Catalysis Letters最新文献

{"title":"The Enhanced Catalytic Activity of N-Doped OMS-2 Catalyst for Direct Decomposition of N2O","authors":"Ruifang Wu,&nbsp;Hui Dang,&nbsp;Ziying Su,&nbsp;Chengming Zhang,&nbsp;Xiangqian Lin,&nbsp;Ke Zheng,&nbsp;Liangliang Zhang,&nbsp;Yongzhao Wang","doi":"10.1007/s10562-026-05541-y","DOIUrl":"10.1007/s10562-026-05541-y","url":null,"abstract":"<div><p>A series of N-doped OMS-2 catalyst were prepared by a simple and mild one-step sol-gel method using urea as nitrogen dopant, and were tested for catalytic decomposition of N₂O. The addition of N improved catalytic activity of pure OMS-2, and N₁-OMS-2 catalyst exhibited optimal catalytic performance. For N₁-OMS-2 catalyst, N was successfully doped into the OMS-2 lattice, which although did not induce obvious change of crystal structure and morphology of OMS-2, resulted in slight increase of specific surface area, more abundant oxygen vacancies and enhanced surface basicity. These changes facilitated adsorption and activation of N₂O molecules. Meanwhile, N-doping also weakened the Mn-O bonds, promoting the desorption of oxygen species. All these factors endowed N₁-OMS-2 with a lower E_a for N₂O decomposition. As a result, the complete conversion temperature of N₂O over N₁-OMS-2 was 60 ℃ lower than that over pure OMS-2. Moreover, N₁-OMS-2 displayed a good stability under the reaction condition of 1000 ppm N₂O+3vol% O₂ + 3.3vol% H₂O mixed gas. Overall, this study offered a facile and promising proposal to obtain high-performance OMS-2 catalyst for catalytic decomposition of N₂O.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 11","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149098472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective Oxidation of Benzyl Alcohol to Benzaldehyde in a Non-aqueous Solution Using a Quaternary Nanocomposite Photocatalyst","authors":"Khaled M. AlAqad,&nbsp;Basheer Chanbasha","doi":"10.1007/s10562-026-05537-8","DOIUrl":"10.1007/s10562-026-05537-8","url":null,"abstract":"<p>In this work, functionalized nanostructured quaternary photocatalysts based on graphitic carbon nitride (g-C₃N₄) and graphene oxide (RGO) as a support, with iron oxide (FeNPs) and zinc oxide (ZnO) (g-C₃N₄/FeNPs/RGO/ZnO), were synthesized by a hydrothermal method and used as an efficient visible photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde using atmospheric oxygen. The g-C₃N₄/FeNPs/RGO/ZnO photocatalyst shows good oxidation activity and selectivity for benzyl alcohol under visible light. The as-synthesized catalyst was thoroughly characterized using powder X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Raman spectroscopy to identify its chemical structure and composition. Various experiments were conducted to fine-tune reaction selectivity, including reactions with the support, with the support doped with iron and zinc oxide, and control experiments using benzaldehyde and without catalysts. The optimized amount of the developed photocatalyst was 10 mg. Various concentrations of benzyl alcohol were studied using the g-C₃N₄/FeNPs/RGO/ZnO photocatalyst, and the conversion and selectivity for benzyl alcohol to benzaldehyde were 65% and 67%, respectively, at room temperature. Interestingly, (i) the reaction proceeds only from benzyl alcohol to benzaldehyde, and (ii) no reaction was observed in the absence of a catalyst and light. The reaction was monitored by liquid chromatography/mass spectrometry. The synergistic effect among the surface Fe NPs, ZnO, and g-C₃N₄ plays a vital role in achieving good photocatalytic performance.</p>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 11","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149098271","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient Removal of Endocrine Disrupting Chemicals by BiOBr/Bi2O2CO3 Heterojunctions with the Presence of Chlorite: Photocatalytic and Chlorite Activation Mechanisms","authors":"Yuhan Wang,&nbsp;Guocong Liu,&nbsp;Jinyu Yang,&nbsp;Yuanhao Wang,&nbsp;Ming Lu,&nbsp;Zhu Liu,&nbsp;Yuqiu Shen,&nbsp;Wenqi Xian,&nbsp;Guangji Zhang","doi":"10.1007/s10562-026-05536-9","DOIUrl":"10.1007/s10562-026-05536-9","url":null,"abstract":"<div><p>The visible light-driven chlorite activation process has demonstrated remarkable potential for wastewater treatment applications. In this study, a series of flower-like S-scheme heterojunction photocatalysts (composed of BiOBr and Bi₂O₂CO₃, denoted as xyDBi) were successfully synthesized, with the (001) facet serving as the predominantly exposed crystal plane. An integrated ClO₂-photocatalytic system was established using xyDBi to enhance the degradation of bisphenol A (BPA) in aqueous