ABSTRACT Meeting the growing global demand for energy while mitigating environmental impacts requires efficient solar‐energy technologies. Photothermal conversion enhances solar‐to‐thermal performance through multiscale control of light absorption, energy conversion, and thermal management. Despite substantial progress, previous reviews have often focused on individual materials or applications rather than shared physical principles and the links among mechanisms, material and structural design, and diverse energy applications. This review summarizes recent advances in solar photothermal conversion for energy applications. It describes the principal light‐to‐heat conversion mechanisms, including plasmonic localized heating, non‐radiative relaxation, and molecular vibrations. By integrating the intrinsic optical properties of materials with nanostructure engineering, hierarchical porous networks, multilayer films, and biomimetic structures, spectral responses, heat transfer, and mass transport can be controlled across micro‐ and nanoscales. This framework guides the design of systems for interfacial solar evaporation, photothermal catalysis, building energy conservation, and thermoelectric power generation. Key challenges to large‐scale deployment, including environmental adaptability, long‐term stability, and cost‐effectiveness, are also analyzed. Finally, emerging directions such as coupled dynamic spectral modulation and AI‐driven inverse design are highlighted as routes toward practical photothermal technologies. This review provides insights into the development of multifunctional materials and intelligent systems for the broader deployment of solar photothermal technologies.
ABSTRACT Excellent stability is essential for multi‐stimuli‐responsive luminescent materials toward high‐performance multifunctional optoelectronics. However, integrating cyclic‐stable mechanoluminescence (ML) and thermally stable photoluminescence (PL) into a single chemically stable material remains a critical challenge. Herein, we present a novel narrow‐band green‐emitting Ba 0.79 Al 10.9 O 17.14 :0.25Mn 2+ (BAO:0.25Mn 2+ ) phosphor with rigid β ‑Al 2 O 3 ‑type structure, which exhibits a high internal quantum efficiency (IQE) of 60.3% and exceptional zero‐thermal‐quenching (ZTQ) PL behavior up to 523 K. This phosphor exhibits positive moisture resistance, preserving its PL intensity, IQE, and ZTQ feature even after immersion in water for 7 days. Particularly, the BAO:0.25Mn 2+ /polydimethylsiloxane (PDMS) elastomer demonstrates self‐recoverable and ultrastable cyclic ML without obvious degradation even after 15 000 rapid continuous stretching cycles. The ML is confirmed to originate from an interfacial triboelectric effect. By integrating narrow‐band emission, robust thermal and environmental PL stability, as well as superior cyclically stable and self‐recoverable ML within a single material platform, the BAO:0.25Mn 2+ phosphor demonstrates promising applications in wide‑gamut display backlighting, flexible fire‑safety indicators, optical encryption, and interactive pressure mapping. This study not only sheds new light on the integration of PL and ML, but also establishes a promising material platform for advanced multifunctional optical applications, laying a solid foundation for next‐generation intelligent luminescent materials and devices.
ABSTRACT Oxide coatings, owing to their electronic insulation and ionic conductivity, are promising artificial interfacial layers for stabilizing Zn anodes. However, conventional single‐phase, multiphase, and low‐entropy oxides remain insufficient to simultaneously address the complicated interfacial challenges in aqueous zinc‐ion batteries. Herein, inspired by high‐entropy engineering, an ultrathin amorphous high‐entropy‐engineered oxide TiYZrAlSnO x (TYZAS) coating is in situ constructed on Zn anodes via atomic layer deposition to achieve durable interfacial stabilization. Beyond the conventional perception that strong zincophilicity is universally beneficial, a lever‐like thermodynamic–kinetic balance between Zn adsorption and ion migration is revealed, demonstrating that insulating oxide coatings favor weak yet effective Zn adsorption coupled with rapid Zn 2+ migration. Both experimental and theoretical results demonstrate that the TYZAS coating simultaneously reduces Zn adsorption strength and migration barrier, thereby promoting homogeneous Zn nucleation and accelerated interfacial ion transport. Consequently, the TYZAS‐protected Zn anode delivers an ultralong cycling lifespan of 4000 h at 5 mA cm −2 and 1 mAh cm −2 . This work establishes a generalizable interfacial thermodynamic–kinetic regulation principle for the rational design of advanced Zn metal anodes.
