Real exhaust streams rarely contain a single pollutant: NOx coexists with volatile organic compounds (VOCs) in flue gas from petrochemical production, chemical manufacturing, and waste incineration, yet catalysts that couple NH3-SCR with VOC oxidation typically suffer competitive adsorption, sulfur poisoning, and HCN byproduct formation. Here we engineer an epitaxially stabilized CuO overlayer on Ti1-xInxO2 that breaks the activity-selectivity-stability constraint by creating electron-poor, high-symmetry Cu-O sites and activating lattice-oxygen redox at the oxide-oxide interface. Interfacial strain and charge transfer increase Cu-O covalency and Lewis acidity, accelerating NOx reduction via an Eley-Rideal pathway while diverting sulfate deposition away from Cu. Concurrently, interface-activated lattice oxygen sustains deep oxidation of CH3SH (a representative S-VOC) through a Mars-van Krevelen cycle, suppressing HCN. Epitaxial interfaces thus offer a general route to poison-resistant multipollutant catalysis.
The catalytic hydrolysis of per- and polyfluoroalkyl substances (PFAS) holds significant potential for environmental remediation; however, the chemically inert C-F bond poses substantial challenges for achieving efficient low-temperature activity. Herein, we demonstrate that RuOx clusters embedded in mesoporous Al2O3 nanosheet (RuOx/Al2O3) catalysts achieved the complete decomposition of CF4, one of the most chemically inert PFAS, at an unprecedented low temperature of 450 °C, outperforming all catalysts reported to date. The extraordinary CF4 hydrolysis performance is attributed to synergistically enhanced C-F bond activation and proton supply. Specifically, the strong electronic interaction between RuOx clusters and Al2O3 promotes the CF4 adsorption and C-F cleavage on Al sites in RuOx/Al2O3. Furthermore, the Ru sites in RuOx/Al2O3 promote H2O dissociation into *H and *OH, which enables the continuous regeneration of adjacent Al-OH groups and supplies sufficient protons for defluorination in the CF4 hydrolysis reaction. This study paves the way for designing and developing highly efficient catalysts for low-temperature catalytic hydrolysis of PFAS.
Dry reforming of methane (DRM, CH4 + CO2 → 2H2 + 2CO) offers a promising route for converting two greenhouse gases into valuable syngas. However, conventional thermal catalysis requires extreme temperatures (>800 °C) to overcome high energy barrier, leading to significant energy consumption and catalyst deactivation. Herein, we develop a Pt1-Ni1/CeO2 photothermal catalyst with atomically dispersed Pt1-Ni1 paired active sites for DRM under mild conditions. At 450 °C under light illumination, the catalyst exhibits high H2 and CO production rates of 4.62 and 4.65 mmol gcatalyst-1 min-1, respectively, with a H2/CO ratio close to unity (0.99). Mechanistic investigations reveal that light irradiation induces photogeneration of electrons and holes in CeO2, which directionally transfer to atomic Ni and Pt sites, respectively, inducing asymmetric charge polarization that promotes the activation of reactants. Steady-state isotope transient kinetic analysis combined with diffuse reflectance infrared Fourier transform spectroscopy (SSITKA-DRIFTS) measurement identifies the critical *CHxO intermediate formed via *CHx + *O → *CHxO, a key step that suppresses deep dehydrogenation and carbon deposition. This work elucidates the regulation of parallel reactions over asymmetric dual-atom pairs in the transformation of CH4 + CO2 via photothermal synergy, paving the way for the targeted conversion of C1 molecules under mild conditions.
Dysregulated osteoclast activity underlies pathological bone resorption in skeletal metastases and metabolic bone disorders such as diabetes, yet effective therapeutic strategies remain scarce. Here, we present a mesenchymal stem cell (MSC)-based cellular backpack platform for metabolism-guided and bone-targeted therapy. This biohybrid system couples MSCs with lipid-coated, biotin-streptavidin-linked nanoparticles that encapsulate the phosphoglycerate dehydrogenase (PHGDH) inhibitor NCT503 and are enriched with calcium via biomineralization. Driven by CXCR4-mediated MSC homing, the cellular backpacks selectively localize to osteoclast- and tumor-rich bone microenvironments. NCT503 inhibits the serine synthesis pathway, suppressing NFATc1-dependent osteoclastogenesis and tumor progression, while calcium ions disrupt the reciprocal metabolic coupling between osteoclasts and cancer cells. Simultaneously, calcium enrichment enhances MSC chemotaxis, migration, and osteogenic differentiation, enabling precise delivery and bone regeneration. In murine models of bone metastasis and diabetic fracture, this strategy mitigates osteolysis, restrains tumor growth, and accelerates skeletal repair. Collectively, this study introduces a multifunctional, cell-guided therapeutic platform that synergistically integrates metabolic intervention, osteoclast-tumor modulation, and regenerative repair, offering a promising avenue for the treatment of dysregulated bone diseases.
