The development of high-performance iron-based Fischer-Tropsch synthesis (FTS) catalysts necessitates innovative strategies to precisely modulate the electronic state of active sites. While Fe2N presents a promising platform, its inherent electron deficiency due to the electronegativity of nitrogen limits its catalytic potential. In this work, we constructed a pyrrolic-nitrogen-enriched carbon-encapsulated Fe2N catalyst (Fe2N@C), in which the N-doped carbon shell modulates the electronic structure of the catalyst. Specifically, the lone-pair electrons of pyrrolic nitrogen delocalize into the π-system of the carbon shell, transforming the shell into an "electron reservoir" that injects electrons into the electron-deficient Fe2N core via Fe−N interfacial coordination. This precise electronic modulation facilitates bridge-type CO activation, generating abundant −CH2− intermediates that subsequently undergo C−C coupling. The Fe2N@C catalyst achieves a CO conversion of 91.6%, nearly double that of Fe2N (51.2%), and achieving a C5+ yield of 116.5 mmol gcat−1 h−1 at a high space velocity of 30000 mL g−1 h−1. Furthermore, the carbon shell imparts structural stability, effectively suppressing oxidation during the reaction. This work highlights interfacial modulation as a powerful strategy to optimize the electronic structure of catalysts, offering a promising approach for designing high-performance FTS catalysts.
Electrolyte additive engineering is regarded as an effective strategy for dual-interface optimization in four-electron aqueous zinc-iodine batteries (AZIBs). However, realizing durable Ah-level AZIBs with industrial-grade parameters (≥10 mg cm-2 I2 cathode mass loading, ≥5 mAh cm-2 Zn anode areal capacity) remains a significant hurdle. Here, we compare various nitrogen-containing cationic ligands to evaluate their synergistic regulation on iodine immobilization and Zn nucleation. This screening successfully establishes N-methylimidazolium chloride (MImCl) as a premier electrolyte additive for stabilizing dual-interface coordination. Upon discharging, the adsorption of MIm+ on the I2 cathode enables electrostatic binding with polyiodides and ICl2-. This interaction not only suppresses the polyiodide shuttle but also shields the I+ species from hydrolysis, promoting a robust and reversible four-electron I-/I0/I+ redox chemistry at elevated I2 mass loading. On the Zn anode, MIm+ preferentially adsorbs onto its surface during charging, accelerating Zn2+ deposition kinetics for dendrite suppression while passivating parasitic reactions, realizing uniform large-capacity Zn plating/stripping. As a result, the engineered 1.4 Ah four-electron Zn||I2 pouch cells achieve an excellent cyclability of 800 cycles and an ultrahigh cathode-mass-specific energy density of 455 Wh kg-1, surpassing most aqueous Zn-based systems in the Ah-class regime.
Biodegradable supercapacitors represent a promising alternative to conventional power sources for implantable electrical stimulation therapies. However, their development has been impeded by the lack of electrode materials that simultaneously offer high-density redox-active sites, efficient charge transport, and biocompatibility under physiological conditions. To overcome these challenges, we developed a biodegradable supercapacitor incorporating iron single-atom catalysts anchored on carbonized bioinspired self-assembled architectures (Fe SA/cBSAs). Electrochemical experiments and density functional theory (DFT) calculations revealed that the single-atom Fe sites not only introduced additional pseudocapacitance via the reversible Fe3 +/Fe2 + redox pair but also weakened the Na & horbar;O interaction through surface-potential redistribution, accelerating Na+ desorption and diffusion. This dual mechanism-combining enhanced redox activity with weakened Na+ binding-intensifies capacitive kinetics to synergistically improve both faradaic and electric-double-layer charge storage efficiencies, thereby yielding a marked increase in areal capacitance, energy density, and voltage stability without compromising charge-discharge rate capability. Fabricated using a polyvinyl alcohol/phosphate-buffered saline (PVA/PBS) hydrogel electrolyte and polylactic acid (PLA) encapsulation, the device exhibited excellent biocompatibility and outstanding biodegradability in vivo. In a murine inflammatory pain model, electrical stimulation delivered at the ST36 acupoint via our biodegradable supercapacitor markedly alleviated pain behavior and reduced inflammatory markers, confirming its therapeutic potential.
