The Journal of Physical Chemistry C最新文献

{"title":"Analysis of Fe 2p Core-Hole Resonances in Fe2O3 and Fe3O4 Photoemission Spectra Using Asymmetric Coupled-Resonance Peak-Fitting","authors":"Dagoberto Cabrera-German,&nbsp;Dulce Maria Guzman-Bucio,&nbsp;Abraham Carmona-Carmona,&nbsp;Anthony D. Dutoi,&nbsp;Alberto Herrera-Gomez","doi":"10.1021/acs.jpcc.6c03815","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c03815","url":null,"abstract":"<p>The quantitativeanalysis of Fe 2<em>p</em> spectra remainschallenging because multiplet splitting, strong asymmetry, satelliteintensity, and extended background contributions overlap over a broadbinding energy range. Here, we revisit the Fe 2<em>p</em> spectraof hematite Fe₂O₃ and magnetite Fe₃O₄, using the Coupled Resonances (CR) line shape combinedwith the Narrow Shirley (NS) background and a Tougaard extrinsic background.Among the tested approaches, CR Type III provides the best balancebetween spectral fidelity, integrability, and quantitative stability.It reproduces the main Fe 2<em>p</em> doublet, multiplet-relatedstructure, and satellite region without relying on empirical asymmetrictails or nonintegrable profiles. The extracted resonance energies,lifetime widths, and interference terms show that Fe 2<em>p</em> asymmetry arises from coupling between overlapping final-state resonances.This interference produces a CR-induced shift that accounts for thesteep low-binding-energy onset and extended high-binding-energy decayof the Fe 2<em>p</em> envelope. Comparison with cluster-modelcalculations shows that CR fitting complements multiplet simulationsby grouping unresolved final states into experimentally constrainedresonances. The Fe₂O₃ composition analysis furthershows that recovering nominal stoichiometry does not validate a quantificationstrategy by itself. The calculated Fe/O ratio depends on O 1<em>s</em> component selection, background implementation, end pointdefinition, and photoionization correction scheme. Overall, CR TypeIII plus NS analysis provides a mechanistically interpretable andquantitatively stable framework for Fe 2<em>p</em> modelingand Fe/O assessment in iron oxides.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13970–13990"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149130634","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polarization-Inducible Metal–Semiconductor Transition and Bifunctional Catalysis in Sc2CO2/ZrSeO Heterostructures","authors":"Cheng Wang,&nbsp;Qiheng Ma,&nbsp;Deqiang Yin,&nbsp;Shufang Ma,&nbsp;Bingshe Xu,&nbsp;Xiaodong Hao","doi":"10.1021/acs.jpcc.6c03540","DOIUrl":"10.1021/acs.jpcc.6c03540","url":null,"abstract":"<p>Solar-driven photocatalytic water splitting representsa pivotalstrategy for addressing global energy shortages and environmentaldegradation. Although van der Waals (vdW) heterostructures enhancecarrier efficiency via band engineering, their intrinsic electricfields are often restricted by fixed work functions. Taking the ferroelectricSc₂CO₂ monolayer with switchable polarizationand the Janus ZrSeO monolayer with strong visible-light absorptionas a representative system, first-principles calculations are employedto investigate the band alignment, carrier transport behavior, andphotocatalytic efficacy of the Sc₂CO₂/ZrSeOferroelectric heterojunction. The study reveals that the interplaybetween the switchable Sc₂CO₂ polarization andthe intrinsic ZrSeO dipole explicitly governs the electronic properties.Combining the two ZrSeO orientations with the two Sc₂CO₂ ferroelectric states yields tunable semiconducting bandgaps(0.76–1.50 eV) and establishes a Type-II band alignment inspecific configurations, promoting efficient carrier separation alongsideenhanced visible-light absorption. Crucially, at a fixed ZrSeO orientation,reversing the Sc₂CO₂ polarization induces areversible metal-to-semiconductor transition. Gibbs freeenergy calculationsfurther evaluate the catalytic performance of these representativesemiconducting and metallic configurations. These findings highlightthe Sc₂CO₂/ZrSeO heterostructure’s potentialfor multifunctional catalytic applications and ferroelectric electronicdevices.