The treatment of biofilm-associated drug-resistant bacterial infections remains a formidable clinical challenge, primarily due to the limited permeability of therapeutic agents through the dense extracellular matrix and the inherent drug resistance of biofilm-embedded microorganisms. Here, to overcome this challenge, we report the design of an atomic Fe-O-Mo/Fe-S-Mo homojunction photothermal nanosheet (Fe-HJPS) to synergize reactive oxygen species (ROS)-biocatalysis and biofilm penetration for eradicating drug-resistant bacterial infections. Spectroscopic and computational analyses reveal that the homojunction sites in the Fe-HJPS, comprising asymmetric Fe-S-Mo/Fe-O-Mo coordinations around Fe centers, downshift the high d-p hybrid orbital energy level compared to the original symmetric Fe-S-Mo coordination. This optimization enhances the adsorption affinity of oxygen intermediates and improves ROS-biocatalytic activities. Notably, under near-infrared (NIR) irradiation, the Fe-HJPS generates localized heat and disturbs the extracellular polymeric substances (EPS) in biofilms to increase the permeability of bacterial membranes, thereby facilitating ROS influx into bacterial cells. This dual-action mechanism of ROS production and biofilm penetration enables effective biofilm eradication at ultralow concentration (40 mu g & sdot;mL- 1), demonstrating superior efficacy against drug-resistant infections in both in vitro and in vivo models. Our findings establish atomic-scale homojunction in photothermal artificial enzymes as a versatile strategy for designing non-antibiotic antimicrobial nanomaterials that overcome drug-resistant bacterial infections.
Conventional fabrication of integrated carbon electronics often requires material deposition or transfer, which inevitably leads to surface contamination and structural defects. Here, we present a monolithic “Write-Rewrite-Direct” approach for in situ sequential programming of carbon's optical, electrical, and chemical properties from a single parent graphite crystal, overcoming the challenges of material transfer. First, we introduce Catalyst-Enhanced Electrochemical Lithography (CEEL), an acid-free route that exploits MoS2 electrocatalysis to "write" atomically smooth epitaxy-like graphene oxide (GO) directly onto graphite. In contrast to conventional electrochemical oxidation of graphite, which yields rough surfaces, CEEL produces mechanically robust, vivid photonic structures with intense structural colors. We validate this monolithic integration by fabricating the first all-carbon field-effect transistor with a vertical gate-dielectric-channel configuration, without any lithographic patterning of contacts or lift-off processes. Second, we "rewrite" these films with a tightly focused laser to produce laser-reduced graphene oxide (LrGO) vertical interconnects. This enables us to draw all-carbon free-form, high-resolution LrGO circuits within the larger, electrochemically defined GO structure. Finally, we exploit this hierarchical control to "direct" the selective assembly of plasmonic nanostructures onto the LrGO patterns, integrating plasmonic microreactors and chemical sensing capabilities. This "Write-Rewrite-Direct" paradigm is a potential enabler of next-generation all-carbon electronics, offering a maskless route to creating dynamic, reconfigurable surfaces, including field-effect transistors and advanced sensing and photocatalytic platforms monolithically integrated in a single device.
