Advanced Functional Materials

Inspired by biological mechanisms of impact protection, nanocellulose and linear polyurethane molecular chains are simultaneously tailored and expanded using supramolecular chemistry. This approach has led to the development of a novel impact protection strategy that leverages multilevel hydrogen bonding interactions. These abundant interactions effectively hinder the crystallization of polycaprolactone (PCL) chain segments, resulting in uniformly distributed microphase separation. This configuration achieves a significant fracture strength of 47.5 MPa, while maintaining an exceptional elongation at a break of 974.2%. The results demonstrate that supramolecular polyurethane‐cellulose nanofiber (SPU‐CNF) elastomer significantly reduces impact force and extends the impact buffer time. Crucially, the underlying mechanisms responsible for energy dissipation and impact protection in SPU‐CNF are elucidated. To validate these properties, impact protection tests at varying impact rates are conducted, underscoring the potential applications of the proposed SPU‐CNF in impact‐resistant materials.

A bioglue with fast blood absorption and strong adhesion, capable of stopping bleeding through physical blockage rather than coagulation, is imperative for treating arterial hematorrhea during surgery and in wilderness first aid. Here, we developed a two‐component polyurethane‐based arterial glue (PAG). The key strategy of this work is to optimize the hydrophilicity and crosslinking density of the bioglue by modulating the proportion of hydrophilic polyethylene glycol (PEG)‐based urethane prepolymer, the hydrophobicamine crosslinkers, and the functionality of the crosslinkers. Compared with commercial PEG‐based bioglue, PAG has a similar water absorption rate but less swelling. Furthermore, owing to the hydrogen bonding originating from the urethane/urea bonds and extracovalent bond formation with tissue, PAG showed ≈2 times greater adhesive strength than commercial PEG‐based bioglues. In addition, PAG has good hemocompatibility and maintains cured integrity even under circulating blood flushing conditions, thereby reducing the risk of arterial embolism. This bioglue demonstrated a more reliable sealing effect with a higher survival rate compared to commercial fibrin and PEG‐based bioglues on the rat abdominal aorta and rabbit carotid artery in open operations; moreover, it can be assembled into a commercial balloon dilation catheter system, enabling minimally invasive surgeries on the porcine femoral artery.

Carbon nanotubes (CNTs) are promising candidates for photodetectors due to their excellent electrical and optical properties. However, the strong binding energy of excitons, structural defects, and short lengths of CNTs seriously limited the full utilization of the inherently extraordinary properties of CNTs in photodetector construction. Herein, a new strategy is designed for fabricating high‐performance VIS and NIR photodetectors based on suspended ultralong CNTs‐MoS2 heterojunction networks. The MoS2 layers are directly grown on suspended ultralong CNT bundles (s‐UCNTBs). The suspended and defect‐free structures of s‐UCNTBs ensure rapid heat dissipation and perfectly avoid the electron‐phonon interactions from substrates. The interfaces between s‐UCNTBs and MoS2 effectively improve the generation and transport of photogenerated carriers, thus remarkably enhancing the photodetection performance of s‐UCNTBs‐MoS2 networks. The s‐UCNTBs‐MoS2 networks‐based photodetectors exhibit a high responsivity (8.51 A W⁻¹), a high detectivity (3.74 × 10¹¹ cm Hz1/2 W⁻¹), an ultrafast response speed (30 µs/40 µs for response/decay), and a broad detection range (405–1064 nm), far outperforming the most reported carbon materials‐based photodetectors. Moreover, the s‐UCNTBs‐MoS2 photodetector exhibits good structural and performance stability after being kept in ambient conditions for more than 200 days. This work provides a reliable way to construct high‐performance CNTs‐based devices via structural design.