ABSTRACT Metal single‐atom catalysts (SACs) for sodium−sulfur (Na−S) batteries typically rely solely on thiophilic binding sites to interact with the polysulfide anions of sodium polysulfides (NaPSs), which intrinsically restricts their catalytic efficiency in sulfur redox reactions. Herein, the sulfonic acid‐functionalized Zn single‐atom catalysts (Zn−N 4 −SO 3 H/C) featuring dual thiophilic and sodiophilic binding sites are designed to improve the energy storage performance of Na−S batteries. The resulting Zn−N 4 −SO 3 H/C provides Zn single‐atom sites and sulfonic acid groups to selectively interact with the polysulfide anions and the sodium cations of NaPSs, respectively. This dual interaction simultaneously strengthens the adsorption of NaPSs and facilitates the Na─S bond cleavage by Na−O interaction, thereby lowering the energy barrier of the rate‐limiting step and accelerating sulfur redox kinetics. The S@Zn−N 4 −SO 3 H/C exhibits a high reversible capacity of 1284 mAh g −1 at 0.1 C after 100 cycles and long‐term stability with a low capacity decay rate of 0.023% per cycle over 1200 cycles at 3.0 C. This work highlights that incorporating metal‐free chemical groups adjacent to metal single‐atom sites offers a synergistic strategy to boost sulfur redox kinetics for high‐efficiency Na−S batteries.
ABSTRACT Reducing building energy consumption requires passive materials that buffer environmental fluctuations and lessen reliance on energy‐intensive heating, ventilation, and air‐conditioning systems. Wood is attractive for humidity regulation because its hydrophilic cell walls enable reversible moisture sorption; however, absorbed water also induces swelling, anisotropic deformation, and mechanical relaxation, imposing a long‐standing trade‐off between moisture‐buffering capacity and dimensional stability. Here, we report a cell wall reconstruction strategy in which D‐sorbitol forms a flexible multivalent hydrogen‐bond network with cellulose, while reconfigured lignin features strengthened covalent connectivity and enhanced interfacial coupling with cellulose, thereby modifying cell wall interactions associated with moisture uptake and deformation. The resulting wood combines a moisture buffer value of 3.9 g m − 2 %RH − 1 with a reduction in volumetric swelling from 13.6% to 2.5%. It exceeds native wood in modulus of rupture and impact toughness by 32% and 33%, respectively. Building energy simulations show that replacing gypsum board with reconstructed wood reduces office‐building energy demand, achieving a nationwide weighted energy‐saving rate of 12.9%. By coordinating cellulose, D‐sorbitol, and lignin interactions, this work establishes a molecular design principle for adaptive biomass‐based building materials that convert moisture into a functional resource for passive environmental regulation.
ABSTRACT The application of traditional photocatalysts is fundamentally constrained by inefficient charge separation and limited redox capability. To address these challenges, a 2D/2D S‐scheme heterojunction was constructed through precise assembly of ultrathin bismuth oxybromide (BN) and black phosphorus nanosheets (PN). This well‐defined interface clearly promoted charge separation and transport while maintaining strong redox potentials through the S‐scheme mechanism, thereby significantly boosting the oxygen activation capacity and overall reactive oxygen species (ROS) yield through both direct oxidation and H 2 O 2 ‐mediated pathways. The 1.0PN/BN was identified as the optimal composite through a systematic screening process, demonstrating superior charge separation and ROS production efficiency compared to other ratios and individual components, leading to potent and reliable disinfection performance. H 2 O 2 served as a crucial precursor sustaining continuous ·OH generation, thereby promoting the disinfection performance. Finally, the practical potential of this material was further evaluated in an oxygen‐aeration “water wheel reactor”, where it exhibited excellent H 2 O 2 activation, disinfection, and stability throughout 2 h continuous operation. This work provides a blueprint for translating advanced photocatalyst design into practical water treatment.
ABSTRACT Mg–CO 2 batteries present promising potential for integrated energy storage and carbon fixation, though their advancement is limited by slow cathodic CO 2 conversion kinetics and insufficient reversibility. Here, we report an In‐mediated electrolyte that couples solvation structure regulation with cathodic pathway control to realize highly reversible Mg─CO 2 chemistry in a conventional electrolyte system. Experimental and theoretical analyses demonstrate that, in addition to stabilizing the Mg anode and ensuring Mg 2+ transport, In species serve as an “electron sink and relay” to accelerate CO 2 conversion kinetics. They undergo preferential reduction prior to CO 2 , generating in situ atomically dispersed active sites that subsequently activate CO 2 via electron injection. This process directs the conversion pathway toward the formation of more reversible discharge products with favorable transport morphologies. As a result, the Mg─CO 2 battery delivers a long‐term cycling life of over 1300 h at 100 mA g −1 with a minimum voltage gap of 0.25 V during cycling, and maintains robust performance under extreme conditions, including 3000 mA g −1 rate capability and operation at −20°C. This concept of mediator‐enhanced electrolyte provides an effective route for a high‐performance Mg–CO 2 battery system.