Acute kidney injury (AKI) is a clinical syndrome that frequently progresses to chronic kidney disease (CKD) and end-stage renal failure. To address the lack of targeted clinical treatments, we developed a self-powered bioelectronic medicine (sp-BEM) integrated with a hybrid triboelectric-piezoelectric nanogenerator (h-TPENG) for precise low-level vagus nerve stimulation (LL-VNS). The passive device architecture eliminated the conventional bioelectronic medicine reliance on and limitations of batteries and pulse generators. By outputting biosafe pulsed electrical signals sufficient to activate vagus (parasympathetic) nerves, sp-BEM enabled flexible, portable, and long-lasting neurostimulation therapy. Electrophysiological assessments confirmed that sp-BEM precisely transmits electrical signals downstream. sp-BEM could reverse and restore renal dysfunction and histological deterioration in an established AKI progression model by administering LL-VNS. Mechanistic studies demonstrated that the renal protective effects of sp-BEM were mediated through gut-kidney axis modulation, with coordinated suppression of fibrotic cascades, activation of tissue-reparative signaling, and replenishment of microbiota-dependent renal protective metabolites.
Conventional RNA-based vaccines rely on lipid nanoparticles (LNPs) for delivery; however, concerns exist regarding the potential systemic toxicity of their chemical composition, and their immune-activating capabilities require further enhancement. Inspired by Mg2+ as a key ion for maintaining RNA secondary structure stability, we developed a one-pot method for directly synthesizing a circular RNA-based formulation-adjuvant integrated nanovaccine (CircRNA@FAiNVac) capable of delivering programmed circular RNA (circRNA) based on biomimetic mineralization principles. Specifically, during circRNA rolling circle transcription, the controllable crystallization of magnesium pyrophosphate (MgPPi) nanoparticles was achieved by enhancing the reaction kinetics between ribonucleotide triphosphates and Mg2+, thereby encapsulating circRNA within the nanoparticles and forming a protective carrier that also functions as an adjuvant. Based on the specific hydrolysis of MgPPi by pyrophosphatase, CircRNA@FAiNVac can efficiently release RNA intracellularly, thereby facilitating gene expression. Unlike LNPs, which often contain toxic excipients, the vector structure of CircRNA@FAiNVac consisted only of nucleic acid precursors and ions, exhibiting good biocompatibility and reducing adverse reactions. More importantly, CircRNA@FAiNVac possessed potent immune activation capabilities; its self-adjuvanting activity promoted multimodal immune activation, enhancing both humoral and cellular responses. Animal experiments confirmed that the innovative design of CircRNA@FAiNVac ensured stable and sustained autonomous expression of the SARS-CoV-2 receptor-binding domain, while the nanostructure activated multiple immune pathways, providing potent protection. The formulation-adjuvant integration strategy of CircRNA@FAiNVac based on biomimetic mineralization principles provides an alternative approach for the development of next-generation vaccines. Based on antigen sequence optimization, it enables rapid customized development of vaccines targeting variant strains.
Single-atom and nanocluster (SA/NC) catalysts represent the forefront of SA catalysis due to their synergistic catalytic active sites while maintaining exceptional atomic efficiency. However, the intrinsically high surface energy of both SAs and NCs drives their aggregation on carriers, typically resulting in the formation of stable nanoparticles rather than isolated atomic species. In this work, we proposed a biphasic interfacial atomic etching strategy (BIAES) to construct atomically defective black phosphorus nanosheet (ad-BP NS) carriers, enabling the universal high-density loading of metal SAs and NCs on ad-BP NSs (M-SA/NC@ad-BP, M = Co, Fe, Ni, Cu). Experimental and theoretical calculations indicated that the high reactivity and spatial confinement of the atomic-scale defective sites in ad-BP NSs were crucial for the synthesis of M-SA/NC@ad-BP. Strong metal-support interactions, coupled with NC-induced electronic modulation of SA, confer exceptional electrocatalytic activity across multiple reactions. This strategy lays the foundation for the design of high-performance 2D carrier-based SA/NC electrocatalysts.