Sneak‐path current is one of the biggest barriers for large‐scale passive memristor array integration. An ideal self‐rectifying resistance random access memory (SR‐RRAM) is a desirable solution but it has not been demonstrated today for optimizing comprehensive indexes for neuromorphic computing. The HfOx/FeOx semiconductor heterojunction SR‐RRAM with a robust self‐rectifying switching behavior featured by an average rectifying ratio (≈10⁴), high resistance ratio (>10⁶), high cycling endurance (>10⁴ cycles), high computing precision (>6 bits) and synaptic plasticity such as paired‐pulse facilitation (PPF) and the spike‐timing‐dependent plasticity (STDP) for artificial intelligence recognition is developed using the unidirectional conductivity feature of p‐n junction. The electron hopping, tunneling, and blocking in this semiconductor heterojunction that is verified by the energy band mode based on UV photoelectron spectroscopy (UPS) technology and low‐energy inverse photoelectron spectroscopy (LEIPS) and in situ high resolution transmission electron microscopy (HR‐TEM) observation plays a dominant role in the self‐rectifying analog switching behaviors. This work provides energy‐band engineering for the large‐scale memristor array integration, representing a significant advancement in hardware for neuromorphic computing.

Metallic materials serving as indispensable conductors critically influence the performance of flexible electronics. Conventional structural designs have restricted metallic materials to exhibiting pure elastic deformation, but recent developments have emphasized an increased significance of plastic deformation, showing great potential for new breakthroughs in developing novel flexible electronics. This review first introduces the elastoplastic behavior of metallic materials, especially those capable of withstanding remarkable plastic deformation. The main design strategies toward flexible and stretchable electronics expanding elastic deformation range are then summarized, incorporating both strain alleviation and strain delocalization. Innovative studies exploiting plasticity for enhancing device performances or achieving shape‐forming and reconfigurable electronics are further highlighted. Some perspectives on utilizing the elastoplastic behavior of metallic materials to innovate the next generation of flexible electronics are finally provided.

Human skin provides crucial tactile feedback, allowing to skillfully perceive various objects by sensing and encoding complex deformations through multiple parameters in each tactile receptor. However, replicating this high‐dimensional tactile perception with conventional materials' electronic properties remains a daunting challenge. Here, a skin‐inspired method is presented to encode strain vectors directly within a sensor. This is achieved by leveraging the strain‐tunable quantum properties of electronic bands in the van der Waals topological semimetal Td‐WTe2. Robust and independent responses are observed from the second‐order and third‐order nonlinear Hall signals in Td‐WTe2 when subjected to variations in both the magnitude and direction of strain. Through rigorous temperature‐dependent measurements and scaling law analysis, it is established that these strain responses primarily stem from quantum geometry‐related phenomena, including the Berry curvature and Berry‐connection polarizability tensor. Furthermore, the study demonstrates that strain‐dependent nonlinear Hall signals can efficiently encode high‐dimensional strain information using a single device. This capability enables accurate and comprehensive sensing of complex strain patterns in the embossed character “NJU”. The findings highlight the promising application of topological quantum materials in advancing next‐generation, bio‐inspired flexible electronics.

Flexible electronics with sophisticated 3D architectures enable multidimensional functionalities and multi‐component integration, thus surpassing their 2D counterparts in soft robotics and wearable sensors. Because of its unique metallic and fluidic characteristics, liquid metal (LM) has proven to be an excellent material for fabricating flexible electronics. However, its low viscosity and high surface tension have primarily restricted LM to the creation of 2D‐patterned films on flat surfaces, significantly limiting the complexity and functionality of the resulting flexible devices. In this work, inspired by the capillary‐driven liquid flow in a hierarchical lattice matrix, a 3D patterning method is proposed for LM and extended to the fabrication of porous materials with flexible conductivity. The feasibility and versatility of the proposed method are showcased by fabricating tunable electromagnetic interference shielding materials, programmable 3D circuits, and customizable wearable sensors, highlighting its potential for promoting the development of integrated circuits and wearable electronics.

Owing to the superior stimulus perception, tactile function of skin is always the desire of flexible pressure sensor array (FPSA). However, achieving sensor arrays with high sensitivity and high resolution for tactile recognition like skin still remains a challenge. In this paper, an FPSA with high sensitivity (10.50 kPa⁻¹), high density (1134.63 cm⁻²), and sufficient sensing units (4096 units) is developed, which is one of the best results up to now. The spinous microstructures, transferring from the abrasive papers, endow the sensor array with high sensitivity. Additionally, the high density array with adequate sensing units contributes to achieving high spatial resolution for identifying various surface features. This high‐performance FPSA can obtain detailed pressure distribution for complex carved patterns. With the assistance of machine learning, the FPSA can realize precise tactile recognition, 98.48% accuracy for 12 types of mahjong tiles, indicating a promising potential in an intelligent recognition system. It is worth noting that the relationship between surface microstructures and consistency is systematically investigated for the first time, which offers valuable insights for the preparation of high‐performance sensor arrays.