ABSTRACT The escalating cooling demands of high‐heat‐flux electronic systems require materials that deliver efficient heat spreading, phase‐change enhancement, and scalable manufacturability—capabilities rarely found simultaneously on a single platform. Here, we introduce a microlaminate strategy that translates graphene's intrinsically two‐dimensional phonon transport into three‐dimensional heat removal from localized hot spots, without relying on volumetric composites or geometry‐dominated architectures. As a representative implementation, we demonstrate graphene‐based microlaminates integrated with laser‐microstructured copper, where the metal serves as a technologically relevant model substrate rather than a fundamental constraint. The interface‐engineered microlaminates preserve graphene's ultrahigh in‐plane thermal conductance, while enabling efficient coupling to macroscopic heat‐rejection pathways. Experiments and supporting analyses reveal exceptional performance across multiple thermal‐management regimes: (a) ∼20% reduction in hotspot temperature under single‐phase liquid cooling at heat fluxes approaching ∼150 W cm −2 , (b) ∼15% enhancement in heat‐transfer coefficient during dropwise condensation, and (c) record in‐plane effective thermal conductivity of ∼1.5 × 10 4 W m −1 K −1 in vapor‐chamber heat spreaders – among the highest reported for thermal‐management devices to date. While copper is employed here as a model system, the microlaminate framework is material‐agnostic and readily extendable to other thermally conductive substrates, establishing a general pathway for integrating planar nanomaterials into three‐dimensional thermal platforms.
ABSTRACT Lithium metal batteries (LMBs) are regarded as promising next‐generation energy storage systems owing to their ultrahigh theoretical energy density. However, conventional polyolefin separators suffer from poor electrolyte wettability and limited capability to regulate ion transport, leading to uncontrolled dendritic growth and unstable solid electrolyte interphases (SEIs) that severely compromise battery safety and cycling stability. Herein, a biodegradable polybutylene succinate@polylactic acid (PBS@PLA) composite separator is developed to synergistically regulate Li‐ion transport and enhance interfacial stability. The PBS domains facilitate efficient electrolyte uptake and enhance ionic conductivity, while the highly polar PLA domains modulate Li‐ion distribution through ion–dipole interactions. This cooperative ion‐regulation architecture accelerates charge‐transfer kinetics and promotes the formation of a dense LiF‐rich SEI. Leveraging these advantages, the PBS@PLA separator enables an ionic conductivity of 2.1 mS cm −1 in the regular 1 M carbonate electrolyte and sustains stable Li plating/stripping at a high current density of 10 mA cm −2 . The Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 full cells also retain 80.2% of their initial capacity after 300 cycles at 5C. Moreover, the intrinsic biodegradability of the PBS@PLA separator enables controllable end‐of‐life degradation, facilitating material recycling. This work establishes a viable separator‐engineering strategy that integrates high performance with eco‐friendly recyclability for LMB technologies.
ABSTRACT Independent dual alignment of the anisotropic, conductive metal–organic framework (MOF) crystals and liquid‐crystal polymer (LCP) network enables a multi‐responsive soft actuator capable of both UV‐driven photothermal and electrothermal operation. In this design, LC alignment ensures reversible actuation, whereas Cu 3 (HHTP) 2 (HHTP = 2,3,6,7,10,11‐hexahydroxytriphenylene) alignment governs bilayer structure and charge transport pathways, enabling advanced functionalities including on/off switching, region‐selective actuation, and programmable directionality. In the photothermally driven mode, strong UV absorption and efficient non‐radiative relaxation of Cu 3 (HHTP) 2 , combined with a horizontal bilayer structure, induce rapid and reversible bending. A Hercules beetle‐inspired horn actuator lifted loads up to 40 times its own weight. In the electrically driven mode, Cu 3 (HHTP) 2 produced uniform Joule heating and large bending only when horizontally aligned, reflecting the creation of long‐range conductive pathways. As a proof of concept, this principle was applied to a self‐protective smart wire that autonomously disconnects under overcurrent. Collectively, these findings provide valuable insights into the alignment, manipulation, and utilization of anisotropic conductive MOFs for diverse applications, including soft grippers, adhesive/reconfigurable electrical wiring, and microelectronics.
