This study delves into the impact of phosphorus poisoning and hydrothermal aging on the selective catalytic reduction of nitrogen oxides by vanadium-based catalysts during mobile source exhaust purification.The findings reveal that phosphorus poisoning is more likely to reduce the nitrogen oxide purification efficiency of vanadium-based catalysts compared to hydrothermal aging,particularly leading to a significant decline in selective catalytic reduction activity in the low-temperature range.Utilizing various characterization techniques such as powder diffraction pattern,Raman spectroscopy,temperature-programmed adsorption and reduction process,photoelectron spectroscopy,and in-situ diffuse reflectance Fourier transform infrared spectroscopy,the study uncovers the deactivation mechanisms of phosphorus poisoning and hydrothermal aging in vanadium-based nitrogen oxide purification catalysts during mobile source exhaust treatment.The research indicates that phosphorus poisoning primarily causes catalyst deactivation by inducing the formation of phosphate structures on the catalyst surface,altering the redox capabilities of active vanadium species,and inhibiting the generation of key reaction intermediates.The hydrothermal aging process further exacerbates the effects of phosphorus poisoning on the crystal structure,active species morphology,and redox properties of the catalyst,leading to a significant reduction in nitrogen oxide purification efficiency.The systematic understanding of the deactivation effects of phosphorus poisoning and hydrothermal aging on vanadium-based catalysts provided by this study offers crucial theoretical foundations and scientific support for the development of efficient nitrogen oxide purification catalysts that resist phosphorus poisoning and hydrothermal aging.

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.

A grand challenge for ethanol oxidation reaction (EOR) catalysts lies in the well trade-off between catalytic activity, C1 pathway selectivity, and long-term stability. Herein, a novel type of PtFeCoIrRh fishbone-like high-entropy alloy nanowires (FHEANWs) with miscibility gaps between metal components was fabricated. The multiple structural defects associated with lattice distortion characteristic of HEAs endow PtFeCoIrRh FHEANWs with the exceptional activity of 2.85 A mgPt -1/1.77 A mgNoble metal -1 and 4.48 mA cm-2, 7.50/4.66 and 6.69 times more efficient than that of Pt/C, respectively. After long 50 000 s chronoampermetric and 2000 consecutive cycling stability tests, PtFeCoIrRh FHEANWs retain 68.42% and 76.39% of the initial activity. Also, X-ray adsorption spectroscopy elucidates the structural stability based on the variation in coordination configuration due to elemental migration within the FHEANWs. The attenuated total reflection-surface enhanced infrared absorption spectroscopy, coupled with theoretical calculations, reveals that the elemental synergism and dynamic balance between hydrogen-bonded H2O and isolated free H2O at the solid-liquid interface facilitate OH* generation and timely replenishment and the more efficient C1 pathway (58.54% selectivity at 1.0 V) while preventing H2O passivation. This work paves a new path for designing HEA anisotropic nanostructures featuring structural defects toward superb catalytic activity, stability, and selectivity.

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.

ABSTRACT Overcoming sulfur poisoning in dry reforming of methane (DRM), which is a critical process for biogas upgrading, is particularly challenging. In this study, we illustrate that a reverse lattice oxygen spillover (RLOS) from CeO 2 to Pt on the Pt‐O‐Ce interface, induced by CO 2 , can oxidize S into SO 2 , aiding in the removal of S deposits. A low oxygen migration barrier at the Pt–O–Ce interface and Pt's high activity for oxidizing sulfur to SO 2 make Pt/CeO 2 uniquely effective at self‐recovering after H 2 S poisoning. Furthermore, the atomically dispersed Pt/CeO 2 catalyst undergoes reaction driven adaptive restructuring, which amplifies the RLOS effect and enables dynamic S deposition and removal. As a result, the catalysts maintain constant DRM activity for 100 h, even in the presence of H 2 S. This discovery paves the way for designing catalysts that resist sulfur poisoning in H 2 S‐containing streams.

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.