Ammonia (NH3)-based selective catalytic reduction (SCR) is a mainstream flue gas denitration technology for stationary and mobile sources, but NH3 slip remains a critical challenge from mismatches between stoichiometric reaction requirements and fluctuating nitrogen oxides (NOx) concentrations. Herein, we show organic amines (e.g., n-butylamine, n-B) act as smart reductants for SCR systems. Unlike NH3, n-B reacts stoichiometrically with NOx and undergoes NO-accelerated self-elimination when overdosed over TiO2-supported VOx catalysts. Mechanistic studies reveal Ti─OH sites on the catalyst facilitate n-B adsorption and activation, with the *NH3 intermediate driving NOx reduction. *NH2 from excess n-B oxidizes to nitrites and NO2 under NO+O2, which further react with *NH3 via an internal SCR pathway, avoiding free NH3 formation and slip. We propose a hybrid reductants system (NH3 + n-B) enabling efficient NH3 slip suppression over a reductant/NOx molar ratio of 1.2, providing a promising strategy without modifying existing SCR hardware or structures.
Intelligent gas-sensing technology that accurately and stably identifies gas categories in complex atmospheres is critical for protecting public safety and environment. However, competing interactions among different gases on sensing surfaces can trigger interference even poison of sensors. Here, we present a bio-inspired atomic internalization process that produces locally enriched single Pt species, enabling highly selective and interference-resistant gas detection. By engineering Sn/C precursors as homologous receptors, Pt3Sn alloys are two-step redistributed into high-density single Pt species within regionalized SnO2 surface. This structure constitutionally alters the distribution patterns of NO2 molecules and thus delivers accurate NO2 monitoring in multicomponent atmospheres and stable detection for over 550 days, surpassing state-of-the-art commercial devices. Further integrating characteristic-specific sensors into arrays, the resulting device further achieves 100% classification accuracy for single and mixed gases at ultralow cost. Moreover, we demonstrate an autonomous “cruise-monitoring” system by equipping the sensor on a robot to detect and identify NO2 in real time. Our findings thus guide the accurate analysis and interference-resistant detection in complex gas mixtures. Accurate gas sensing remains challenging because conventional semiconductor sensors often struggle with selectivity and interference from complex gas mixtures. Here, the authors use a single-atom catalyst strategy to stabilize isolated Pt atoms on regionalized SnO₂ surfaces, enabling selective and antiinterference NO₂ detection. The resulting sensor operates continuously in air for more than 550 days and achieves high classification accuracy across a library of 37 gases, highlighting the promise of single-atom-engineered sensors for reliable gas monitoring.
MRSA associated infections in skeletal and soft tissues remain formidable clinical issues with limited treatments, due to antibiotic resistance, biofilm formation and pathological hypoxia. Herein, yolk-shell nanoplatform (BMP@M) is developed for targeted mild photothermal-triggered cascade gas therapy against MRSA infections. BMP@M features a polydopamine photothermal yolk and mesoporous MnO2 shell loaded with NO donor (BNN6), enabling spatially separated heat generation and cascade NO release via gradual photothermal conduction. Macrophages are preactivated with MRSA membrane vesicles (MVs) to obtain engineered macrophage MVs with elevated Toll-like receptor 2, endowing BMP@M with MRSA-specific targeting and infectious lesion-targeting ability. The photothermal effect of BMP@M further promotes injectable thermosensitive chitosan to form tissue repair matrix (BMP@M/C). The synergistic photothermal-gas therapy effectively eradicates MRSA and disrupts biofilms. Moreover, the MnO2 shell in situ decomposes pathological H2O2 into O2, alleviating hypoxia. The coordinated release of NO and O2 restores mitochondrial function, scavenges ROS, suppresses NF-κB/NLRP3 inflammatory axis, and drives M2 polarization. In models of MRSA-induced osteomyelitis and full-thickness skin defects, BMP@M/C achieves effective infection control, anti-inflammatory, osteogenesis and angiogenesis effects. This study offers a combined antibacterial, immunomodulatory, and regenerative approach for infected tissue repair.