solutions. Comprehensive characterization and theoretical calculations revealed the formation of a robust internal electric field at the heterojunction interface, enabling efficient spatial separation of photogenerated charges through an S-scheme charge transfer mechanism. Density functional theory (DFT) calculations and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analyses indicated that oxygen vacancies (OVs) functioned as Brønsted acid sites, facilitating the adsorption of chlorite ions (ClO₂⁻). Chlorine dioxide (ClO₂) was identified as the primary reactive species, generated through two distinct pathways involving OVs and hydroxyl radicals (∙OH). Under visible light irradiation, the addition of chlorite to the 11DBi-based photocatalytic system achieved 92.7% removal of BPA within 25 min. The 11DBi catalyst demonstrated exceptional stability across a broad spectrum of reaction conditions, encompassing initial pH variations, coexisting anions and cations, catalyst recyclability, and diverse water matrices. Additionally, the degradation mechanism of BPA was deduced to be demethylation, hydroxylation, and cleavage of the isopropylidene bridge. This study elucidated the synergistic interaction between oxygen vacancy-rich S-scheme heterojunctions and chlorite activation, providing a novel approach for advanced oxidation processes in wastewater treatment.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 11","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149098101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Citrate Impregnation Solutions for the Preparation of Co-Mo/Ni-Mo Hydrotreating Catalysts: How Does Citric Acid Concentration Affect Solution Stability and Catalyst Performance","authors":"Sergey V. Budukva,&nbsp;Mikhail V. Parfenov,&nbsp;Mikhail E. Revyakin,&nbsp;Evgenii A. Suprun,&nbsp;Elizaveta S. Bykova,&nbsp;Daria D. Uvarkina,&nbsp;Maxim O. Kazakov","doi":"10.1007/s10562-026-05535-w","DOIUrl":"10.1007/s10562-026-05535-w","url":null,"abstract":"<div><p>This work investigates the stability of concentrated citrate-based Co-Mo and Ni-Mo impregnation solutions used for hydrotreating catalyst preparation, with particular emphasis on the composition and catalytic consequences of precipitates formed unintentionally at insufficient citric acid concentrations. The samples were characterized using a variety of techniques, including XRD, IR spectroscopy, SEM, EDS, and XPS. It was found that the dominant compounds in the precipitates are Anderson-type heteropoly compounds. The results show that Ni–Mo citrate solutions predominantly form Anderson-type ammonium 6-molybdonickelate, whereas Co-Mo citrate solutions form sparingly soluble polymolybdates in the absence of alumina and Anderson-type (ammonium 6-molybdocobaltate and ammonium 6-molybdoaluminate) heteropoly compounds upon contact with γ-Al₂O₃. Catalytic activity was evaluated in the hydrotreating of SRGO. Hydrotreating tests showed that the precipitated heteropoly compounds are transformed during sulfidation into sulfide species and may contribute to the overall HDS performance. Therefore, the higher activity observed for catalysts prepared with precipitate formation is mainly attributed to increased actual metal loading.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149132136","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synergistic Effect of Zn and Zr Co-modified ZSM-5 Zeolite for Catalytic Cracking of Waste LDPE to High-Yield Light Olefins","authors":"Weiji Wang,&nbsp;Zhiguo Shao,&nbsp;Chengjian Wang,&nbsp;Haibin Shi,&nbsp;Ping Geng","doi":"10.1007/s10562-026-05530-1","DOIUrl":"10.1007/s10562-026-05530-1","url":null,"abstract":"<div><p>Waste low-density polyethylene (LDPE) causes severe environmental issues, and catalytic pyrolysis serves as one feasible approach for the high-value utilization of such plastic. Commercial ZSM-5 zeolites contain abundant strong Brønsted acid sites, which readily induce undesired aromatization side reactions during the process, consuming light olefin intermediates. Neither Zn nor Zr modification alone can achieve satisfactory catalytic performance. In this work, Zn/Zr co-modified ZSM-5 catalysts with different molar ratios were prepared by the incipient wetness impregnation method, and their catalytic performance for LDPE cracking was evaluated in two-stage fixed-bed reactor. The experimental results reveal that loading of metal does not destroy the MFI topological framework of ZSM-5. Nevertheless, Zn species tend to interact with framework bridging hydroxyl groups to form ZnOH⁺ species, which may account for the marked decrease in crystallinity and loss of long-range framework order observed for the