ABSTRACT Ferroelectric materials, characterized by their spontaneous and reversible polarization under an electric field, have attracted extensive research interest. Their unique properties render them ideal for applications ranging from data storage and energy harvesting to sensing and catalysis. Driven by the demand for miniaturized and energy‐efficient nanoelectronic devices, precise control over ferroelectric performance has become a central focus. This review comprehensively summarizes key strategies for tailoring ferroelectric properties, with a focus on external field manipulation, low‐dimensional confinement, interface engineering, and topological structuring. We subsequently highlight recent advances in cutting‐edge applications in memory, neuromorphic computing, sensors, energy conversion, and catalysis. Finally, we present future research directions to guide the development of next‐generation ferroelectric materials and devices.
Acute liver injury is closely linked to the pathophysiological cascade effect of iron dysregulation and oxidative stress caused by ferroptosis. Existing monotherapies using iron chelators or antioxidants fail to meet the need for bidirectional regulation and lack targeting and specificity. In this study, nanomedicine composed of piezoelectric materials and nanozyme (BTO@CeO2) was developed for piezo-mediated dual-mode therapy of iron homeostasis regulation and free radical scavenging under localized ultrasound excitation: piezoelectric polarization reduced CeO2’s energy barriers and enhanced its superoxide dismutase-like enzyme activity through electron injection and orbital hybridization for efficient reactive oxygen species (ROS) scavenging; BTO-generated holes reduced unstable iron pools by oxidizing divalent iron ions to achieve iron homeostasis; ultimately achieving efficient and high spatiotemporal precision in reversing ferroptosis. BTO@CeO2 achieved antioxidant and iron metabolism reprogramming by regulating ferritinophagy, successfully alleviating drug-induced acute liver injury. This work demonstrates the great potential of piezoelectric-nanozyme synergistic precision treatment of metabolic diseases.
Integrating biological proton transport with semiconductor photoelectronics offers a powerful route toward next-generation bioelectronic sensing. Here, a light-driven bio-p-n junction integrating bacteriorhodopsin (bR) with poly(3-hexylthiophene) (P3HT) is presented. Electron-proton coupling facilitates controlled modulation of bR-mediated proton transport, leading to a stable and highly linear electronic response along with enhanced interfacial charge separation. Mechanistic analysis reveals that photoexcited electrons from P3HT lower the energy barrier for proton translocation in bR, while pH-regulated surface charges modulate ion mobility at the interface. This molecular-level coupling strategy bridges biological specificity with semiconductor scalability, providing a generalizable framework for precise, stable, and biocompatible real-time pH monitoring in biomedical and environmental applications.
Microbial electrosynthesis (MES) leverages microorganisms to biologically convert CO2 into value-added chemicals under mild conditions, making it a promising approach to effectively capture and utilize CO2. MES systems can also integrate renewable energy sources (e.g., light) to create photosynthetic biohybrid systems that link biosynthetic pathways with inorganic light absorption. Carbon quantum dots (CQDs), as a type of nanomaterials, have shown broad application prospects in the field of bioenergy production due to their excellent optical properties and biocompatibilities. In this study, we coupled pyrrolic-N CQDs (pN-CQDs), which are Ntype semiconductors and exhibit significant photoresponsive activities, with electroautotrophic bacteria (EAB) to construct a photosynthetic hybrid system for converting CO2 to acetate. This system achieved an acetate yield of 0.41 g L- 1 d- 1, which was two times higher than that in the control group (no pN-CQDs and light). Microbial community analysis showed that the addition of pN-CQDs significantly increased the relative abundance of acetogen Acetobacterium from 23.40 % to 31.52 %. Metatranscriptomic analysis further suggested that genes related to electron transfer (cytochrome, hydrogenase, riboflavin synthase) were significantly up-regulated in the presence of pN-CQDs and under light conditions. Concurrently, genes related to carbon fixation pathways (Wood-Ljungdahl pathway and reductive citric acid cycle) were highly expressed under light conditions. These results suggested pN-CQDs promoted the efficiency of extracellular electron transfer in MES systems under photoexcitation. This study highlights the synergistic potential of combining the high light absorption efficiency of solid-state semiconductors with the exceptional catalytic capabilities of microorganisms, resulting in a transformative advancement in MES performance.