Developing highly efficient selective catalytic reduction catalysts possess both outstanding alkali metal resistance and thermal endurance remains a great challenge to effective NOx reduction under harsh operation conditions. Herein, self-adaptive Ce-Nb dual-metal embedded attapulgite catalyst enabling durably alkali-resistant and thermal-tolerant NOx reduction has been innovatively demonstrated. In details, experimental results reveal that inherent Si-OH groups on the attapulgite skeleton and implanted Nb2O5 species can efficiently anchor alkali metal poisons through coordination bonding and ion exchange, thereby safeguarding active sites against deactivation and structural damage. Moreover, adsorbed alkali metal cations facilitate the reconstruction of original attapulgite framework, stabilize dual-chain Si-O tetrahedral structure, and substantially mitigate skeleton structural collapse caused by severe thermal treatment. Owing to the unique self-adaptive structural regulation effect of dual-metal embedded attapulgite architecture, the catalyst exhibits excellent and durable NOx removal performance with prominent alkali resistance and thermal stability. This study offers a novel and reliable strategy for rational design and fabrication of high-performance denitrification catalysts suitable for long-term nitrogen-containing gaseous contaminant purification.
SO2-induced catalyst deactivation from the sulfation of active sites remains a critical challenge for selective catalytic reduction (SCR) of NOx with NH3 at low-temperatures. Herein, we developed a data-driven machine learning strategy to discover highly active and SO2-tolerant MnOx-based catalysts. A catalyst database was constructed from literature with NOx conversion as the target, and regression methods imputed missing values. An SVR model combined with three-step feature selection and repeated random-split validation achieved accurate prediction. This model facilitates high-throughput virtual screening, thereby reducing reliance on trial-and-error experimentation. Mn0.63La0.05Ni0.32Ox was identified, synthesized, and experimentally validated, showing excellent low-temperature NH3-SCR activity and SO2 tolerance. Systematic experiments and density functional theory (DFT) calculations revealed the SO2-resistant mechanism. La-doped MnNiO3 (La-MnNiO3) increased electron occupancy of eg orbitals of Mn, enhancing energy matching with S 3p orbitals of SO2 and strengthening SO2 adsorption on La-MnNiO3 sites of Mn0.63La0.05Ni0.32Ox. La-MnNiO3 could act as protective sites that preferentially bind SO2 to form sulfate species, preventing MnOx active sites of Mn0.63La0.05Ni0.32Ox from sulfation. Consequently, Mn0.63La0.05Ni0.32Ox achieved an efficient and stable NOx removal in presence of SO2. This work demonstrates that integrating machine learning with experimental validation offers an efficient approach for the rational design of SO2-tolerant low-temperature NH3-SCR catalysts.
ABSTRACT In this paper, we develop a photothermal‐responsive hydrogel (CNB‐ePRP) based on engineered platelet‐rich plasma (PRP)/sodium alginate (SA) hydrogel integrating thrombin‐functionalized composite nanobottle (CNB) to treat diabetic wounds. Within CNB‐ePRP, the CNB consists of polydopamine nanobottle loaded with thrombin, personalized drugs and a phase‐change material. As a photothermal agent and dual‐stage controller, CNB not only enables in situ PRP activation at physiological temperature to slowly release various growth factors (GFs) via thermal‐triggered thrombin release, avoiding premature burst release of GFs, but also accelerates the release of GFs from the CNB‐ePRP hydrogel through mild photothermal heating under 808 nm laser irradiation. Meanwhile, SA enhances hydrogel stability and prolongs GF release kinetics. Consequently, CNB‐ePRP achieves on‐demand delivery of GFs, significantly promoting angiogenesis, cell proliferation and M2 macrophage polarization. Moreover, CNB‐ePRP can mitigate oxidative stress via the antioxidant activity of CNB. Furthermore, vancomycin is loaded into CNB to construct a multimodal antimicrobial hydrogel (VCNB‐ePRP) that combines antibiotic and photothermal therapy to efficiently eradicate MRSA and promote healing in MRSA‐infected diabetic mouse wounds. Collectively, this study offers a smart PRP‐derived platform, characterized by in situ PRP activation, on‐demand GFs release, personalized antimicrobial loading and multifunctional therapy, for managing diabetic wounds with great translational potential.
