Fine-Tuning Alkyl Chains on Quinoxaline Nonfullerene Acceptors Enables High-Efficiency Ternary Organic Solar Cells with Optimizing Molecular Stacking and Reducing Energy Loss

Material design of guest acceptor is always a big challenge for improving the efficiency of ternary organic solar cells (OSCs). Here, a pair of isomeric nonfullerene acceptors based on quinoxaline core, Qx–p-C₇H₈O and Qx–m-C₇H₈O, is designed and synthesized. By moving the alkoxy chain attached on side phenyl from meta-position to para-position, both π–π stacking distance and crystallinity are enhanced simultaneously. They obtain the uplifted lowest unoccupied molecular orbital level. Compared to Qx–m-C₇H₈O, Qx–p-C₇H₈O exhibits wider absorption spectrum and higher extinction coefficient. Using D18-Cl:N3 as host materials, the addition of guest acceptor Qx–p-C₇H₈O significantly improves the power conversion efficiency (PCE) from 17.61% to 18.49% because of higher open-circuit voltage (0.875 V) and short-circuit current density (27.85 mA cm⁻²). This can be attributed to the faster exciton dissociation, more balanced carrier mobility, fine fiber morphology, and lower energy loss in the ternary devices. However, Qx–m-C₇H₈O-based ternary device achieves relatively low PCE of 17.17% because this device shows extremely low electron mobility. The results indicate that molecular stacking, film morphology, etc., can be effectively modulated by fine-tuning the side chains of guest materials, which may be an effective design rule for further improving the PCE of OSCs.     

19.28% Efficiency and Stable Polymer Solar Cells Enabled by Introducing an NIR-Absorbing Guest Acceptor

Here, a near-infrared (NIR)-absorbing small-molecule acceptor (SMA) Y-SeNF with strong intermolecular interaction and crystallinity is developed by combining selenophene-fused core with naphthalene-containing end-group, and then as a custom-tailor guest acceptor is incorporated into the binary PM6:L8-BO host system. Y-SeNF shows a 65 nm red-shifted absorption compared to L8-BO. Thanks to the strong crystallinity and intermolecular interaction of Y-SeNF, the morphology of PM6:L8-BO:Y-SeNF can be precisely regulated by introducing Y-SeNF, achieving improved charge-transporting and suppressed non-radiative energy loss. Consequently, ternary polymer solar cells (PSCs) offer an impressive device efficiency of 19.28% with both high photovoltage (0.873 V) and photocurrent (27.88 mA cm⁻²), which is one of the highest efficiencies in reported single-junction PSCs. Notably, ternary PSC has excellent stability under maximum-power-point tracking for even over 200 h, which is better than its parental binary devices. The study provides a novel strategy to construct NIR-absorbing SMA for efficient and stable PSCs toward practical applications.     

Femtosecond Laser 4D Printing of Light-Driven Intelligent Micromachines

Intelligent micromachines that respond to external light stimuli have a broad range of potential applications, such as microbots, biomedicine, and adaptive optics. However, artificial light-driven intelligent micromachines with a low actuation threshold, rapid responsiveness, and designable and precise 3D transformation capability remain unachievable to date. Here, a single-material and one-step 4D printing strategy are proposed to enable the nanomanufacturing of agile and low-threshold light-driven 3D micromachines with programmable shape-morphing characteristics. The as-developed carbon nanotube-doped composite hydrogel simultaneously enhanced the light absorption, thermal conductivity, and mechanical modulus of the crosslinked network, thus significantly increasing the light sensitivity and response speed of micromachines. Moreover, the structural design and assembly of asymmetric microscale mechanical metamaterial unit cells enable the highly efficient additive nanomanufacturing of 3D shape-morphable micromachines with large dynamic modulation and spatiotemporal controllability. Using this strategy, the world's smallest artificial beating heart with programmable light-stimulus responsiveness for the cardiac cycle is successfully printed. This 4D printing method paves the way for the construction of multifunctional intelligent micromachines for bionics, drug delivery, integrated microsystems, and other fields.     