ABSTRACT Altermagnetic multiferroicity is rapidly emerging as a transformative paradigm for both condensed matter physics and advanced spintronics. However, existing magnetoelectric mechanisms are inherently restricted to structural inversions, which merely reverse the momentum‐space spin splitting. Here, guided by symmetry principles and microscopic modeling, we unveil an emergent class of altermagnetic multiferroicity in 2D heterobilayers. This mechanism utilizes out‐of‐plane ferroelectric polarization to govern the interlayer coupling, thereby tuning the competition between localized antiferromagnetic superexchange and itinerant ferromagnetic double‐exchange. Crucially, this interfacial modulation triggers a reversible magnetic phase transition between a trivial ferromagnetic state and an altermagnetic state, establishing a distinct magnetoelectric coupling mechanism. Using first‐principles calculations, we demonstrate this mechanism in MnPS 3 /Sc 2 CO 2 heterostructure, where we further predict the emergence of two distinct altermagnetic phases. Our findings transcend geometric restrictions, establishing a physical framework for nonvolatile and programmable altermagnetic spintronics.
ABSTRACT Organisms achieve adaptive survival through highly integrated closed‐loop systems of perception, feedback, and execution. This highly coordinated structure–function collaboration mode provides important inspiration for the design of soft robots. However, current intelligent soft robots are typically based on modular integration of discrete sensing and actuation units, making it difficult to achieve organism‐like highly coordinated full‐surface sensing–actuation coupling. As functionally tunable intelligent materials with high water content, softness, biocompatibility, and stimulus‐responsive behavior, hydrogels can integrate sensing and actuation into one material structure, which lays a material foundation for the development of next‐generation intelligent soft robotic systems. In this review, we comprehensively discuss the design requirements for hydrogels used in soft robots across different application fields in terms of material properties, sensing capabilities, and actuation functions. Based on the diverse functionalities of hydrogels, we emphasize the importance of integrating sensing and actuation, with particular attention to the evolutionary trajectory from the integration of discrete functional modules to structure–function integration and ultimately to closed‐loop feedback intelligent systems. Finally, we provide insightful perspectives on the current challenges and prospects in the field. This review aims to provide a systematic reference for the design and development of highly integrated, adaptive, and autonomous soft robotic systems.
ABSTRACT Ruthenium is a promising alkaline water splitting cathode due to its fast water dissociation kinetics and cost‐effectiveness. However, its excessively strong binding affinity for reaction intermediates severely hampers catalytic efficiency. To address this challenge, we demonstrate a work‐function‐engineered synthesis of sub‐2 nm ruthenium‐copper clusters hosted on oxygen‐rich carbon via a ligand‐driven spontaneous reduction pathway. Electrochemical measurements and theoretical calculations reveal that copper incorporation and strong coupling with oxygen‐containing moieties induce electron‐deficient states at Ru sites. The electronic modulation optimizes the adsorption energy of reactant intermediates, ultimately accelerating water dissociation and hydrogen desorption kinetics. Consequently, the catalyst delivers a high turnover frequency of 16.3 s −1 at an overpotential of 100 mV, representing a 5.8‐fold improvement over the benchmark platinum catalyst. When integrated into a pure water‐fed anion exchange membrane water electrolyzer, it achieves 1.8 A cm −2 at 2.0 V and operates stably for 840 h at 0.5 A cm −2 .
ABSTRACT Elevated interfacial friction and acidified microenvironments in osteoarthritis (OA) drive coupled mechanical–biological failure, destabilizing lubrication and amplifying cellular stress, thereby accelerating cartilage degeneration and limiting therapeutic efficacy. Here, we report pH‐responsive supramolecular nanogels (NGs) composed of benzimidazole‐modified polyethylene glycol (PEG‐BM) and β‐cyclodextrin‐modified hyaluronic acid (HA‐CD) that undergo a microenvironment‐triggered lubrication‐regime transition. Surface force apparatus measurements directly revealed a transition from interfacial sliding under physiological conditions to rolling‐assisted lubrication under acidic conditions, accompanied by nanoscale interfacial structures consistent with a rolling‐bearing‐like mechanism. All‐atom molecular dynamics simulations identified protonation‐induced weakening of the β‐CD/BM host–guest motif and enhanced guest hydration as molecular drivers of pH‐triggered supramolecular reconstruction, providing a molecular basis for the adaptive interfacial transition. Comparative transcriptomic analysis showed that dexamethasone‐loaded NGs (NGD) were associated with ECM–receptor interaction, focal adhesion, integrin‐mediated adhesion, actin‐cytoskeletal organization and mechanosensitive cellular responses. In vivo, drug‐free NGs achieved therapeutic outcomes comparable to NGD. Mechanistically, protonation‐driven host–guest reconstruction enables pH‐adaptive lubrication, which is associated with matrix‐interactive and mechanosensitive cellular programs favorable for matrix homeostasis and tissue preservation. These findings establish a multiscale mechanobiological framework linking molecular reconstruction, adaptive interfacial lubrication and matrix‐preserving biological remodeling, providing a strategy for microenvironment‐responsive mechanical regulation in OA therapy.