Photocatalytic degradation of toxic and persistent perfluorooctanoic acid (PFOA) represents a promising remediation approach, yet its practical application is hindered by slow surface reaction kinetics and poor defluorination efficiency. Herein, we report the rational construction of dual-functional Bi single atoms (SAs) on Ga2O3 (Ga2O3/Bi) for efficient and chemical-free photodegradation of PFOA. The optimal Ga2O3/Bi composite achieves a degradation rate of 100% and a defluorination ratio of 67.1% for 20 mg L-1 PFOA within 8 min, along with a high reaction rate constant of 0.5429 min-1, placing it among the top-performing photocatalytic systems for PFOA degradation to date. Moreover, the defluorination ratio further increases to 96.7% under prolonged irradiation. The incorporation of Bi SAs not only promotes the adsorption and activation of PFOA via strengthened orbital hybridization between Bi 6p and F 2p orbitals, but also enhances the generation of reactive oxygen species through improved charge separation. Furthermore, the stepwise decarboxylation and defluorination pathway, as well as the reactive species involved in PFOA photodegradation, are systematically elucidated through experimental investigation and theoretical calculations. This work brings deep mechanistic insight into the stepwise degradation of PFOA and proposes an effective active site design strategy for treating persistent pollutants.
Age-related bone defects remain poorly repaired due to a vicious cycle involving senescent bone marrow mesenchymal stem cells (BMSCs) and pro-inflammatory macrophages. We unveil circadian disruption as the underlying driver via single-cell transcriptomics and propose an "internal clock-repairing, external immunity-reprogramming" strategy. Inspired by cardiac pacemakers that sense signals and rectify rhythms, we engineer nanocellular pacemakers (AMC) with a "sense-release-regulate" paradigm for aged bone regeneration. AMC comprises melatonin-loaded, cobalt-based metal-organic frameworks (MOF) coated with membrane vesicles derived from the new generation of probiotic Akkermansia muciniphila. The cobalt-based MOF functions as an artificial sensor that specifically senses senescence-associated signals to release melatonin in the senescent microenvironment. The targeted delivery of melatonin repairs the internal clock and rejuvenates BMSCs by precisely regulating circadian rhythms to inhibit p53 and TNF signaling pathways. While probiotic membrane on AMC actively reprograms macrophages toward a pro-regenerative M2 phenotype in the senescent niche. To enable minimally invasive delivery, a dual-network hydrogel with reactive oxygen species-responsive boronic ester bonds is developed for spatiotemporal release of AMC. In aged mice, this cascade-responsive therapeutic system fully repairs bone defects within 4 weeks by breaking the senescence-inflammation vicious cycle, offering a novel "cellular pacing" paradigm for age-related tissue repair.
The synergistic catalytic removal of multipollutants, such as nitrogen oxides and volatile organic compounds, has emerged as a transformative strategy for air pollution control. It directly tackles the interconnected challenges of PM2.5 and ozone formation. This mini review summarizes recent breakthroughs in this field, encompassing the design of novel catalysts with multifunctional active sites, the elucidation of the kinetic mechanisms underlying synergistic reactions, and the development of anti-poisoning strategies to maintain activity under complex flue gas conditions. We further examine how tailored acid-redox bifunctionality and dynamic active-site cooperation can overcome inherent issues such as temperature-window mismatches and competitive adsorption between pollutant molecules. Finally, by integrating advances in operando characterization and artificial intelligence, we propose a forward-looking roadmap for synergistic catalysis. This roadmap aligns with carbon neutrality goals and highlights the critical role of catalytic innovations in enabling clean and efficient environmental protection.
Electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach to simultaneously realize pollutant removal and ammonia generation. However, this process involves the transfer of eight electrons and nine protons along with multiple by‐products, resulting in a significant challenge for achieving high ammonia yield and selectivity. Herein, we introduced bimetallic covalent organic frameworks catalysts with Cu and Co active sites to achieve a two‐step tandem reaction, avoiding excessive nitrite accumulation and enabling efficient NO 3 RR. For the initial two‐electron process, the Cu sites in the bimetallic catalyst exhibit a strong binding affinity with nitrate, promoting their conversion to nitrite. The Co sites enhance the supply and adsorption of active hydrogen and stabilize the subsequent six‐electron process, thereby improving the overall catalytic efficiency. Compared to monometallic Cu and Co catalysts, the CuCo bimetallic catalyst demonstrates superior ammonia yield and Faradaic efficiency (NH 3 yield rate = 20.8 mg·h −1 ·cm −2 , FE = 92.16% in 0.3 M nitrate). Such coordinated two‐step process advances the efficiency and applicability of NO 3 RR through optimizing a cascade catalytic reaction, thereby establishing an innovative path for the engineering of NO 3 RR electrocatalysts.
Electrocatalytic nitric oxide reduction reaction (NORR) for ammonia (NH 3 ) synthesis represents a sustainable strategy that simultaneously realizes the nitrogen cycle and resource integration. The key issue hindering the NORR efficiency is accelerating proton (*H) transfer to facilitate NO hydrogenation while inhibiting the hydrogen evolution reaction (HER). Herein, we demonstrate an interface-engineered sulfur-mediated Cu@Co electrocatalyst (S-Cu@Co/C) that boosts NORR performance through dual modulation of electronic structure and proton transfer on active sites. A comprehensive program of experimental and theoretical calculations was employed to discover that sulfur incorporation induces electron redistribution in the Cu–Co interface, creating electron-rich sulfur and electron-deficient metals. This electronic configuration synergistically enhances NO adsorption on Cu sites and promotes water dissociation on Co sites. More critically, sulfur could direct the rapid transfer of *H from Co to Cu sites, thereby accelerating the NO hydrogenation and suppressing HER. Consequently, S-Cu@Co/C achieves an NH 3 yield rate of 655.3 µmol h −1 cm −2 in a flow cell and a Faradaic efficiency of 92.4% in an H-cell. Remarkably, the catalyst could maintain continuous electrolysis tests and steady NH 3 yield up to 100 h. This work provides innovative insights into the fabrication of efficient electrocatalysts via heteroatom-mediated interfacial engineering strategies.
Electrocatalytic nitrate reduction (NO 3 RR) is a promising method for pollutant removal and ammonia synthesis and involves the transfer of eight electrons and nine protons. As such, the rational design of catalytic interfaces with enhanced mass transfer is crucial for achieving high ammonia yield rates and Faradaic efficiency (FE). In this work, we incorporated a Cu-bipyridine catalytic interface and fabricated crystalline 2D covalent organic framework films with significantly exposed catalytic sites, leading to improved FE and ammonia yield (FE=92.7 %, NH 3 yield rate=14.9 mg ⋅ h −1 cm −2 in 0.5 M nitrate) compared to bulk catalysts and outperforming most reported NO 3 RR electrocatalysts. The film-like morphology enhances mass transfer across the Cu-bipyridine interface, resulting in superior catalytic performance. We confirmed the reaction pathway and mechanism through in situ characterizations and theoretical calculations. The Cu sites act as primary centers for adsorption and activation, while the bipyridine sites facilitate water adsorption and dissociation, supplying sufficient H* and accelerating proton-coupled electron transfer kinetics. This study provides a viable strategy to enhance mass transfer at the catalytic interface through rational morphology control, boosting the intrinsic activity of catalysts in the NO 3 RR process.