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13947–13958"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149021451","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the Molecular Mechanism of Action of 4,4′-Bipyridine as a Suppressor for Superconformal Cobalt Electrodeposition","authors":"Binyu Li,&nbsp;Qian Li,&nbsp;Xiujie Hao,&nbsp;Xixun Shen,&nbsp;Lina Qiu,&nbsp;Qunjie Xu","doi":"10.1021/acs.jpcc.6c05446","DOIUrl":"10.1021/acs.jpcc.6c05446","url":null,"abstract":"<p>Molecular-level understanding of additive-mediated regulationofcobalt (Co) electrodeposition remains elusive, although organic additivesare essential for controlling interfacial deposition behavior in advancedinterconnect technologies. Here, 4,4′-bipyridine (4BPY) isemployed as a suppressor to elucidate its adsorption configurationand inhibition mechanism on Co electrodes through electrochemicalmeasurements, in situ electrochemical surface-enhanced Raman spectroscopy(EC-SERS), and density function theory (DFT) calculations. Electrochemicalstudies demonstrate that 4BPY effectively suppresses both Co depositionand hydrogen evolution reaction at the interface between the Co electrodeand the electrolyte. Crystallographic orientation analysis revealsthat 4BPY preferentially adsorbs on Co (110) plane, altering the competitivegrowth behavior among Co (110), Co (100), and Co (002) planes andconsequently modifying the deposition morphology. Combined experimentaland theoretical results reveal that 4BPY anchors onto the Co surfacethrough Co–N coordination with a perpendicular molecular configuration,which blocks active sites and regulates Co deposition kinetics. Thesefindings provide molecular-level insights into the mechanism by whichadditive adsorption regulates Co electrodeposition and offer fundamentalguidance for the rational design of suppressors for advanced interconnectmetallization.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13763–13773"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049371","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comprehensive First-Principles Investigation of Tritium Migration in γ-LiAlO2","authors":"Kashi N. Subedi,&nbsp;Krishna Chaitanya Pitike,&nbsp;Giridhar Nandipati,&nbsp;Mark Lanza,&nbsp;David J. Senor,&nbsp;Andrew M. Casella,&nbsp;Ayoub Soulami","doi":"10.1021/acs.jpcc.6c01612","DOIUrl":"10.1021/acs.jpcc.6c01612","url":null,"abstract":"<p>Inthis work, we employ density functional theory (DFT) calculationsto investigate the atomic-scale mechanisms of hydrogen (H) migration(using H as a model substitute for tritium) in both pristine and lithium-vacancy-containingγ-LiAlO₂. In the pristine lattice, three interstitialconfigurations were identified: oxygen-bonded (BI), tunnel (TI), andcage (CI) interstitial configurations. Charged-defect calculationsshow that protonic H (H⁺) at the BI site is the lowest-energyH configuration for Fermi levels near the valence-band maximum, <em>E_F</em> &lt; 2.82 eV. H⁺, however, is notstructurally stable at the TI and CI sites and instead relaxes towarda BI-like O–H bonded configuration. Neutral H (H⁰) is structurally stable at CI and TI sites and has lower formationenergy than anionic H (H^–) for Fermi levels nearthe valence-band maximum up to approximately midgap, whereas H^– becomes lower in energy toward the conduction-bandminimum and is the most thermodynamically stable species under high-Fermi-levelconditions (<em>E</em>_<em>F</em> &gt; 3.80eV). When all relaxed configurations and charge states are compared, H⁰ is not the lowest-energy isolated H species over theFermi-level range considered. H⁺ migrates between adjacentBI sites with a migration barrier of 0.66 eV, which is comparableto the previously reported vacancy-mediated migration barrier [ <span><span><span><span>Paudel</span>, <span>H. P.</span></span>; et al.</span>. <span>J. Phys. Chem. C</span><span>2018</span>, <span>122</span>, <span>9755</span>–<span>9765</span>.