single Zn-modified sample. Meanwhile, abundant unconstrained ZnOH⁺ species serve as strong dehydrogenation active sites and trigger severe secondary reactions. In bimetallic modified samples, Zr species couple with Zn species through electronic interaction, restrain the consumption of bridging hydroxyl groups by Zn, balance the Brønsted‑to‑Lewis acid ratio (B/L), and render the acid‑site distribution more favorable for light‑olefin production. Among the prepared samples, Zn_0.25Zr_0.75/ZSM-5 exhibited the best catalytic performance, achieving a gas yield of 77.40 wt% and a light olefin yield of 62.54 wt% at 500 °C, with ethylene production superior to that of the monometallic modified samples. Regeneration‑cycle tests were carried out over this catalyst. The results show that the light‑olefin yield can still be maintained at 59.94 wt% after ten regeneration cycles, demonstrating favorable cycling stability.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149132197","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Defect-Rich MoO3@CuxO Heterointerface with Abundant Cu+ Active Sites for Efficient Aerobic Oxidative Desulfurization","authors":"Xi Liu,&nbsp;Wenjian Wu,&nbsp;Ran Wang,&nbsp;Rongkang Li,&nbsp;Yafei Li,&nbsp;Jie Hou,&nbsp;Fuquan Xiao,&nbsp;Linhua Zhu","doi":"10.1007/s10562-026-05533-y","DOIUrl":"10.1007/s10562-026-05533-y","url":null,"abstract":"<div><p>Heterointerface engineering is a catalyst design strategy based on the symbiotic growth of heterogeneous metal oxides. This strategy endows electronic structures, surface properties, and generation of active centers that are unavailable in the individual oxides. It can even generate entirely new active sites, thereby significantly enhancing catalytic performance. Herein, we prepared MoO₃@Cu_xO with symbiotic MoO₃ and CuO as a catalyst for aerobic catalytic oxidative desulfurization. Notably, after symbiosis, the catalyst exhibits new low-valence Cu⁺ active sites absent in the individual oxides, along with defective interfaces more favorable for catalytic reactions and enhanced surface redox properties. Catalytic testing validates these findings: these new low-valence Cu⁺ active sites enable the activation of superoxide radicals, achieving 100% desulfurization of aromatic sulfur compounds under air atmosphere within 5 h. Through the rational design of symbiotic heterogeneous metal oxides, this study not only highlights the pivotal role of heterointerface engineering in catalytic oxidation but also offers an effective strategy for designing oxidative desulfurization catalysts.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149132138","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of Cobalt-Based Carbon Catalysts Derived from Triallyl Isocyanurate for the Highly Efficient Oxidation of 5-Hydroxymethylfurfural to 2, 5-Furandicarboxylic Acid","authors":"Liqiao He,&nbsp;Jingwen Li,&nbsp;Yuxin Li,&nbsp;Zhigang Liu","doi":"10.1007/s10562-026-05534-x","DOIUrl":"10.1007/s10562-026-05534-x","url":null,"abstract":"<div><p>The synthesis of 2,5-furandicarboxylic acid (FDCA) from biomass-derived 5-hydroxymethylfurfural (HMF) has attracted significant attention, as FDCA serves as an exceptionally renewable alternative to petroleum-derived terephthalic acid. However, achieving efficient catalytic oxidation of HMF under mild conditions remains a significant challenge. Herein, Triallyl isocyanurate (TAIC) serves as precursors owing to its attractive structure with inherently high nitrogen content, and a series of highly active cobalt-based porous carbon catalysts is synthesized through TAIC followed by KOH etching. Notably, the Co/NC-KOH catalyst achieves a complete HMF conversion and a high FDCA yield of 93.4%. Characterizations including XRD, Raman, N₂ physisorption, XPS, SEM and TEM demonstrate that achieve an optimal balance between defect density and pore accessibility. The incorporation of cobalt leads to the coexistence of Co groups bonded with nitrogen species. This synergistic architecture enables the efficient oxidation of HMF under low reaction temperature (80 °C) conditions.