Hybrid Catalyst Coupling Zn Single Atoms and CuNx Clusters for Synergetic Catalytic Reduction of CO2

Reverse water-gas shift (RWGS) reaction is the initial and necessary step of CO₂ hydrogenation to high value-added products, and regulating the selectivity of CO is still a fundamental challenge. In the present study, an efficient catalyst (CuZnN_x@C-N) composed by Zn single atoms and Cu clusters stabilized by nitrogen sites is reported. It contains saturated four-coordinate Zn-N₄ sites and low valence CuN_x clusters. Monodisperse Zn induces the aggregation of pyridinic N to form Zn-N₄ and N₄ structures, which show strong Lewis basicity and has strong adsorption for *CO₂ and *COOH intermediates, but weak adsorption for *CO, thus greatly improves the CO₂ conversion and CO selectivity. The catalyst calcined at 700 °C exhibits the highest CO₂ conversion of 43.6% under atmospheric pressure, which is 18.33 times of Cu-ZnO and close to the thermodynamic equilibrium conversion rate (49.9%) of CO₂. In the catalytic process, CuN_x not only adsorbs and activates H₂, but also cooperates with the adjacent Zn-N₄ and N₄ structures to jointly activate CO₂ molecules and further promotes the hydrogenation of CO₂. This synergistic mechanism will provide new insights for developing efficient hydrogenation catalysts.     

Breaking the Responsivity-Bandwidth Trade-Off Limit in GaN Photoelectrodes for High-Response and Fast-Speed Optical Communication Application

Underwater optical communication (UOC) has attracted considerable interest in the continuous expansion of human activities in marine/ocean environments. The water-durable and self-powered photoelectrodes that act as a battery-free light receiver in UOC are particularly crucial, as they may directly face complex underwater conditions. Emerging photoelectrochemical (PEC)-type photodetectors are appealing owing to their intrinsic aqueous operation characteristics with versatile tunability of photoresponses. Herein, a self-powered PEC photodetector employing n-type gallium nitride (GaN) nanowires as a photoelectrode, which is decorated with an iridium oxide (IrO_x) layer to optimize charge transfer dynamics at the GaN/electrolyte interface, is reported. Strikingly, the constructed n-GaN/IrO_x photoelectrode breaks the responsivity-bandwidth trade-off limit by simultaneously improving the response speed and responsivity, delivering an ultrafast response speed with response/recovery times of only 2 µs/4 µs while achieving a high responsivity of 110.1 mA W⁻¹. Importantly, the device exhibits a large bandwidth with 3 dB cutoff frequency exceeding 100 kHz in UOC tests, which is one of the highest values among self-powered photodetectors employed in optical communication system.     

Pre-Activation of CO2 at Cobalt Phthalocyanine-Mg(OH)2 Interface for Enhanced Turnover Rate

Cobalt phthalocyanine (CoPc) anchored on heterogeneous scaffold has drawn great attention as promising electrocatalyst for carbon dioxide reduction reaction (CO₂RR), but the molecule/substrate interaction is still pending for clarification and optimization to maximize the reaction kinetics. Herein, a CO₂RR catalyst is fabricated by affixing CoPc onto the Mg(OH)₂ substrate primed with conductive carbon, demonstrating an ultra-low overpotential of 0.31 ± 0.03 V at 100 mA cm⁻² and high faradaic efficiency of >95% at a wide current density range for CO production, as well as a heavy-duty operation at 100 mA cm⁻² for more than 50 h in a membrane electrode assembly. Mechanistic investigations employing in situ Raman and attenuated total reflection surface-enhanced infrared absorption spectroscopy unravel that Mg(OH)₂ plays a pivotal role to enhance the CO₂RR kinetics by facilitating the first-step electron transfer to form anionic *CO₂⁻ intermediates. DFT calculations further elucidate that introducing Lewis acid sites help to polarize CO₂ molecules absorbed at the metal centers of CoPc and consequently lower the activation barrier. This work signifies the tailoring of catalyst-support interface at molecular level for enhancing the turnover rate of CO₂RR.     

Multifunctional Organic Potassium Salt Additives as the Efficient Defect Passivator for High-Efficiency and Stable Perovskite Solar Cells

Despite the rapid developments are achieved for perovskite solar cells (PSCs), the existence of various defects in the devices still limits the further enhancement of the power conversion efficiency (PCE) and the long-term stability of devices. Herein, the efficient organic potassium salt (OPS) of para-halogenated phenyl trifluoroborates is presented as the precursor additives to improve the performance of PSCs. Studies have shown that the 4-chlorophenyltrifluoroborate potassium salt (4-ClPTFBK) exhibits the most effective interaction with the perovskite lattice. Strong coordination between  BF₃⁻/halogen in anion and uncoordinated Pb²⁺/halide vacancies, along with the hydrogen bond between F in  BF₃⁻ and H in FA⁺ are observed. Thus, due to the synergistic contribution of the potassium and anionic groups, the high-quality perovskite film with large grain size and low defect density is achieved. As a result, the optimal devices show an enhanced efficiency of 24.50%, much higher than that of the control device (22.63%). Furthermore, the unencapsulated devices present remarkable thermal and long-term stability, maintaining 86% of the initial PCE after thermal test at 80 °C for 1000 h and 95% after storage in the air for 2460 h.     