Photocatalytic reactive oxygen species (ROSs) plays an important role in photodynamic therapy and photochemical reactions. However, most reported photocatalysts suffer from insufficient utilization of visible light and low conversion of O2, which requires the development of higher performance catalysts toward practical applications. Herein, a series of porphyrin‐based COFs have been prepared. Comparative experimental and theoretical studies have revealed that the synergistic interaction between the two building blocks can significantly enhance the yields of ROSs by independently accomplishing photon harvesting and oxygen capture with smooth energy transfer between them. Particularly, the ¹O2 yield of 3P‐Por‐COF is increased to 1.3 and 3.4 times that of the classical PCN‐224 and porphyrin molecular aggregates. Furthermore, the TOF of 3P‐Por‐COF is as high as 271 h⁻¹ with ≈100% selectivity under red light irradiation in catalyzing thioanisole to methyl phenyl sulfoxide. The conversion and stability of degradation of toluene gas under natural light are also superior to the conventional Fenton catalytic system. The present results should contribute to the design of high‐performance frameworks‐based photocatalysts for ROSs production.

Phototoxicity poses a substantial challenge in photodynamic therapy, resulting in intolerable skin damage, visual impairment, and reduced quality of life. Current coping strategies, primarily focus on avoiding inappropriate photoactivation and developing targeted photosensitizers, have not effectively addressed this problem. Hence, this study aims to develop a “sunlight‐friendly” photodynamic therapy strategy. Here, 1‐methoxyphenazine methosulfate (MPMS) is innovatively identified as a key substance in achieving modified oxygen metabolism. MPMS demonstrates efficient catalytic shuttling under abnormal intracellular H2O2 levels, introducing a novel protective approach for oxygen metabolism and numerous life processes. By controlling MPMS administration, the switch of the photosensitizer states between “ON” (killing tumor cells) and “OFF” (safeguarding normal cells) can be achieved. This approach effectively mitigated phototoxicity and holds the potential for widespread clinical application.

Thermoelectric materials, as key materials for realizing efficient conversion of thermal and electrical energy, are crucial for renewable energy utilization and efficient energy management. However, materials with high negative thermoelectric coefficients are relatively rare. Herein, inspired by the structure and function of plant stem which is capable of blocking heavy metal ions, chitosan/CuCl2 hydrogel (ChCu) with a huge negative thermoelectric coefficient is reported. The ChCu displayed lamellar porous structure, which is constructed synergistically by freeze‐casting technique and complexation between Cu²⁺ and chitosan. In a ChCu hydrogel subjected to a temperature gradient, most of the Cu²⁺ is immobilized within the chitosan matrix by complexation, while the thermal migration of the unbound Cu²⁺ is further intercepted by the special layered porous structure. On the contrary, Cl⁻ migrates unhindered to the cold end and accumulates, which realizes selective migration and distribution of ion/counterion. As a result, ChCu exhibits a thermoelectric coefficient as high as ‐23.8 mV K⁻¹, and can respond rapidly with a thermal voltage of 4.0 mV under a small temperature difference (ΔT = 0.3 K). This work reveals the significant influence of the polymer aggregate structure on the thermal diffusion of ions, providing an innovative strategy in designating thermoelectric materials with high‐performance, high‐efficiency and environmentally friendly.