The co-presence of alkali metals and phosphorus impurities in exhausts of biodiesel-powered vehicles poses a great challenge to the durability of emission control catalysts. To address this issue, we investigated the poisoning effects of K, P, and K&P on the SCR activity of a Cu-SSZ-13 catalyst and their underlying mechanisms. Loading 1 wt% K resulted in a moderate activity decrease at high temperatures (>400 degrees C). The same amount of P (1.2 wt%) dramatically reduced the activity below 350 degrees C. The poisoning effect of P was substantially reduced when K was also present, resulting in an activity profile between those of the individually poisoned catalysts. Their respective poisoning mechanisms were investigated through extensive catalyst characterizations using a variety of spectroscopy and in situ techniques. K depletes the Br & oslash;nsted acid sites first, and with increased K loading it tends to convert isolated Cu cations to extra-framework CuO clusters/particles. P on the other hand poisons the catalyst primarily by attacking the Cu sites directly, forming strong Cu phosphate bonds, which eliminate a large number of exchanged Cu sites. The coexistence of K and P results in the formation of even more stable K-phosphate compounds, consequently liberating some of the Cu sites from P poisoning. However, after hydrothermal aging, these K-phosphate compounds become stable and difficult to remove, certainly hindering activity recovery compared with the P-only poisoned sample. Overall, K exhibits a dual effect in mitigating P poisoning, being protective in the fresh state but certainly retarded after aging.

Chiral-at-cage o-carboranes represent a class of three-dimensional boron-cluster-based chiral molecules. Herein, we report a Pd-catalyzed regio- and enantioselective B(4)-H arylation of o-carboranyl benzaldehydes enabled by a chiral transient directing group (cTDG) strategy using l-threonine. The reaction proceeds via reversible imine formation and enantioselective B-H arylation, affording chiral-at-cage products in up to 87% yield and 98% ee. Chiroptical characterizations confirm the potential of the products in optoelectronic materials. This work provides a practical approach to asymmetric B-H functionalization using in-situ-formed cTDGs.

The design of Passive NOx Adsorbers (PNA) is essential for controlling cold-start emissions, yet Pd-ceria systems often encounter limitations in storage capacity and hydrothermal durability. In this work, we stabilize Pd by incorporating atomically dispersed Zr as neighboring atoms in ceria, establishing a framework for efficient and stable NOx capture. Zr doping in CeO2 modifies the electronic environment by intensifying Pd-O hybridization and broadening electronic states near the Fermi level. These modifications, alongside emergent Pd-O-Zr interfacial sites, facilitate the dynamic reconfiguration of oxygen vacancies. This process promotes the oxidation of NO to NO2, enabling the optimized catalyst to yield a NOx storage capacity of 166.6 & micro;mol/gcat-a value that surpasses the theoretical limit derived from Pd content. Structural stabilization further underpins these performance gains. Zr doping reinforces the CeO2 lattice, enhancing the thermal resilience of the support. Simultaneously, the atomically dispersed Zr adjacent to Pd sites modulates metal-support interactions to an optimal state, effectively inhibiting Ostwald ripening, particle migration, and coalescence. These combined effects significantly improve hydrothermal stability under rigorous conditions. Our findings provide a mechanistic basis for the rational design of high-performance PNA and offer a viable pathway to mitigate cold-start NOx emissions in advanced after treatment systems.

The escalating environmental impacts of food waste and CO2 emissions demand sustainable mitigation strategies. Here, we report a value-added approach for CO2 capture using self-nitrogen-doped carbon (NC) derived from fruit peels, banana, orange, and pomegranate, evaluated through techno-economic and life-cycle assessments. Nitrogen-enriched carbons were prepared via a two-step carbonization and chemical activation process to enhance adsorption performance. Among the materials, banana peel-derived NCB-600, carbonized at 450 degrees C and chemically activated at 600 degrees C (KOH/NC mass ratio 1:1), exhibited the highest CO2 uptake of 2.6 mmol g-1 at 25 degrees C and 1 bar. The enhanced adsorption was attributed to the optimized distribution of nitrogen functionalities, rather than high surface area or porosity. Techno-economic analysis indicates a competitive production cost of 0.93 $ kg-1 and a CO2 capture cost of 0.00457 $ kgCO2-1 . This study demonstrates that valorizing fruit peel waste into nitrogen-functionalized carbons provides an effective, low-cost, and environmentally sustainable strategy for CO2 capture and circular resource utilization.