Macrophage Membrane-Coated Nanoparticles Sensitize Glioblastoma to Radiation by Suppressing Proneural–Mesenchymal Transformation in Glioma Stem Cells

Radiotherapy is identified as a crucial treatment for patients with glioblastoma, but recurrence is inevitable. The efficacy of radiotherapy is severely hampered partially due to the tumor evolution. Growing evidence suggests that proneural glioma stem cells can acquire mesenchymal features coupled with increased radioresistance. Thus, a better understanding of mechanisms underlying tumor subclonal evolution may develop new strategies. Herein, data highlighting a positive correlation between the accumulation of macrophage in the glioblastoma microenvironment after irradiation and mesenchymal transdifferentiation in glioblastoma are presented. Mechanistically, elevated production of inflammatory cytokines released by macrophages promotes mesenchymal transition in an NF-κB-dependent manner. Hence, rationally designed macrophage membrane-coated porous mesoporous silica nanoparticles (MMNs) in which therapeutic anti-NF-κB peptides are loaded for enhancing radiotherapy of glioblastoma are constructed. The combination of MMNs and fractionated irradiation results in the blockage of tumor evolution and therapy resistance in glioblastoma-bearing mice. Intriguingly, the macrophage invasion across the blood-brain barrier is inhibited competitively by MMNs, suggesting that these nanoparticles can fundamentally halt the evolution of radioresistant clones. Taken together, the biomimetic MMNs represent a promising strategy that prevents mesenchymal transition and improves therapeutic response to irradiation as well as overall survival in patients with glioblastoma.     

Creating Atomic Ordering in Electrocatalysis

Catalysis always proceeds in a chaotic fashion. Therefore, identifying the working principles of heterogeneous catalysts is a challenging task. Creating atomic order in heterogeneous catalysts simplifies this task and also offers new opportunities for rationally designing active sites to manipulate catalytic performance. The recent rapid advances in heterogeneous electrocatalysis have led to exciting progress in the construction of atomically ordered materials. Here, the latest progress in electrocatalysts with the periodic atomic arrangement, including intermetallic compounds with long-range order and metal atom-array catalysts with short-range order is summarized. The synthesis principles and the intriguing physical and chemical properties of these electrocatalysts are discussed. Furthermore, the compelling prospects of atomically ordered catalysts in the frontier of catalyst research are outlined.     

Self-Mineralizing Dnazyme Hydrogel as a Multifaceted Bone Microenvironment Amendment for Promoting Osteogenesis in Osteoporosis

The accumulation of reactive oxygen species (ROS) and minimal osteogenic raw material in the osteoporotic bone microenvironment greatly inhibits the activity of osteoblasts. Herein, it is originally proposed to construct a biomatrix multifaceted bone microenvironment amendment -Mineralized zippered G4-Hemin DNAzyme hydrogel (MDH)-to improve osteoporotic osteogenic capacity and promote high-quality bone defect repair. The programmed design of the rolling circle amplified DNA hydrogel synthesis system allows the introduction of massive amounts of zippered G4-Hemin DNAzyme in MDH. The zippered G4-Hemin DNAzyme highly mimics the tight catalytic configuration of horseradish peroxidase and exerts excellent enzyme-like activity with considerable ROS molecule scavenging ability. In addition, the DNA amplification by-product pyrophosphate is ingeniously employed as a sufficient phosphorus source, thus constituting an autonomous mineralization system for waste reuse through the introduction of pyrophosphate hydrolase and calcium ions, which deposits in MDH as an osteogenic raw material and addresses the challenge of DNA hydrogel bio-application stability. The remarkable in vitro and in vivo outcomes demonstrate that MDH can effectively improve the oxidative stress status of osteoblasts, restore the balance of mitochondrial membrane potential, and reduce apoptosis, ultimately demonstrating superior osteogenic capacity.