2D architectures and superior physiochemical properties of MXene offer an exciting opportunity to develop a new class of polymer electrolyte membranes by controlling the stacking behavior of MXene nanosheets. However, assembling MXene nanosheets into macroscopic stable and high‐performance proton conductors is challenging. Here, a general strategy is reported for achieving stable and high‐performance MXene‐based heterogeneous proton conductors via crosslinked cellulose nanofiber/sodium alginate (CNF/SA). Through the coordination of calcium ions with 1D CNF/SA, MXene nanosheets with abundant hydrogen‐bonding networks are firmly locked into the heterogeneous polymer network, and meanwhile, the heterogeneous polymer chains are transformed from a randomly arranged state to a long‐range ordered arrangement, and such arranged polymer molecular channels collaborate with the tightly‐stacked MXene nanosheets jointly guide the stable and efficient proton conduction. Thus, the as‐built CNF/SA/MXene (CSM) composite membrane exhibits superior mechanical properties (164.7 MPa), proton conductivity (45.4 mS cm⁻¹), power density (49.5 mW cm⁻²), and low open circuit voltage (OCV) decay rate (0.4 mV h⁻¹). The design principle of 2D material anchoring through ionic‐cross‐linking and mixed‐dimensional assembly can inspire the synthesis of various ion exchange membranes for ion filtration, ion transport, ion sieving, and more.

The hard carbon (HC) anodes with desirable electrochemical performances including high initial Coulombic efficiency, superior rate performance and long‐term cycling play an indispensable role in the practical application of sodium ion batteries (SIBs), which are closely related to the electrolytes them matched. Fully analyzing the mechanism of electrolyte engineering for HC anodes is crucial for promoting the commercialization of SIBs, but is still lacking. In this review, the correlation between physicochemical properties of the electrolyte and the electrochemical performance of HC is first summarized. And point out the crucial role of electrolyte properties, including ion conductivity, de‐solvation energy, and interface passivation ability for the Na⁺ storage in HC. Then, the formation process, composition, as well as structure of solid electrolyte interphase (SEI) on HC surface are mainly discussed, and the structure‐activity relationship of SEI is analyzed in depth. Moreover, based on the mechanism analysis, relevant electrolyte design strategies have been summarized. Finally, the challenges and future development directions of the electrolyte engineering of HC are proposed. This review is expected to provide professional theoretical guidance for the development of electrolyte and contribute to the rational design of high‐performance HC anodes, promoting the industrialization of SIBs.

The advancement of aqueous zinc‐ion batteries (AZIBs) faces significant obstacles due to the typically loose and unstable solid electrolyte interphase (SEI), which fosters dendrite formation and undermines cycling performance, especially in cold environments. Here, a quasi‐high‐entropy solid electrolyte interphase (QHE‐SEI) formulated is introduced with diverse and functional inorganic compounds, achieved through the incorporation of dual salts and a blend of solvents. Shielded by the QHE‐SEI, AZIBs exhibit uniform zinc deposition and attain remarkable cycling stability, enduring for 1300 h in Zn||Zn symmetric cells under conditions of 3 mA cm⁻² and 3 mAh cm⁻² at room temperature. Furthermore, the full cell maintains over 4300 cycles at −20 °C with nearly full capacity retention. Notably, the pouch cell maintains a high capacity of ≈25 mAh across 50 cycles, even at −20 °C. This study offers a novel approach to designing a stable SEI and elevates the performance of AZIBs.

Developing multifunctional construction materials with advanced functionalities and excellent mechanical toughness remains a significant challenge within the field of civil engineering. Herein, a scalable and cost‐effective approach for fabricating versatile cement‐based composites is introduced. This is achieved by pre‐embedding a 3D‐printed conductive lattice framework (LF) into cement pastes with the incorporation of carbon black (CB). LFs contribute significantly to the flexural extension of the composite structure and when combined with CB, they substantially improve the conductivity of the matrix, enabling its self‐sensing applications. Moreover, the obtained conductivity enables the application of electrochemical deposition techniques for in situ polymerization and deposition of polypyrrole (PPy) onto the composite surface. PPy coatings further endow the cement‐based composites with excellent electrothermal and electrochemical performance. For instance, applying a direct current voltage of 18 V for 10 min results in a temperature increase exceeding 45 °C, indicating promising de‐icing capabilities. When assembled as a supercapacitor, it exhibits an outstanding energy density, reaching 61.7 µWh cm⁻² at a power density of 150 µW cm⁻² and demonstrating its potential for energy storage application in the construction sector. In conclusion, this study introduces an innovative strategy for the advancement of intelligent and multifunctional cement‐based construction materials, emphasizing the importance of multifunctionality in modern construction practices.