ABSTRACT Surgical resection of the primary tumor and simultaneous postsurgical adjuvant therapy for undetected metastases are the gold standard for the treatment of metastatic triple negative breast cancer (TNBC). Although near‐infrared fluorescent imaging/theranostic probes are widely used for TNBC, they suffer from photobleaching, low signal‐to‐background ratio, and insufficient photothermal conversion efficiency (PCE). To overcome these barriers, we developed a fluorescence‐free near‐infrared imaging probe that combines surface‐enhanced resonance Raman scattering (SERRS)‐guided surgery with photothermal immunotherapy. Two black hole quenchers (Q820/Q920) with near‐zero fluorescence background were designed and used to modify gold nanorods, yielding fluorescence‐free SERRS nanoparticles (NPs) with outstanding performance, including an ultralow detection limit (95 fM), ultrahigh signal‐to‐background ratio (69.9) in vitro and remarkable photostability, outperforming conventional fluorescent counterparts. Notably, these fluorescence‐free SERRS NPs exhibited a synergistic photothermal effect arising from quencher‐plasmon interactions, achieving a high PCE of 63.9%. Functionalized with a CXCR4 antagonist, the targeted SERRS NPs allow for intraoperative delineation of the tumor margin with an ultrahigh signal‐to‐background ratio of 22.6 for complete resection of the primary TNBC tumor. Combined with anti‐PD‐1 monoclonal antibody, the SERRS NPs effectively eliminated residual lesions and suppressed distal lung metastasis in vivo postoperatively through the synergy of photothermal ablation and immune activation.
ABSTRACT Room‐temperature sodium–sulfur (RT Na–S) batteries offer high energy density and low cost but suffer from poor conductivity, sluggish redox kinetics, and polysulfide shuttling. This study introduces a multifunctional Cu 2 O@MXene separator with a hierarchical porous structure and a 3D MXene network for fast electron transport. The hierarchical porous structure provides physical confinement, while the polar Cu─O bonds and Cu + Lewis acid centers in Cu 2 O provide chemical anchoring and catalytic sites for sodium polysulfides (NaPSs). Experimental evidence and theoretical calculations reveal that MXene serves as an electronic reservoir to protect Cu + catalytic active sites from reduction, enabling NaPSs anchoring through interfacial Cu─S and Ti─S bonds. Benefiting from this synergistic adsorption‐catalytic mechanism, the Cu 2 O@MXene interlayer enhances NaPSs confinement and accelerates sulfur redox kinetics. Consequently, Cu 2 O@MXene‐PP cells achieve 942.1 mAh g −1 after 100 cycles at 0.2 C and ultralong cycling stability of 574.9 mAh g −1 after 3500 cycles at 2 C. Under a sulfur loading of 4.65 mg cm −2 , the cell retains 3.1 mAh cm −2 after 105 cycles. Theoretical calculations further reveal that Cu 2 O@MXene enables stronger NaPSs adsorption and improves the thermodynamical favorability of the Na 2 S 2 to Na 2 S conversion. This work provides reasonable guidelines for designing Cu‐based catalytic separators in high‐performance RT Na‐S batteries.