</span> ]. H^– migrates along the tunnel direction with a relativelylow barrier of 0.13 eV, suggesting that H^– may contributeto tunnel-directed transport under electron-rich conditions. In contrast,higher barrier along the cage-involving pathway (0.72 eV) suggeststhat H^– migration through the cage is less favorable.For locally stable H⁰ configurations, even though theTI–TI migration barrier is exceptionally small (0.021 eV),this pathway is best interpreted as a kinetically fast but thermodynamicallylimited migration channel. Furthermore, in the intermediate Fermi-levelrange 2.82 eV &lt; <em>E</em>_<em>F</em> &lt; 3.80 eV, an interstitial H₂ molecule is thermodynamicallyfavorable within the tunnel and retains a gas-phase-like H–Hbond length and dissociation energy; once present, it migrates alongthe tunnel with a barrier of ∼0.36 eV. Finally, a negativelycharged lithium vacancy can bind up to two H⁺ ions, whereasthe addition of a third H⁺ is thermodynamically unfavorable.The estimated detrapping energies indicate that the bound H⁺ ions are strongly trapped at Li-vacancy-associated configurations.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13653–13668"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149003381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ion and Polymer Dynamics in Solid Electrolytes for Sodium-Ion Batteries via Conductivity and NMR","authors":"Andreas Markert,&nbsp;Niklas Röttgen,&nbsp;Hermann Nirschl,&nbsp;Gisela Guthausen","doi":"10.1021/acs.jpcc.6c02912","DOIUrl":"10.1021/acs.jpcc.6c02912","url":null,"abstract":"<p>The quality of asolid electrolyte is determined by its ionic conductivity,among other factors. The mobility of the ions is, therefore, of majorrelevance. The interplay between conducting ions and the polymer networkwas studied by wide-line NMR and ionic conductivity at specific timeand length scales. Here, the electrolytes are the polymer electrolytepoly(ethylene oxide) (PEO) with the salt sodium-bis(trifluoromethanesulfonyl)imide(NaTFSI), as well as the composite polymer electrolyte PEO:NaTFSI+ 50% wt NaSICON (Na_3.4Zr₂Si_2.4P_0.6O₁₂). The experiments show a reduction in ionicand polymer chain mobility with increasing salt content. Furthermore,NaSICON particles reduce the chain and ionic mobilities as well asthe ionic conductivity.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13916–13923"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic Origins of Selective Aromatic Amino Acid Oxidation by Mn-Doped TiO2 Nanozymes","authors":"Filip Kozłowski,&nbsp;Fredric G. Svensson,&nbsp;Tatiana Agback,&nbsp;Peter Agback,&nbsp;Suresh Gohil,&nbsp;Gulaim A. Seisenbaeva,&nbsp;Lars Kloo,&nbsp;Vadim G. Kessler","doi":"10.1021/acs.jpcc.6c03260","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c03260","url":null,"abstract":"<p>Metal oxide nanozymes are emerging as robust redox catalysts,yetthe molecular basis of their substrate selectivity and reaction pathwaysremains poorly understood. Here, we identify 20 mol% Mn-doped TiO₂ as a nanozyme platform that selectively oxidizes aromaticamino acids through a surface-confined pathway distinct from conventionaldiffusible radical-mediated oxidation. Using tyrosine, histidine,and phenylalanine together with ¹³C/¹⁵N isotopicallylabeled analogues, we combined high-resolution NMR spectroscopy, LC-MS/MS,X-ray photoelectron spectroscopy, and density functional theory calculationsto resolve the underlying reaction mechanism. The data show that substrateoxidation proceeds through direct coordination to Mn-modified surfacesites, followed by oxidative deamination, <em>C</em>_α–<em>C</em>_β bond cleavage, and decarboxylationto yield the corresponding aldehydes: 4-hydroxybenzaldehyde, 1H-imidazole-4-carbaldehyde,and benzaldehyde. Isotopic labeling establishes that this transformationfollows a Strecker-type degradation pathway localized at the nanozymeinterface. XPS analysis demonstrates preservation of the Mn surfaceredox profile during catalysis, consistent with reversible Mn(III)/Mn(IV)cycling within the TiO₂ lattice. Computational modelingfurther supports the thermodynamic feasibility of sequential proton-coupledelectron-transfer steps leading to oxidative fragmentation. Thesefindings establish that Mn doping programs TiO₂ surfacesfor selective dehydrogenase-like reactivity, through surface-directedinterfacial oxidation, distinct from conventional diffusible radical-mediatedpathways. The results provide a framework for rationally engineeringmetal oxide nanozymes with enzyme-like selectivity for targeted biomoleculartransformations.