Self‐assembled monolayers (SAMs) have significantly improved the device performance of inverted perovskite solar cells (PSCs). However, the inadequate chemical bonding affinity between SAMs and the substrate as well as the uneven SAM distribution can lead to the decrease in device performance. Herein, the study reports a bilayer NiOx hole transport layer (HTL), consisting of ultrathin NiOx buffer film prepared through atomic layer deposition (ALD‐NiOx) and spin‐coated NiOx film (Spin‐NiOx). The work function difference between the two NiOx films will facilitate the hole transfer from the ALD‐NiOx to the Spin‐NiOx in the ALD‐NiOx/Spin‐NiOx bilayer structure. These holes will undergo surface hydroxylation reactions with water molecules on the Spin‐NiOx film surface, generating additional hydroxyl groups covalently bonded to the Spin‐NiOx film, which can provide more anchoring sites for SAM molecules. Stable covalent bonds can be formed between the Spin‐NiOx film and the subsequently coated SAM film. As a result, SAM films with better coverage and molecular arrangement can be obtained. The ALD‐NiOx/Spin‐NiOx/SAM composite HTL also demonstrates superior charge transport capability and thermal stability. For small area PSCs (0.06 cm²) prepared by using the composite HTL, a champion power conversion efficiency (PCE) of 25.25% is achieved, and the device stabilities are also significantly improved.

Nanoscale redox‐active molecular films are promising candidates for next‐generation energy storage applications due to their ability to facilitate long‐range charge transport. However, establishing stable and efficient electrode‐molecule interfaces remains a critical challenge. In this study, the properties of redox‐active copper‐polypyridyl thin films covalently bonded to graphite rods are explored, investigating their potential as supercapacitors. Using an electrochemical grafting method, robust covalent interfaces are created, resulting in copper‐polypyridyl films prepared on graphite rods and indium tin oxide (ITO) electrodes, exhibiting both Cu(II) and Cu(I) redox states. These redox‐active mettalo‐oligomeric films demonstrate a structural transition between octahedral and tetrahedral geometries around the Cu(II), and Cu(I), respectively contributing to their charge storage capabilities. The combination of an electrical double‐layer capacitance and pseudocapacitance through Faradaic charge transfer is evaluated in different acidic electrolytes, showing significant capacitance enhancement. Notably, proton‐coupled electron transfer (PCET) at free pyridine‐N sites in Cu(I) polypyridyl complex is identified as a key factor in their distinct behavior in aqueous solutions, a finding supported by computational studies. This study shows the potential of binder‐free thin films for efficient supercapacitor applications, with a maximum areal capacitance of 6.8 mF cm⁻² in aqueous media, representing an 1840% improvement over bare graphite rods.

To achieve ultra‐high gain deep‐ultraviolet (DUV) detectors based on ultra‐wide bandgap semiconductors comparable with those of bulky photomultiplier tubes (PMTs), avalanche photodiodes have usually been adopted. However, the high‐operation voltage (∼100 V) is not compatible with monolithic integration. Herein, it is demonstrated that the ultra‐high gain DUV photodetectors (PDs) with low operation voltages (<5 V) can be achieved by using the synergistic effect of surface states and deep defects in a type‐Ib single‐crystal diamond (SCD) substrate. The overall photoresponse, such as the sensitivity, dark current, spectral selectivity, and response speed, of the diamond DUV‐PDs can be simply tailored by the surface hydrogen or oxygen termination of the SCD substrate. The DUV responsivity and external quantum efficiency are more than 2.5 × 10⁴A/W and 1.4 × 10⁷%, respectively, at 220 nm‐wavelength light, comparable with those of PMTs. The DUV/visible light rejection ratio (R220 nm/R400 nm) is as high as 6.7 × 10⁵. The depletion of the 2D hole gas by deep nitrogen defect provides a low dark current and the filling of the ionized nitrogen upon DUV illumination induces a huge photocurrent. The synergistic effect of the surface states and the bulk deep defects opens the avenue for the development of DUV detectors compatible with integrated circuits.