Modulating the catalytic environment through metal-support interactions is a promising strategy to advance electrocatalytic water splitting, yet designing robust, efficient hydrogen-evolution sites on metal oxides remains difficult. We report a titania-iridium interfacial cathode fabricated from a Ti-metal-organic framework that uniformly anchors electron-rich Ir clusters on TiO2. This TiO2-Ir catalyst achieves ultra-low overpotential and exceptional durability in both alkaline and seawater electrolytes. Experimental and density function theory (DFT) calculations reveal that the TiO2-Ir interface lowers the water-dissociation barrier, accelerates OH* desorption, and enriches electron density on adsorbed H*, strengthening antibonding states and facilitating H-2 formation. Molecular-dynamics simulations show that the surface electrostatically repels Cl-, Mg2+, and Ca2+, preventing precipitation fouling. An anion-exchange-membrane (AEM) electrolyzer with TiO2-Ir electrodes achieves 1 A cm(-2) at the cell potential of only 1.78 V, and it operates >100 h in alkaline seawater with negligible decay. This work highlights electron-rich interfacial environments as critical for high-rate, sediment-tolerant hydrogen evolution and provides a route toward industrial seawater electrolysis. (c) 2026 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
The poor proton coverage of electrocatalysts in neutral hydrogen evolution reaction (HER) and the incapacity to resist alkali hydroxides for seawater electrolysis have resulted in a large kinetics gap from acidic water splitting. Facing this challenge, a cluster‐in‐cluster solid solution catalyst with a proton‐rich microenvironment and anti‐interference interface composed of an amorphous hafnium oxide cluster penetrating in crystalline iridium cluster (HfO x ‐in‐Ir SSC), is reported which can achieve superior activity for direct seawater splitting. The structure characterizations, in situ FT‐IR and Raman, and theoretical calculations reveal that the HfO x clusters in the Ir cluster endow an interfacial proton‐rich microenvironment by increasing the coverage and optimizing the adsorption of * H, thereby achieving a low overpotential of 30 mV in neutral electrolytes. Fascinating, the interfaces of HfO x ‐in‐Ir SSC catalysts present abundant * H and OH * species and simultaneously superior anti‐poison to Cl − /ClO − and anti‐deposition to Mg(OH) 2 , eventually achieving an ultra‐low overpotential of 117 mV at 10 mA cm −2 and excellent stability in seawater splitting.
Oxygen (O2) is utilized in various applications, including medical use, industrial manufacturing, tunnel construction, and scientific research, serving as an important resource for essential technologies and life support systems. However, current O2 generation methods are complex, dependent on heavy equipment and considerable power, and exhibit limited adaptability to harsh environments. Here, to address this challenge, we propose the de novo design of single-atomic Pt lattice-doped molybdenum carbide catalysts with synergistic Pt-Mo pair sites (Pt-Mo@MoCx) to serve as bioinspired O2-evolution catalysts for cost-effective, portable, and environmentally friendly O2 generation. Our experimental and theoretical studies indicate that Mo coordination enhances the electron density at the Pt active site, increasing its interaction with oxygen species and thereby reducing the activation energy of the O2 evolution reaction. Accordingly, the prepared Pt-Mo@MoCx catalysts demonstrate high efficiency and durability in O2 generation, achieving a turnover number of 18.92 s−1, which exceeds the performance of state-of-the-art H2O2-catalytic materials reported in the literature. We believe that this bioinspired and portable technology, which does not rely on traditional electrical energy, will provide a reliable solution for O2 applications in areas with limited O2 availability and in emergency situations such as power outages.
Periodontitis-induced alveolar bone loss represents a complex therapeutic challenge that demands simultaneous resolution of chronic inflammation and restoration of bone homeostasis. Drawing inspiration from natural antioxidases, the de novo design of an interlaminar ruthenium-coordinated covalent organic framework (COF) is reported that functions as an artificial antioxidase system. This fully condensed COF architecture (TTf-Ru) combines extended π-electron delocalization with precisely engineered asymmetric ruthenium coordination sites, thereby creating optimal electronic environments for scavenging reactive oxygen species (ROS). Spectroscopic and computational analyses reveal that TTf-Ru exhibits dual enzyme-mimetic activities, demonstrating both catalase- and superoxide dismutase-like functionality through tailored adsorption energetics for oxygen intermediates. At the cellular level, TTf-Ru effectively mitigates oxidative stress in mesenchymal stem cells, preserving their osteogenic differentiation capacity even under pro-inflammatory conditions. The artificial antioxidase simultaneously orchestrates an immunomodulatory response, suppressing pro-inflammatory macrophage polarization while promoting a tissue-reparative phenotype. In periodontitis models, this coordinated action translates to significant therapeutic outcomes, which reduce alveolar bone resorption and maintain periodontal tissue architecture. The findings establish a material design paradigm for COF-based enzyme mimics, highlighting how spatially organized biocatalytic centers can be engineered to address multifactorial diseases through integrated redox modulation and immune regulation, which provides new possibilities for treating ROS-mediated inflammatory disorders.