Photoelectrochemical water oxidation is limited by sluggish interfacial charge transfer and fragile catalyst photoanode contacts. We introduce a polydopamine (PDA) interlayer that bridges NiFeOx and cobalt-doped bismuth vanadate (Co:BiVO4), forming an intimate and ligand-bonded interface with strong electronic coupling. The bridge strengthens the interfacial electric field (IEF) strength, accelerates carrier separation and transfer, suppresses surface recombination, and stabilizes oxygen evolution intermediates, lowering kinetic barriers and external bias. First principles density functional theory with crystal orbital Hamilton population shows optimized adsorption at Fe sites and a reduced barrier at the rate-determining step (RDS), consistent with performance. Under air mass 1.5 global (AM 1.5 G) illumination, the optimized photoanode delivers 5.47 mA/ cm2 at 1.23 V versus reversible hydrogen electrode (vs. RHE) and 95.03% oxygen Faradaic efficiency with excellent stability. Because the electrode operates under low energy input, we demonstrate a closed-loop self powered system in which a compact triboelectric and electromagnetic harvester, with a wind-to-electricity conversion efficiency of 49.5%, supplies sufficient power for continuous water splitting under ambient wind, achieving near stoichiometric gas evolution.
Using the density functional theory(DFT), the comprehensive and in-depth exploration was conducted into the structure, electronic properties, CO adsorption and activation performance of Fe atoms modulated by graphene confinement to reveal the influence of different coordination environment of Fe active centers on Fischer-Tropsch (FT) performance. The binding energies of Fe-doped single-atom defect graphene(Fe-C@graphene) and Fe-doped di-atom defect graphene are-7.49 and-6.50 eV, respectively, which indicates that Fe-C@graphene structure exhibits greater stability compared to the Fe-2C@graphene. The density of states(DOS) of Fe-C@graphene exhibits the more significant left-shift compared to that of Fe-2C@graphene, with values of 1.5 and 0.8 eV, respectively. The greater left-shift indicates that the Fe-C@graphene structure possesses lower energy, and the higher stability. The adsorption energies of CO on Fe-C@graphene and Fe-2C@graphene are-1.43 and-1.69 eV, respectively, which reflects that CO adsorption on Fe-2C@graphene is more stable than that of Fe-C@graphene. The d band center values of Fe-C@graphene and Fe2C@graphene are-1.26 and-0.83 eV, respectively, while their energy band gaps are 0.45 and 0.01 eV, respectively. The closer the d-band center is to the Fermi level, and the smaller the band gap, which is more conducive to the adsorption of species. Thus, compared with Fe-C@graphene, CO has a higher propensity to be adsorbed onto Fe-2C@graphene. The band gap of Fe-2C@graphene-CO increases by 0.25 eV, while Fe-C@graphene decreases by 0.04 eV; the antibonding component of Fe-C@graphene-CO is more than that of Fe-2C@graphene-CO, and the integrated crystal orbital Hamilton population(ICOHP) values are-1.99 and-2.50 eV. These suggest that the interaction between Fe-2C@graphene and CO is stronger, while strong interaction is unfavorable for CO activation. On the Fe-C@graphene and Fe-2C@graphene, the most favorable pathway for CO activation follows the sequence: CO* -> CHO* -> CH*+ O*, with an effective energy barrier of 2.53 and 3.50 eV, respectively. It is easier for CO activation on Fe-C@graphene. Therefore, the three-coordination structure of the active center Fe is more stable and beneficial for enhancing FTS activity.
Abstract The Fischer−Tropsch synthesis (FTS), the key industrial process for the transformation of syngas into valuable chemicals and clean fuels, benefits from advanced catalyst design. Iron carbide nanoparticles (Fe3C) and their graphene oxide-derived counterpart (Fe3C/Graphene) were successfully synthesized. Fe3C/Graphene exhibits a large specific surface area, high pore volume, and abundant surface defective sites provided by the reduced graphene oxide support. Together with the stabilized Fe3C active phase, these features promote CO activation and C−C coupling, leading to enhanced CO conversion, higher C5+ selectivity, and suppressed CH4 formation comparedwith Fe3C. Density functional theory calculations reveal that the improved CO activation on Fe3C/Graphene originates from reduced electron transfer and weakened Fe−C and C−O bonds. For Fe3C, the rate-determining step is CO* + H* → CHO*, whereas for Fe3C/Graphene, the rate-determining step is CHO* → CH* + O*. It also reveals that Fe3C/Graphene accelerates this step, corroborating the enhanced CO activation observed experimentally. Furthermore, the simulations confirm that defective graphene significantly raises the effective barrier for methanation, perfectly rationalizing the suppressed CH4 formation. These findings demonstrate that the introduction of graphene oxide is a effective strategy for tailoring the catalytic performance of Fe-based FTS catalysts.