ABSTRACT Electrocatalytic nitric oxide reduction to ammonia couples pollutant valorization with sustainable nitrogen conversion, but high activity and selectivity require concurrent control of NO transport, NO activation, and hydrogenation at the gas‐liquid‐solid interface. Here, we report a self‐supported, noble‐metal‐free Fe 3 C/Fe 3 N@C catalyst, composed of earth‐abundant Fe, C, and N, featuring defect‐rich Fe 3 C/Fe 3 N Janus nanostructures confined within graphitic carbon. The catalyst achieves an NH 3 yield rate of 468.3 µmol h −1 cm −2 with a Faradaic efficiency of 94.2% at −0.6 V versus RHE, placing it among the most efficient reported NORR electrocatalysts. Mechanistic studies reveal that the graphitic carbon shell facilitates NO diffusion by alleviating the steric and dynamic constraints imposed by the hydrogen‐bonded water network. At the Janus interface, Fe 3 C sites preferentially adsorb and activate NO, whereas nitrogen‐vacancy‐rich Fe 3 N sites promote H 2 O dissociation to supply reactive *H for subsequent hydrogenation. This spatial coupling of mass‐transfer promotion, NO activation, and interfacial *H generation enables efficient and selective NO‐to‐NH 3 electroreduction. These findings establish carbon‐confined, earth‐abundant carbide/nitride Janus interfaces as a promising design principle for high‐performance NORR catalysts.

The limited thermal stability of Cu-based zeolite catalysts remains a major challenge for lean NO x after treatment under extreme exhaust conditions. Here we show that Cu/LTA with a Si/Al ratio near 20 and optimized Cu loading combines nearly full NO x conversion with good hydrothermal stability even after aging up to 900 degrees C. In situ temperature-dependent X-ray absorption spectroscopy captures the progressive evolution of Cu species during thermal activation in oxidizing environments, revealing that mobile Cu(II) ions gradually dehydrate to form Z2Cu(II) and ZCu(II)OH, with partial conversion of the latter into Cu(I). Upon high-temperature hydrothermal aging, the Cu speciation shifts toward Z2Cu(II), consistent with enhanced framework stabilization and the suppression of bulk CuO formation. A qualitative wavelet-transform EXAFS analysis further evidences the emergence of proximal Cu sites, indicating increased structural connectivity between copper centers. These results unravel the dynamic redox and coordination behavior of Cu species in high-silica LTA and establish Cu/LTA as a hydrothermally resilient NH3-SCR catalyst, clarifying how framework stability and Cu speciation interplay to sustain long-term catalytic performance. This work sheds light on the role of Cu speciation and its dynamic evolution in governing the hydrothermal stability of Cu/LTA catalysts and provides a rational framework for the design of durable Cu-based zeolite catalysts for NH3-SCR under harsh exhaust conditions.

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.

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.