Sonodynamic therapy (SDT) has emerged as a promising strategy for neuroblastoma treatment, leveraging ultrasound to induce the production of reactive oxygen species (ROS) at tumor sites, thereby enhancing the efficacy of immunotherapy. However, a major challenge in SDT is the efficiency of ROS generation, particularly in the context of hypoxia within the tumor microenvironment. Herein, inspired by the natural peroxidase, an imide‐linked metal‐phthalocyanine‐based conjugated organic polymer (COP) (COP TPcFe ) has been designed with a well‐defined π‐conjugated nanostructure and peroxidase‐mimetic atomic Fe‐N sites for sonochemodynamic immunotherapy against neuroblastoma. This work demonstrates that COP TPcFe can efficiently produce potent ROS (•OH and •O 2 − ) by utilizing localized H 2 O 2 and the effects of ultrasound, thereby achieving efficient and synergistic tumoricidal activity. Notably, the highly π‐conjugated structure endows COP TPcFe with excellent electron transport capabilities, enabling rapid catalysis of H 2 O 2 to O 2 , thus alleviating the hypoxic conditions within tumors. Moreover, by encapsulating COP TPcFe with neuroblastoma cell membranes, this study achieveshomologous targeting of tumor cells and tissues, leading to efficient accumulation within tumor cells, mitochondrial disruption, and apoptosis. Additionally, the proposed sonochemodynamic immunotherapy effectively activates natural killer cells and reverses the immunosuppressive tumor microenvironment, thereby alleviating hypoxia and significantly enhancing the therapeutic efficacy of neuroblastoma treatment.
High-entropy layered (oxy)hydroxides (HE-LDHs), with efficient intrinsic activity and ideal "cocktail effect," are considered promising candidates for achieving stable and active oxygen evolution reaction (OER). However, due to the dissolution of high-valence intermediates and unpredictable phase transition during the OER process, it remains challenging to solve the trade-off problems occurring between the stability and activity of HE-LDHs. Herein, HE-LDHs with an intercalation structure constructed on a metal-organic framework with heterointerface confinement are reported, realizing the alleviation of metal dissolution and optimized valence of catalytic sites during the OER process, for highly active and durable water electrooxidation. The prepared HE-LDH@Mn-MIL-100 shows ultralow overpotential of 211 mV at 10 mA cm-2 and wonderful stability operated in 1.0 m KOH for 100 h. Besides, the constructed anion exchange membrane water electrolyzer (AEMWE) delivers 1.0 A cm-2 at only 2.33 V for cell voltage in 1.0 m KOH, indicating promising prospects for practical applications. This work provides an innovative strategy in improving high-entropy materials systems by confined ligand release for intercalation and offers new insights for tailoring highly active and stable catalysts for alkaline water electrooxidation.
Radiotherapy (RT) remains a cornerstone treatment for head and neck squamous cell carcinoma (HNSCC), yet its clinical efficacy is frequently compromised by intrinsic radioresistance. To address this challenge, we developed an iron-doped semiconducting artificial enzyme (Fe-SAE) that synergizes with RT to enable effective and controllable tumor eradication. Notably, due to its dendritic cell biomimetic topological structure and atomic-level iron catalytic centers, Fe-SAE, composed of low atomic number elements, can not only enhance the interaction with tumor cells, controllably enhance the generation of reactive oxygen species (ROS) under radiation, and activate the immune microenvironment but also exhibit good biocompatibility. Moreover, Fe-SAE reshapes the immune microenvironment by promoting M1 polarization of macrophages and activation of CD8+ T cells, facilitating robust tumor suppression. Collectively, our findings establish Fe-SAE as a promising artificial enzyme platform with potent radiosensitizing and immunomodulatory capacities, offering a compelling therapeutic avenue for refractory HNSCC.