Effective in situ regeneration and functional reconstruction of large-scale bone defects remain a formidable clinical challenge. The endogenous metal ions have been shown to critically regulate immune responses and bone remodeling, but methods for precisely regulating the spatiotemporal recruitment dynamics of endogenous ions are still lacking. Here, we develop a novel endogenous metal ion-enriched immunostimulation-amplified bone biomimetic scaffold (emia-BBS) based on the hierarchical multi-level assembly of nano-hydroxyapatites (nHAs), collagen fibrils, and mussel adhesion proteins (MAPs). The emia-BBS not only mimics the nanostructure and mechanical properties of native bone, but notably, the assembled MAPs endow emia-BBS with abundant lysine and dopamine chemical structures, enabling efficient capture of endogenous metal ions to amplify ion-mediated immunomodulation. Functionally, in large-scale mandibular defects, emia-BBS-induced enrichment of endogenous metal ions could recruit and reprogram macrophages, thereby enhancing the innate immune response. These M2 macrophages, recruited by the emia-BBS-metal ion complex, in turn, facilitate the recruitment and osteogenic activation of endogenous LepR⁺ skeletal stem cells via the CCL5/CCR5/STAT3 axis. This study introduces an immunomodulatory strategy that harnesses endogenous ion dynamics to amplify regenerative signals, providing a precisely guided and clinically applicable approach for critical-sized bone defect repair.
Adjuvant skincare formulations possessing anti-inflammatory and antibacterial properties can alleviate treatment-related side effects and enhance patient adherence in acne management. Paeonol (PAE), totarol (TOT), and ergothioneine (ERG) demonstrate promising anti-acne activity. However, their clinical translation is hindered by poor solubility, limited stability, and insufficient skin permeation. To address these limitations, we coencapsulated PAE, TOT, and ERG into hyaluronic acid (HA)-modified nanoliposomes (NLPs). Compared to the NLPs modified with HA with high-molecular-weight, those formulated with miniHA (3-10 kDa) exhibited superior skin penetration capability and cellular uptake efficiency. The miniHA modified NLPs co-encapsulated PAE, TOT, and ERG (PTE-NLPs) exhibited excellent biocompatibility in both in vitro cytotoxicity and chicken embryo chorionic allantoic membrane irritation assays. Compared to free functional ingredients, PTE-NLPs demonstrated significantly enhanced anti-inflammatory and antibacterial efficacy in cellular assays. Furthermore, in 3D skin models, PTE-NLPs suppressed Transient Receptor Potential Vanilloid 1 (TRPV1) expression, indicating a potential mechanism for attenuating neuronal hyperreactivity. The anti-inflammatory activity was subsequently validated in vivo. These findings collectively demonstrate that miniHA-modified NLPs provide a safe and efficient platform for co-delivering synergistic anti-acne actives, highlighting their strong potential as an adjuvant therapy for acne management.
Nanomedicines (NMs) have demonstrated considerable promise in the treatment of diverse diseases. Their dynamic interactions with biological systems often trigger a cascade of complex physiological responses. Revealing the structure-activity relationships that underlie these interactions is critical for the rational design of safer and more effective nanotherapeutics. Among emerging two-dimensional (2D) nanomaterials, black phosphorus (BP) has garnered increasing interest owing to its unique physicochemical properties and inherent biodegradability. Featuring a tunable bandgap, high carrier mobility, and excellent biocompatibility, BP exhibits significant potential in biomedical applications. Due to its multidimensional functional characteristics, BP can elicit a variety of distinct biological effects upon interfacing with biological systems, including oxidative stress, ionic disturbance, and immune activation. A comprehensive understanding of these regulatory effects and their underlying mechanisms will help promote the broader medical application and even clinical translation of BP-based NMs (BP NMs). In this review, we systematically summarize the application of BP as NMs in cancer treatment, tissue engineering, and regenerative medicine based on its intrinsic biological effects rather than carrier effects, and further elaborate the mechanisms underlying BP’s interactions with biological systems across these contexts. Comprehensively mapping the relationship between the structure, properties, and biological activity of BP will provide directions for the future design aimed at improving the safety and effectiveness of BP NMs.