Photocatalytic nitrate reduction to ammonia offers a sustainable route that couples environmental remediation with nitrogen resource utilization. However, this transformation suffers from sluggish kinetics and insufficient hydrogenation, leading to poor selectivity and efficiency. Herein, we report the deposition of Cu4I4 nanocluster onto TiO2 (Cu4I4/TiO2) that achieves efficient and selective photocatalytic nitrate reduction to ammonia under mild conditions. The active site derived from an atomically precise Cu4I4Py4 (Py = pyridine) nanocluster introduces sterically accessible copper sites with intrinsically unsaturated coordination and enhanced Lewis acidity for nitrate adsorption and activation. The iodide ligands in Cu4I4 motif directly bonded to copper atoms are suggestive of promoting the generation of reactive hydrogen species (*H). The atomic-scale proximity of copper and iodide sites facilitates efficient *H utilization in the multistep hydrogenation toward NH3. Consequently, Cu4I4/TiO2 delivers an ammonia generation rate of 26.8 mmol·gcat -1·h-1 with good selectivity in a sacrificial-reagent-assisted photocatalytic nitrate reduction system. In situ characterizations and theoretical calculations support the plausible cooperative dual-site mechanism, which synergistically ensures the deep hydrogenation of nitrate and its intermediates to ammonia. This work establishes an atomic-level design paradigm for constructing multifunctional nanocluster catalysts that address the selectivity and efficiency challenges inherent to complex multiple proton/electron-involved reactions.

The understanding of wetting behaviors on anatase TiO2 is still lacking despite decades of controversy. Here, using neural network potentials molecular dynamics (NN-MD), we have investigated the interfacial water structure on the anatase surfaces with the three main facets of (101), (001), and (100) at room temperature. Our study reveals that an ordered water monolayer structure with a two-dimensional (2D) hydrogen-bond network formed on all three above low-index facets. The ordered water monolayer reduces the number of hydrogen bonds between the ordered water and the water above it, as the hydrogen bonds tend to form between the ordered waters, resulting in the formation of a water droplet above the ordered water monolayer. Particularly, compared to the other two facets with roughly the same adsorption energy, we have found that the dissociated water observed on the anatase (001) surface partly disturbs the ordering of interfacial water, resulting in the smallest contact angle of the three facets.

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.

Accurately monitoring carcinogenic volatile aromatic hydrocarbons (BTXs) is crucial for assessing air-qualities and danger-classes in specific occasions, However, it remains challenging to conduct highly selective identification of them in complex environments. Here, we have developed a gas-shunting strategy by installing function-reversal ZnO materials into Ir-WO3 supports to diminish interference-gas responses and guide special aromatic hydrocarbons sensing. We find that ZnO materials can serve as reactively sacrificial sites for small-molecule H2S and CO and induce main aromatic hydrocarbons reactants into Ir-WO3 supports. This gas-shunting route guarantees highly-selective aromatic hydrocarbons sensing even in dual/ternary gas mixtures. Through integrating functional-opposite sensors into a system, the final sensing arrays achieve 100% classification accuracy for 10 single gases and 75 multi-compose gases with low training costs. In addition, we also show an autonomic "cruise-detection" system by equipping sensor arrays into robotic dog to accurately identify complex gases. Our findings emphasize sensors designs with selective features and may broaden integrated sensing-system analysis in complex environment.

V2O5-WO3/TiO2 (VWTi) catalysts for NH3-SCR suffer severe poisoning by alkali metals, especially K, yet the site-specific poisoning mechanism remains unclear. Herein, we elucidate the poison mechanism based on a comprehensive investigation consisting of experimental work, theory calculation, and machine learning, conducted by controlling the VOx density and K/V ratio. Using a variety of characterization techniques, we found that the SCR activity of a VWTi catalyst was governed by its redox ability and the Lewis acidity dominated by V4+. The terminal V=O group is a Lewis acid and can adsorb NH3, while the bridging V-O-V group serves as a redox center, capable of activating NO/O2. K poisons a VWTi catalyst by attacking the strong Br & Oslash;nsted acids first and then the strong Lewis sites, resulting in a nonlinear progression of activity decline, which is slow initially but accelerates with increasing K accumulation. This phenomenon is especially evident for high-V loading catalysts dominated by the polymeric VOx species. Density functional theory calculations reveal that K poisons VWTi catalysts by binds K to the terminal V=O sites, forming the chemically inactive KVO3 compound and weakening the NH3 adsorption on the neighboring VOx. This work offers a comprehensive understanding of the site-specific sensitivity of VOx species to alkali metal poisoning and provides important insights to the deactivation process, which could be used to design practical VWTi catalysts for commercial applications.