Designing mechanical metamaterials to control wave propagation often requires extensive finite element analysis and discrete Fourier transform simulations before fabricating 3D printed structures and conducting experiments. Here, an alternative approach is presented to developing a metamaterial informatics framework by integrating dataset collection with artificial intelligence (AI), which can significantly accelerate the advancement of phononic wave chip technologies based on the triply periodic minimal surface (TPMS). Visualized data analysis is performed to evaluate the sensitivity of phononic band frequency numbers (BNF). Subsequently, various machine learning algorithms are compared for the prediction of sonic BNFs to create a unique identificable encoded mechanical identification tag (EMIT) interacting with sound waves. Then, for the mechanical decoding part with the help of acoustic analogy, a novel concept technology is developed that integrates 3D‐printed EMITs with a deep‐learning audio classifier for the ownership identification of instruments. Underwater application is discussed further for civil accident investigations, such as echolocating missing aircraft, divers, sunken ships, and containers with valuable cargo. These TPMS‐based EMITs represent the first‐generation passive sonic frequency identification (SFID) transponder‐tags, marking the advent of SFID transponder systems.

Phase transition materials have the potential to be utilized as high‐resolution temperature‐sensitive materials. However, it is a challenge to develop them into temperature sensors with good stability and repeatability. In this work, inspired by phase transition theory and the electrical double‐layer capacitance principle, a novel high‐resolution flexible capacitive temperature sensor based on Polyethylene oxide(PEO)/Poly(vinylidene fluoride‐co‐hexafluoropropylene)/H3PO4 is proposed for the first time. By blending high and low molecular weight PEO and adding ionic solution, the proposed sensor exhibits high resolution (0.05 °C) and response speed (<12 s) within 35–43 °C. The novel introduction of a mesh structure aids the material in achieving microdomain control of PEO crystallization and improves the repeatability (Ex < 2.2%) of the sensor. The sensor is used for monitoring human body temperature and diabetic foot ulcers, and the results show that the sensor can achieve continuous and comfortable body temperature monitoring and early‐stage diabetic foot ulcer diagnosis, offering broad applications in health monitoring and rehabilitation medicine.

Ocular gene therapy targets eye diseases at the genetic level. Systemic transport of nucleic acids to ocular tissues poses a significant challenge, as the effectiveness of crossing the blood‐retina barrier limits nucleic acid penetration. Therefore, local administration, such as topical, periocular, or intraocular, can improve the outcome of in vivo gene therapy by bypassing the first‐pass effect and minimizing the systemic toxic effects. The eye is an immune‐privileged organ with limited local immune response, making it an ideal candidate for local gene therapy. Ocular gene therapy offers a promising solution for the treatment of a wide range of retinal diseases including age‐related macular degeneration, diabetic retinopathy, retinitis pigmentosa, and Leber congenital amaurosis. Gene therapy enables replacement of mutated genes essential for visual function, delivery of genes expressing neurotrophic factors and anti‐apoptosis factors for retinal degeneration, and delivery of genes expressing anti‐angiogenic proteins for ocular neovascularization. This perspective discusses the potential of nanoparticles for nucleic acid delivery to the retina, explores challenges, and evaluates different delivery methods, including non‐viral agents such as liposomes and polymers. These nonviral agents present advantages over traditional viral vectors, showing promise in overcoming limitations and offering a viable option for retinal gene therapy.

Glioblastoma multiforme (GBM), one of the most aggressive brain cancers, presents substantial therapeutic challenges, particularly concerning postsurgical recurrence and inherent drug resistance. In this study, a nanofiber‐based drug delivery system integrating platinum pro‐drugs and hemoglobin into mesoporous silica nanoparticles (HB/HSPt@MS NPs) is reported, which are surface‐modified with poly(ethylene glycol) (PEG) and targeting molecules, and subsequently embedded into nanofibers using an electrostatic spinning approach. Applied to the tumor site, these nanofibers leverage folate receptor overexpression on the tumor and the tumor's redox state to enable precise platinum release, inducing cell death through a targeted drug resistance pathway. The incorporation of hemoglobin is crucial as it disrupts the redox balance within GBM cells by facilitating the influx of iron ions, leading to lipid peroxidation through the Fenton reaction. This induces oxidative stress and overwhelms the cellular antioxidant mechanisms. This dual mechanism of action—direct cytotoxicity through sustained drug release and indirect cytotoxicity through induced oxidative stress—enhances the therapeutic efficacy of platinum drugs. The system effectively bypasses the blood‐brain barrier and reduces systemic toxicity, significantly improving delivery efficacy. Both in vitro and in vivo evaluations demonstrate substantial inhibition of tumor growth and recurrence, highlighting the potential for personalized GBM therapy.