The clinical efficacy of platinum-based chemotherapeutics is frequently diminished by the emergence of resistance during prolonged treatment. Cisplatin (DDP)-resistant tumors adapt to chemotherapeutic stress by establishing a new state of adaptive homeostasis that sustains cellular survival under drug pressure, albeit at the expense of high metabolic burden and acquired vulnerability. Exploiting this intrinsic weakness, we designed a DDP-doped black phosphorus (BP) nanomedicine protected by polydopamine coating (DDP-BP@PDA) that synergistically delivered DDP and piezoelectric BP to precisely disrupt resistance homeostasis and thereby reverse DDP resistance. DDP-BP@PDA altered the intracellular uptake pathway of DDP and disrupted the redox balance of resistant cells via piezocatalysis. Concurrently, piezoelectric polarization enhanced the peroxidase-like activity via electron injection, leading to the generation of substantial reactive oxygen species (ROS). This ROS burst compromised the integrity of the endoplasmic reticulum (ER) membrane and exacerbated the protein-folding burden, thereby amplifying ER stress. Mechanism study reveals that excessive ER stress downregulated the expression of DNA repair proteins, making resistant cells highly sensitive to DDP-induced DNA damage. Through these synergistic effects, DDP-BP@PDA disrupted the adaptive homeostasis of DDP-resistant cells, thereby significantly inhibiting the progression of DDP-resistant tumors. This study establishes a promising therapeutic strategy to combat DDP-resistance via piezoelectric-driven disruption of adaptive homeostasis.
The utilization of solar energy in driving chemical reactions through photocatalysis is essential in promoting a sustainable future. However, the development of synthetic materials with photochemical properties continues to pose a significant challenge in the field of materials science. Metal-organic frameworks (MOFs) provide a powerful platform for establishing effective photocatalyst systems due to their atomically precise structures, modifiable chemical environment, and semiconductor-like behavior. This work comprehensively reviews the design and synthesis strategies of MOF-based photocatalysts, with particular emphasis on light absorption, photogenerated carrier separation, catalytic active sites, and reaction selectivity. The objective of these approaches is to identify and rationalize design parameters to generate optimized chemical composition, functional nanostructures, and corresponding performance parameters. In this review, we highlight how the parameters of MOFs can serve as the knobs for maneuvering light harvesting, charge separation and migration, as well as altering subsequent surface chemical reaction. We hope that this will contribute towards further understanding and inspiration for developing photocatalytic reaction based on MOFs materials.
Piezo-photocatalysis regulates the spatial and energy distribution of photogenerated carriers through mechanical energy, offering a promising strategy for enhancing photocatalytic activity. However, piezo-photocatalysts still suffer from inferior carrier concentration and separation efficiency. Herin, a Bi4Ti3O12-CuBi2O4 p-n heterojunction piezo-photocatalyst (BTO-CBO) was prepared, combining with a Cu(II)-catalyzed Fenton-like reaction to realize efficient removal of colored dyes (MB) and recalcitrant antibiotics (LEV and OTC). Due to the co-drive of p-n heterojunction and piezoelectric polarization certified by photoelectrochemical measurements, PFM and DFT calculations, the degradation performance of as-prepared BTO-CBO on MB was dramatically improved under co- excitation of visible light and ultrasound compared with under single light irradiation and single ultrasound conditions, and typically was always significantly better than the pure BTO, CBO and BTO/CBO mechanical mixtures. Impressively, after the introduction of trace H2O2, the piezo-photocatalytic performance of the optimum composite ratio BTO-CBO-0.7 was further improved, and the outstanding piezo-photocatalytic performance also displayed in LEV and OTC degradation, with a removal of nearly 87.8 % and 96.0 % of LEV, and OTC within 80 and 50 min, respectively. Such superior performance highly depended on the vibrating piezoelectric field and the interfacial electric field, which significantly increased the driving force and suppressed the recombination of photogenerated carriers, and thereby promoted Cu(II)/Cu(I) cycling and H2O2 activation in photo-Fenton-like system to produce more active species verified by sacrificial agent experiments and XPS, based on which and energy band theory, the catalytic degradation mechanism was proposed. Overall, this study provides new insights for the design of high-performance catalysts.