The improvement of low‐temperature catalytic activity still remains a paramount scientific challenge in environmental catalysis. To address this issue, an aluminum‐rich molecular sieve interface regulating electron‐enriched Mn‐O‐Ce active sites for highly efficient environmental catalysis has been demonstrated. Specifically, the surface aluminum‐rich hollow ZSM‐5 zeolites are constructed through dissolution‐recrystallization and coupled with MnCeO x composites owning strong redox properties to amplify contact between acidic and active sites that manipulate effective environmental catalytic reactions. Taking the selective catalytic reduction of nitrogen oxide (NO x ) as a probing reaction, the engineered Al‐rich interface significantly facilitates the electron transfer from ZSM‐5 zeolite to MnCeO x composite, creating electron‐enriched Mn‐O‐Ce active sites that artfully establish adjacent centers for reactant molecules adsorption and activation: Mn‐end of Mn‐O‐Ce sites for NO x coordination and Ce‐end of Mn‐O‐Ce sites for partial ammonia (NH 3 ) adsorption to achieve superior catalytic activity and selectivity below 150 °C. Concurrently, the modulated zeolite‐metal oxide interface with electron‐enriched Mn‐O‐Ce active sites and sufficient Brønsted acid sites also demonstrates exceptional efficiency in synergistic removal of nitrogen oxide with representative volatile organic compounds. Beyond superior multifunctional catalytic performance, this work pioneers interfacial electron engineering as a universal strategy to design advanced functional materials for efficient environmental catalysis.
Biodiesel, a carbon-neutral alternative to fossil fuels, plays a vital role in decarbonizing transportation, with global production exceeding 40 million tons annually. However, its widespread use introduces elevated phosphorus and metal cations into vehicle exhaust, severely deactivating Cu-SSZ-13 catalysts for NO X reduction through pore blockage, framework degradation, and Cu sites loss. We present a Cu–Ce dual-atom catalyst embedded in SSZ-13 that maintains high performance in ammonia-selective catalytic reduction under phosphorus-rich conditions. Ce species, precisely positioned in eight-membered rings, displace P-sensitive [ZCu 2+ OH] + sites, enriching the catalyst with P-tolerant Z 2 Cu 2 ⁺ species in six-membered rings. Concurrent Ce─P interactions restore the electronic environment of Cu sites, enhancing NH 3 /NO adsorption and redox cycling. This design sustains 90% NO X conversion and 100% N 2 selectivity at 210 °C, even after phosphorus exposure. The strategy is broadly applicable to impurity-sensitive environmental reactions, including NH 3 oxidation and the coupled removal of NO X with VOCs, offering a practical pathway to durable, poison-resistant catalysts for clean and sustainable mobility.
Hypoxia-related adenosine (Ado) exerts an immunosuppressive effect in tumors by binding to the metabolic checkpoint Ado A2A receptors (A2AR), thereby hindering the activation of antitumor immunity induced by immunogenic cell death (ICD). In this study, a MnO2-assisted photosynthetic bacteria (PSB) biohybrid (MnO2@PSB) is developed to enhance tumor photothermal immunotherapy by interfering with the Ado-A2AR metabolic pathway. Specifically, manganese dioxide (MnO2) nanoflowers are conjugated onto PSB by the carbodiimide reaction to construct the biohybrid MnO2@PSB. As a photothermal agent, MnO2@PSB generates heat to "burn" tumor cells under 808 nm laser irradiation, inducing tumor cell ICD. Meanwhile, MnO2@PSB catalyzes the decomposition of endogenous hydrogen peroxide into oxygen to alleviate tumor hypoxia, thereby reducing Ado production and downregulating the expression of A2AR, further reversing the tumor immunosuppressive microenvironment and amplifying the ICD effects. In various mouse 4T1 tumor models, MnO2@PSB can enhance antitumor immune responses, prolong mouse survival, and significantly inhibit tumor growth, recurrence, and metastasis under 808 nm laser irradiation. Collectively, this study provides a direction for enhanced antitumor immunotherapy through regulating metabolic pathways.
Adeno-associated viruses (AAVs) have emerged as the most favored viral vectors in clinical trials due to their diverse tissue tropism, low integration, and stable gene expression. However, pre-existing neutralizing antibodies and immune responses hinder AAV re-administration and limit its long-term gene therapy. To overcome this, we engineered a biomimetic artificial enveloped AAV (AEV) inspired by natural enveloped viruses, designed to shield against neutralizing antibodies and antigen-presenting cells. In mice, AEVs demonstrated superior transduction efficiency and minimal immune activation compared with AAVs in primary and secondary injections, even in environments with pre-existing antibodies and immune organs. Furthermore, AEVs showed flexibility in its modification for targeting different cells, enabling the use of multiple strategies to precisely target specific cells. This enhanced versatility allowed modified AEVs to provide significant therapeutic benefits in murine models of hemophilia B and diffuse large B cell lymphoma, expressing human factor IX and producing chimeric antigen receptor (CAR)-T cells in vivo.