Mimicking the proton-coupled electron transfer (PCET) pathways of natural enzymes, we engineer a porphyrin-based ruthenium coordination polymer (Ru-PCPN) with precisely positioned atomic-level N4/N2 proximal sites through molecular-scale coordination engineering. This bioinspired architecture establishes a dual-site relay mechanism where the Ru-N2 center accelerates water dissociation kinetics while the adjacent Ru-N4 site optimizes hydrogen recombination. Experimental and theoretical results reveal that the sub-nanometer-proximate N4/N2 sites function as proton donor-acceptor pairs, enabling directional proton transfer via PCET and synergistically enhancing water electrolysis. When integrated with carbon substrates, the Ru-PCPN@CB catalyst demonstrates exceptional hydrogen evolution performance in alkaline conditions, achieving a low overpotential at 10 mA cm-2 (42 mV, comparable to 44 mV of Pt/C), high mass activity and TOF of 9.02 A mg-1 and 4.73 s-1 (∼7.0 and 3.6 times of Pt/C), and good stability. This work establishes atomic-scale coordination proximity as a new paradigm for breaking scaling relationships in multistep electrocatalysis.
Iridium (Ir), with optimal hydrogen binding energy (HBE) and hydroxyl bonding energy (OHBE), is considered a promising platform for achieving bi‐directional hydrogen catalysis. However, traditional Ir‐based catalysts with multiple crystalline facets exhibit a gap between the apparent activity and theoretical value, especially for the hydrogen oxidation reaction (HOR). Here, a molten co‐growth process of Ir and vanadium nitride (Ir‐VN) is reported, realizing precise exposure of lattice‐matched Ir (111) on VN with optimal HBE and OHBE, for highly active hydrogen catalysis. The Ir‐VN catalyst demonstrates exceptional HOR activity with exchange currents 1.8–4.8 times higher than those of noble metal benchmark catalysts, as well as improved durability and CO tolerance. The unique lattice‐matching effect promotes the directional electron transfer and induces shortened Ir─Ir bonds via the strongly coupled interface, therefore resulting in enhanced anti‐oxidation and anti‐CO capability. The Ir‐VN catalyst also demonstrates great HER activity and operational durability in a wide pH range, requiring only 21, 12, and 82 mV to reach 10 mA cm −2 in alkaline, acidic, and neutral conditions, respectively. This work not only deepens the understanding of hydrogen electrocatalysis mechanisms but also inspires the rational design and controllable synthesis of catalysts with active crystal facets for various applications.
In this study, we reported three tungsten compound-supported Ir catalysts with different reduction degrees, Ir-WO3-x, Ir-W/WO3-x, and Ir-W, as pH-universal water splitting catalysts. The Ir-W/WO3-x catalyst, with an optimized local acidic microenvironment for Ir sites under neutral conditions, exhibited the lowest HER overpotential of 60 mV in 1.0 M PBS, while Ir-W achieved the lowest OER overpotential of 336 mV in 1.0 M PBS. Using the Ir-W & Vert;Ir-W configuration, a low cell voltage of 1.593 V at 10 mA cm-2 was achieved in a neutral water electrolyzer.
Although molybdenum nitride (Mo2N) demonstrates exceptional hydrogenation potential, its intrinsic catalytic potential is severely compromised by the unavoidable surface oxidative molybdenum trioxide (MoO3) layer, which severely masks active Mo2N sites for hydrogen dissociation. Here, we report a carbon-supported Mo2N architecture (Mo2N-C) with partially exposed Mo2N sites that strategically balances surface protection and active site accessibility. This engineered Mo2N-C catalyst achieves a CO2 conversion rate of 20.3% at 500 degrees C, with a CO2:H2 ratio of 1:1 and a weight hourly space velocity (WHSV) of 3 x 105 mL gcat-1 h-1, representing a 7-fold enhancement over conventional Mo2N. Remarkably, under a WHSV of 3 x 106 mL gcat-1 h-1, the Mo2N-C catalyst demonstrates unprecedented CO productivity (146.94 x 10-5 molCO gcat-1 s-1), outperforming all reported non-precious metal catalysts. This work establishes a new paradigm for designing oxidation-resistant and high-performance metal nitride catalysts through interface engineering, opening alternative avenues and generalizable approaches for sustainable CO2 conversion technologies.