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149132137","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rh/ZrO2 Catalysts for Cyclohexane Ring Opening: A Role of Synthesis Method","authors":"Evgeny V. Abkhalimov,&nbsp;Vadim A. Ershov,&nbsp;Mikhail Yu. Mashkin,&nbsp;Kristina E. Kartavova,&nbsp;Alexander L. Kustov","doi":"10.1007/s10562-026-05524-z","DOIUrl":"10.1007/s10562-026-05524-z","url":null,"abstract":"<div><p>A series of the catalysts 1 wt% Rh/ZrO₂ was prepared by the methods of wet impregnation, excess impregnation, urea hydrolysis metal deposition, and nanoparticles deposition for a model reaction of cyclohexane ring opening under hydrogenolysis process. The obtained samples were characterized by XRD, SEM, EDX, FTIR, XPS and TEM techniques, TPR-H₂. In TPR-H₂, all the samples showed the consumption of H₂ higher than the stoichiometric value, and the highest value was observed for the sample obtained through wet impregnation. The sample prepared through nanoparticles deposition has much higher Rh content on the surface of the catalyst, and appeared to show the highest yield of n-hexane of 17.3% at 325 °C and the highest selectivity to n-hexane of ca. 87% at 275 °C.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149035419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Germanium-Doped Hematite Nanocrystals via Laser Ablation in Liquids for In-Situ Pt Loading and Enhanced Catalytic Hydrogenation of 4-Nitrophenol","authors":"Yingge Zhang,&nbsp;Wenjin Fang,&nbsp;Rong Zhao,&nbsp;Shiyu Zhou,&nbsp;Wei Shao","doi":"10.1007/s10562-026-05531-0","DOIUrl":"10.1007/s10562-026-05531-0","url":null,"abstract":"<div><p>Controlling the nucleation and growth of noble metals on supports is key to improving catalysis. Importantly, doping the catalyst support itself can also dramatically enhance catalytic performance. Here, we demonstrate that Ge-doped Fe₂O₃ via laser ablation in liquids serves as an efficient support for in situ loading of ultrafine Pt nanoparticles, achieving boosted activity for 4-nitrophenol hydrogenation. Systematic variation of Ge doping levels reveals that the catalytic performance reaches its maximum at an optimal Ge concentration of 5.35 wt%, beyond which further doping leads to a slight decline in activity. The Ge incorporation induces lattice distortion and electronic modulation of Fe, generating defect sites for Pt anchoring while fine-tuning Pt electron density via ligand effects. The optimized Ge-Fe₂O₃/Pt achieves a mass-normalized rate constant (k/m) of 0.39 s⁻¹ mg⁻¹, 1.6 times that of undoped Fe₂O₃/Pt (0.24 s⁻¹ mg⁻¹), while excessive doping (7.6 wt%) slightly diminishes activity. This work highlights precise dopant concentration control as a key factor in designing high-performance supported metal catalysts.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div><div><p>We successfully synthesized Ge-doped Fe₂O₃, with its Ge⁴⁺-induced lattice distortion and defect-rich structure, serves as an effective platform for in situ anchoring of ultrafine Pt nanoparticles, achieving a 1.6-fold enhancement in mass-normalized activity (0.39 s⁻¹ mg⁻¹) for 4-nitrophenol hydrogenation compared to pristine Fe₂O₃/Pt</p></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149035418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unraveling the Role of Dopant Speciation in Oxygen-Vacancy Location and Lattice-Oxygen Supply over Fe-, Co- and Ni-Modified CeO2 NH3-SCR Catalysts","authors":"Lirui Sun,&nbsp;Zhaoyang Chen,&nbsp;Weijie Xu,&nbsp;Lidong Zhang,&nbsp;Zhenguo Li","doi":"10.1007/s10562-026-05532-z","DOIUrl":"10.1007/s10562-026-05532-z","url":null,"abstract":"<div><p>Ceria is a promising vanadium-free catalyst for the low-temperature selective catalytic reduction of NO with NH₃ (NH₃-SCR). To establish an experimental baseline for transition-metal modification, pristine CeO₂ and Fe-, Co- and Ni-modified CeO₂ were prepared and evaluated under an identical protocol. XRD, HRTEM, Raman and XPS resolve three dopant states: Fe dissolves into the lattice and creates bulk vacancies; Ni precipitates as NiO and concentrates vacancies at the NiO/CeO₂ interface; Co phase-separates into strongly oxidising Co₃O₄. Under an oxygen-rich feed (0.5% NO, 0.5% NH₃, 5% O₂), pristine CeO₂ peaks at only 14.83% NO_x conversion at 300 °C and falls to 6.12% at 350 °C as the NO₂ yield rises to 24.92%. FeCe instead reaches 79.8% at 300 °C and retains 75.7% at 350 °C with 8.0% NO₂, demonstrating simultaneous enhancement of turnover and over-oxidation resistance. NiCe shifts the maximum to 250 °C (54.0%) but collapses to 0.3% at 350 °C, whereas CoCe produces only a narrow low-temperature window. Notably, NiCe shows the strongest defect signatures among the three modified samples by both conventional proxies, yet performs worse than FeCe above 250 °C. DFT shows that the lattice-substituted Fe site combines the lowest vacancy formation energy with the widest calculated free-energy separation between selective N–N coupling and non-selective lattice-oxygen dehydrogenation. Oxygen-vacancy location, rather than concentration alone, thus governs the activity–selectivity trade-off.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149035339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}