ABSTRACT Dry‐process electrode technology is an important route for next‐generation lithium‐ion battery (LIB) manufacturing because it eliminates solvent use during electrode production. However, the influence of active material particle characteristics on PTFE fibrillation and electrode design remains insufficiently understood. Here, polycrystalline and single‐crystal NCM811 particles are used as model materials, and their nanoscale surface morphologies are quantified by atomic force microscopy. Polycrystalline particles exhibit a higher mean surface roughness than single‐crystal particles, with Ra values of 60.18 and 32.77 nm, respectively. Their different fibrillation behaviors are analyzed by considering particle morphology, size, and contact geometry. Polycrystalline particles favor PTFE fibrillation but are more susceptible to cycling‐induced structural degradation, whereas single‐crystal particles provide greater structural stability but lower fibrillation capability. Based on these complementary characteristics, a polycrystalline‐single‐crystal grading strategy is proposed. Among the three compositions tested, PS91 containing 10 wt.% single‐crystal particles achieves the best balance between transport kinetics and cycling stability, retaining a discharge capacity of 152.04 mAh g −1 after 50 cycles at 0.33C. Its H1‐M peak shift is 67% smaller than that of PS10, while post‐mortem cross‐sectional SEM reveals less severe particle cracking. A discrete element model shows how mixing speed and particle size ratio affect uniformity, supporting process optimization.
ABSTRACT Communication between living and artificial cells represents a fundamental step toward constructing hybrid systems capable of cooperative behaviors. Here, we introduce an ATP‐mediated energy transduction mechanism that enables bidirectional communication between natural dendritic cells and stimuli‐responsive polymersome artificial cells. The polymersomes were equipped with a photo‐switchable spiropyran derivative, which provides light‐gated control of membrane permeability. Upon UV irradiation, the membrane transiently increases permeability, allowing ATP transport across the boundary. This enables signal transduction from natural cells to artificial ones, demonstrated by ATP uptake triggering internal coacervation and the ATP‐dependent firefly luciferase reaction inside polymersomes. Conversely, artificial cells containing ATP or the pyruvate kinase enzyme release ATP to surrounding dendritic cells, resulting in increased intracellular calcium levels. The system thus establishes a reciprocal molecular dialogue via energy uptake and signal generation from natural to artificial cells, and metabolic stimulation from artificial to natural cells. This study provides a robust platform for dynamic cell‐material interaction and controlled biochemical communication, advancing artificial and living cell integration toward engineered signaling interfaces and programmable bio‐hybrid systems.
ABSTRACT Beyond rational design of active sites, regulation of the local chemical environment of electrocatalysts to promote the reactant transport dynamics is crucial for enhancing the reaction kinetics, which faces significant limitations owing to the rigid hydrogen‐bond networks formed by interfacial water molecules. Here, an entropy‐derived regulation strategy was proposed to engineer disordered interfacial water structures, which induces a flexible and adaptive environment that can substantially enhance the reactant transport dynamics and reaction kinetics. Taking a conjugated coordination polymer aerogel with homogeneous single‐atom metal active sites as the model system, a comparative study investigating high‐entropy and low‐entropy conjugated coordination polymer aerogels (denoted as HE‐CCPA and LE‐CCPA) was carried out. Our findings reveal that, relative to LE‐CCPA, the inhomogeneity of electron density distribution and reactant adsorption across multiple different single‐atom metal sites of the HE‐CCPA profoundly disrupts the rigid hydrogen‐bond network, resulting in disordered interfacial water structures that can appreciably facilitate the transport dynamics of hydroxide ion reactants to improve the alkaline oxygen evolution kinetics. These findings highlight disordered interfacial water engineering as a promising approach for performance enhancement in widespread aqueous electrocatalysis.
ABSTRACT Intractable hypoxia in solid tumors remains a major obstacle for conventional type‐II photodynamic therapy. We report a dye‑sensitized semiconductor strategy to construct high‐efficiency, low oxygen‐dependent type‐I photosensitizers by anchoring proper dyes to zinc oxide ( ZnO ) nanoparticles. Guided by precise energy‐level engineering, a thermodynamic threshold is established to enable efficient interfacial electron transfer. Femtosecond transient absorption spectroscopy directly captures ultrafast electron injection on the picosecond timescale, a process that effectively outcompetes radiative decay and suppresses charge recombination. The resulting ZnO‐Cy7@PDA nanoplatform mediates a unique dual‐pathway redox synergy: the electron‐rich ZnO conduction band drives robust generation of • O 2– and • OH even under extreme hypoxia, while the electron‐deficient dye species catalytically depletes endogenous NADH and GSH. This combined action induces severe oxidative stress, triggering a pro‐death autophagy–ferroptosis cascade that effectively overcomes therapeutic resistance. This work provides a universal physicochemical blueprint for semiconductor‐based phototherapeutics and offers insights bridging ultrafast photonics and organelle‐specific therapy.