The global crisis of antimicrobial resistance demands solutions that transcend conventional antibiotic paradigms. Here, we present an atomically engineered VS4-based nanomaterial (TFB-Fe@VS4) featuring dendritic architectures with single-iron catalytic sites, designed as a multimodal reactive oxygen species (ROS) generator against methicillin-resistant Staphylococcus aureus (MRSA) and its recalcitrant biofilms. This biocatalytic system leverages three synergistic mechanisms: nanodendrite-mediated bacterial capture, microenvironment-responsive ROS generation, and ultrasound-amplified oxidative burst, which collectively address the key challenges in eradicating drug-resistant infections. Structural and spectroscopic analyses reveal that atomic iron sites serve dual functions as peroxidase-mimetic catalytic sites and electronic structure modulators, significantly enhancing ultrasound-triggered ROS production through band engineering. The TFB-Fe@VS4 achieves complete MRSA biofilm eradication and rapid wound sterilization in rabbit models with therapeutic outcomes similar to vancomycin yet without detectable inflammation or systemic toxicity. These findings present a design example for artificial biocatalysts that combines precise atomic engineering with multimodal antimicrobial action. The ability to simultaneously target bacterial adhesion, microenvironment adaptation, and on-demand ROS amplification presents transformative potential for treating resistant infections across diverse clinical scenarios, particularly where conventional therapies fail.
Efficient rhodium-based heterogeneous catalysts with exceptional catalytic activity and efficient atom utilization are crucial for converting alkene feedstocks into valuable fine chemicals. Phosphine-functionalized porous organic polymers (POP) have emerged as promising supports for rhodium catalysts. Herein, we synthesize atomic Rh sites coordinated on conjugated porous monophosphine polymers (Rh@POP) for superior heterogeneously catalytic hydroformylation and hydrosilylation of alkenes. The Rh@POP features triphenyl phosphine-Rh coordination and alkenyl nitrile conjugation. A 2.3 % Rh@POP catalyst (Rh mass loading 2.3 wt%) exhibits exceptional activity and selectivity in mild hydroformylation and hydrosilylation of alkenes. The turnover frequency (TOF) reaches 5549 h- 1 in hydroformylation of 1-octene. Remarkably, this catalyst maintains consistent reactivity over 6 recycling runs. The high dispersion of rhodium atoms, phosphine coordination, and alkenyl nitrile-containing POP framework contribute to its outstanding performance. This study offers insights into designing single-atom heterogeneous catalysts with high activity and recyclability, effectively combining the merits of homogeneous and heterogeneous catalysis.
Direct seawater electrolysis represents a cornerstone technology for sustainable hydrogen production, yet anode materials face persistent challenges from chloride-induced corrosion and competitive oxidation reactions. Herein, a Janus-architected heterophase catalyst (HEA-Mo2C) synthesized through a flash Joule-heating method is demonstrated. The heterophase architecture enables dynamic interface reconstruction under operational conditions and forms a chloride-repulsion shield through molybdate (MoO4 2-) generation on the active high-entropy alloy (HEA). Crucially, this biphasic configuration demonstrates self-adaptive surface reconfiguration that synergistically balances corrosion resistance and catalytic efficiency in alkaline seawater. When deployed in anion-exchange membrane electrolyzers, the heterostructured catalyst achieves industrial-grade current density (1 A cm-2 at 1.96 V) with excellent stability over 1000 h at 500 mA cm-2. Mechanistic studies reveal that the sustained performance originates from the continuous interface remodeling between metallic HEA domains and carbide-mediated protective layers. This work establishes heterophase interface engineering as a paradigm for designing durable seawater oxidation electrocatalysts.
