITD-2 via the solution-based process and vapor diffusion with the maximum adsorption capacities of 831 and 1099 mg/g, respectively. Furthermore, Th-BITD-1 can function as a highly sensitive luminescence sensor for iodate with a quenching constant (K_SV) of 6.6(5)×10³ M⁻¹ and a detection limit of 2.02 μM, respectively, outperforming 2.96(6) ×10³ M⁻¹ and 10.5 μM of Th-BITD-2. Moreover, a positive correlation between the sensing efficacy and the iodate adsorption capacity has been revealed. This work highlights the opportunity in designing novel actinide-based MOFs for their potential applications in radiological fields, e.g., radionuclide separation and detection.

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Comprehensive Summary

With the increasing demand for homoallylic silanes and allylic silanes, the highly efficient and regioselective hydrosilylations of conjugated dienes are urgently needed. Herein, we developed a Ni-catalyzed regiodivergent hydrosilylation of aromatic conjugated dienes by adjusting the temperature and ligands. Under low temperature (-30 ^oC), an eternal-ligand-free system (Ni/t-BuOK) can efficiently facilitate the 3,4-anti-Markovnikov hydrosilylation to provide homoallylic silanes via electrophilic activation process; under room temperature (25 ^oC), a ligand-controlled system (Ni/t-BuOK/PPh₃) can eventuate the 3,4-Markovnikov hydrosilylation to produce allylic silanes via Chalk-Harrod process. Both systems are compatible with various conjugated dienes and primary silanes in excellent yields and regioselectivities.

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The dumbbell-like Au-Pd bimetallic nanomaterials (Au NRs-Pd@HA) were obtained by reducing palladium on gold nanorods with ascorbic acid (AA) and further modified with hyaluronic acid (HA). Au NRs-Pd@HA can induce catalytic conversion of glucose to generate H₂O₂ efficiently, and subsequently undergo cascade reaction to produce abundant ·OH radicals, exhibiting peroxidase-like (POD-like) and glucose oxidase-like (GOD-like) capabilities. The generated ·OH was a key factor for tumor ablation. Meanwhile, Au NRs-Pd@HA exhibit good photothermal performance under 808 nm irradiation, in favor of photothermal therapy (PTT). Especially, the POD-like and GOD-like activities were significantly enhanced due to the photothermal effect. The synergistic PTT and photothermal-enhanced nanozymes with cascade catalytic effect enabled efficient and safe cancer therapy.

Comprehensive Summary

Based on characteristics of the tumor microenvironment (TME), including acidity, hypoxia, inflammation and hydrogen peroxide overload, combined with emerging nanotechnologies, designing nanoplatforms with TME specificity/responsiveness for tumor treatment is a promising nanotherapeutic strategy. In this work, a multifunctional gold-palladium bimetallic cascade nanozyme was constructed for effective photothermal-enhanced cascade catalyzed synergistic therapy of tumors. The dumbbell-like Au-Pd bimetallic nanomaterial (Au NRs-Pd@HA) was obtained by reducing palladium on gold nanorods with ascorbic acid (AA) and further modified with hyaluronic acid (HA). The introduction of HA brings biocompatibility and targeting properties. The zebrafish embryos model showed that Au NRs-Pd@HA had good biocompatibility and low biotoxicity. Au NRs-Pd@HA can induce catalytic conversion of glucose to generate H₂O₂ efficiently, and subsequently undergo cascade reaction to produce abundant ·OH radicals, exhibiting peroxidase-like (POD-like) and glucose oxidase-like (GOD-like) capabilities. The generated ·OH was a key factor for tumor ablation. Meanwhile, Au NRs-Pd@HA exhibits good photothermal performance under 808 nm irradiation, in favor of photothermal therapy (PTT). Especially, the POD-like and GOD-like activities were significantly enhanced due to the photothermal effect. The synergistic PTT and photothermal-enhanced nanozymes with cascade catalytic effect enabled efficient and safe cancer therapy.

Comprehensive Summary

Knowledge of asymmetric catalytic reaction mechanism is very important for rational design and synthesis of new chiral catalysts or catalytic systems with high catalytic activity and stereoselectivity. The studies of nonlinear effect have attracted wide attentions as a simple and practical mechanistic tool to probe complex asymmetric catalytic reactions. This review documents the application of the study of nonlinear effects on how to reveal the mechanism in asymmetric catalytic reactions that were catalyzed by the first-row transition-metals in the last decade and gives a brief discussion on the different models of nonlinear effect.