In addition to open‐circuit voltage (VOC) loss, fill factor (FF) loss is considered another major factor restricting the further optimization of Cu2ZnSn(S,Se)4 (CZTSSe) device efficiency. In this work, a comprehensive investigation into the loss mechanisms of FF has been conducted, and implemented a Li&Ag co‐doping approach to enhance FF. The results indicate that the FF loss caused by insufficient carrier extraction is higher than that caused by non‐radiative recombination. The carrier extraction capability is significantly influenced by the band alignment of the CdS/CZTSSe interface and has little relationship with the carrier concentration of the absorber. Therefore, although Ag doping reduces the hole concentration and conductivity, it reduces the FF loss caused by carrier extraction due to the improvement of band alignment. Ag doping is also superior to Li in passivating harmful defects, which helps reduce FF losses caused by non‐radiative recombination. Correspondingly, Li performs better than Ag in increasing the hole carrier concentration and optimizing band alignment, greatly reducing FF losses caused by insufficient carrier transport. Finally, the Li and Ag co‐doping strategy enables a 14.91% efficient kesterite solar cell with the highest reported FF to date of 74.30% through collaborative optimization of carrier extraction and suppression of non‐radiative recombination.

Photoelectrochemistry (PEC) is a green and sustainable approach in the synthesis of H2O2, depending on the semiconductor to initiate two‐electron water oxidation into hydrogen peroxide (H2O2). However, the photoanodes generally have sluggish charge transfer and a limited number of active sites, which limit the yield and faradaic efficiency (FE) for the production of H2O2. Herein, Ti‐doped Fe2O3 photoanode with the modification of ZnO passivation layer (ZnO/Ti‐Fe2O3) for PEC H2O2 production is developed. The optimized photoanode has shown a high FE and selectivity for two‐electron water oxidation, achieving a yield approaching 0.56 µmol min⁻¹ cm⁻² at 1.23 VRHE and an average FE over 80% in the potential range from 1.0 to 1.6 VRHE. Impressively, an unassisted PEC system is designed to generate H2O2 at the ZnO/Ti‐Fe2O3 photoanode while performing an oxygen reduction reaction (ORR) at the Fe(Co)‐NC cathode. The integrated system enables the average PEC H2O2 production rate of 0.275 µmol min⁻¹ cm⁻² without applying any additional bias. Moreover, an unassisted PEC cell obtains a long‐term stability of 100 h. This work demonstrates new possibilities in designing efficient and stable PEC assemblies using low‐cost earth‐abundant materials for light‐driven catalysis.

In tissues where the vasculature is either lacking or abnormal, biomaterials can be designed to promote vessel formation and enhance tissue repair. In this work, the microstructure and bioactivity of microporous annealed particle (MAP) scaffolds are independently tuned to guide cell growth in 3D and promote de novo assembly of endothelial progenitor‐like cells into vessels. Both in silico characterization and in vitro experimentation are implemented to elucidate an optimal scaffold formulation for vasculogenesis. It is determined that MAP scaffolds with pore volumes on the same order of magnitude as cells facilitate cell growth and vacuole formation. Spatial control over cell spreading is achieved by incorporating adhesive microgels in well‐mixed, heterogeneous MAP scaffolds. While it is demonstrated that integrin engagement is the primary driver of network formation in these materials, introducing adhesive microgels loaded with heparin nanoparticles leads to the formation of vascular tubes after 3 days in culture. It is then shown in vivo that this unique scaffold formulation enhances vessel maturation in a wound‐healing model and instructs differential vascular development in the tumor microenvironment. Taken together, this work determines the optimal microstructure and ligand presentation within MAP scaffolds that leads to vascular constructs in vitro and facilitates vessel formation in vivo.