Producing high-purity oxygen (O2) has a wide range of applications across diverse sectors, such as medicine, tunnel construction, the chemical industry, and fermentation. However, current O2 production methods are burdened by complexity, heavy equipment, high energy consumption, and limited adaptability to harsh environments. Here, to address this grand challenge, the de novo design of Ru-doped metal hydroxide is proposed to serve as bioinspired O2-evolution catalysts with proton-coupled electron transfer (PCET) pathway for low-energy, environmentally friendly, cost-effective, and portable O2 generation. The comprehensive studies confirm that the lattice H species in Ru-Co(OH)x-based O2-evolution catalyst can trigger a PCET pathway to optimize Ru-oxygen intermediates interactions, thus ultimately reducing reaction energy barriers and improving the activities and durabilities. Consequently, the prepared Ru-Co(OH)x-loaded membrane catalysts exhibit rapid and long-term stable O2 production capabilities. Furthermore, the proposed material design strategy of lattice H-species shows remarkable universality and adaptability to broad Ru-doped metal hydroxides. This efficient, portable, and cost-effective O2 generation technique is suggested to ensure an uninterrupted O2 supply during emergencies and in regions with limited O2 availability or air pollution, thus offering significant societal benefits in broad applications.
Adsorbents are the key components for removing toxic and pathogenic substances in blood purification systems. A good adsorbent is expected to have the properties of high toxin removal efficiency, high selectivity, and reliable biocompatibility. Although conventional materials, such as active carbon, polysaccharides, and resins, have been widely used as adsorbents, their blood purification performances are still limited owing to the small surface area and poor biocompatibility. Nanomaterial-based adsorbents have attracted great attention owing to their unique physicochemical properties, high porosity, and low toxicity. Diverse kinds of nanomaterial-based adsorbents have been used for blood purification, such as carbon nanotubes, graphene, carbon nanofibers, metal–organic frameworks (MOFs), covalent–organic frameworks (COFs), microporous and mesoporous polymers, MXenes, and transition metal chalcogenides/dichalcogenides. These developed nanomaterial-based adsorbents possess extraordinary physicochemical properties, such as adjustable active sites, multifunctional groups, and large specific surface areas, which offer great opportunities for fabricating more advanced nanoadsorbents for hemodialysis and hemoperfusion. This chapter provides a comprehensive discussion on the structural engineering and performance optimization of these 2D nanomaterial-based adsorbents and offers new insights into the design of nanomaterials for blood purification systems.
Chronic refractory wounds present substantial clinical difficulties, owing to their complex wound microenvironments featuring bacterial colonization, sustained inflammation, and deficient angiogenesis. Existing treatment options often fall short of concurrently overcoming these interconnected obstacles, underscoring the demand for integrated therapeutic platforms that combine antimicrobial, anti-inflammatory, and pro-angiogenic properties. Drawing inspiration from natural peroxisomes, a lattice-reconstructed Ru-clusters are designed on FeOOH-based self-adaptive artificial peroxisome with programmed reactive oxygen species (ROS) regulation for infectious and inflammatory chronic wounds. Within this architecture, electron-rich Ru clusters and hole-rich FeOOH domains establish an efficient electron-transfer network. Density functional theory calculations demonstrate that this distinctive electronic structure lowers reaction energy barriers, enabling pH-switchable ROS-catalytic behaviors. Under acidic wound pH, LR-RuC@FeOOH catalyzes ROS generation to disrupt bacterial metabolism and eliminate infections, while under neutral conditions, it efficiently scavenges ROS to alleviate oxidative stress and support tissue repair, enabling a logically sequenced therapeutic progression from infection control to inflammation resolution. In vivo experiments using diabetic foot ulcers confirmed that LR-RuC@FeOOH significantly enhanced bacterial clearance, attenuated inflammatory responses, stimulated neovascularization, and accelerated wound closure. These results position LR-RuC@FeOOH as an artificial peroxisome with stage-specific therapies and promising translational potential for the treatment of refractory diabetic wounds and other infection-related pathologies.
The reverse water-gas shift (RWGS) reaction is crucial for sustainable CO2 conversion, yet catalyst surface remodeling at high temperatures remains a complex and pivotal phenomenon. This study investigates the complex relationship between surface reconstruction and catalytic performance using a series of molybdenum-based catalysts, which can generate different catalytic MoO3 surface layers under RWGS conditions. In-situ characterization techniques and theoretical analyses reveal that the MoO3 layer on MoO3/MoO2-C and MoO3/Mo2N-C is in-situ reduced to MoO2 and metastable MoOx (2