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13688–13700"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124931","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lead-Free FA3BiI6 Perovskite Memristor for Logic Gate Circuits and Data Encryption","authors":"Xuyang Ren,&nbsp;Tuo Zhao,&nbsp;Ciman Chai,&nbsp;Kai Hu,&nbsp;Yuchan Wang","doi":"10.1021/acs.jpcc.6c05402","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c05402","url":null,"abstract":"<p>The heavy metal toxicity of lead-based halide perovskiteshinderstheir practical application in memristors. Herein, we report a lead-freeFA₃BiI₆-based sandwich-structured memristor.The device exhibits stable bipolar resistive switching with negligibledegradation over 200 DC cycles and a retention time of 3000 s, andexcellent uniformity in switching voltages and resistance states.Mechanistic analysis reveals that electric-field-driven Ag⁺ migration, inducing local conductive filaments, is the key to theresistive-switching behavior. Pulse tests demonstrate that the devicecan mimic various biological synaptic plasticity, including excitatorypostsynaptic current (EPSC), paired-pulse facilitation (PPF), andlong-term potentiation/depression (LTP/LTD). Furthermore, OR, AND,and XOR basic logic gate circuits are constructed, with XOR operationsbeing employed for lossless symmetric encryption/decryption of RGBcolor images, and the original image features being completely masked.This work provides a new approach for the development of environmentallyfriendly halide perovskite-based hardware encryption devices.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"14069–14076"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124963","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Moisture-Triggered Solid-Phase Molecular Self-Assembly with Facial Amphiphiles for Efficient and Full-Color Organic Room-Temperature Phosphorescence","authors":"Xue Bai,&nbsp;Yiteng Cai,&nbsp;Letian Yuan,&nbsp;Jianbin Huang,&nbsp;Yun Yan","doi":"10.1021/acs.jpcc.6c04249","DOIUrl":"10.1021/acs.jpcc.6c04249","url":null,"abstract":"<p>Although room-temperature phosphorescent (RTP) materialshave beenextensively investigated, the facile generation of efficient RTP atambient conditions remains a long-standing challenge. Here, we demonstratea moisture-triggered solid-phase molecular self-assembly (SPMSA) strategyto construct RTP materials through the coassembly of facially rigidamphiphiles─such as sodium cholate (SC)─and fluorescentdyes. This approach simultaneously achieves particle adhesion, molecularrearrangement, and the effective isolation and rigidification of dyes.Mechanistic studies reveal that dye molecules spontaneously diffuseinto the hydrophobic pockets formed by SC, where intermolecular interactionspromote spin–orbit coupling (SOC) and facilitate intersystemcrossing (ISC). These factors, combined with the rigid environmentprovided by the facially rigid SC matrix, cooperatively suppress nonradiativetransitions of triplet excitons. Consequently, we achieve a long phosphorescencelifetime of up to 830 ms and full-spectrum visible RTP. Leveragingthese advantages, we demonstrate water-based RTP inks, RTP coatingsand RTP 3D origami, offering a green and sustainable pathway for thedevelopment of advanced luminescent materials.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13999–14006"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A First-Principles Study of Surface-Dependent Synergy between H2O and O2 on Silver-Based Oxide Semiconductors","authors":"T. T. Dorini,&nbsp;J. Andrés,&nbsp;E. Longo,&nbsp;M. A. San-Miguel","doi":"10.1021/acs.jpcc.6c03959","DOIUrl":"10.1021/acs.jpcc.6c03959","url":null,"abstract":"<p>Silver-based ternary oxides, including Ag₃PO₄, β-Ag₂MoO₄, and the α-and γ-Ag₂WO₄ polymorphs, are promisingphotocatalysts forgenerating reactive oxygen species (ROS). In this work, density functionaltheory calculations were employed to disclose the atomic site-specificelectronic properties governing the activation of coadsorbed O₂ and H₂O molecules, a key step in ROS formation,at these semiconductor surfaces. We found that O₂ activation,as characterized by O–O bond weakening, is enhanced by H₂O coadsorption on Ag₃PO₄(110), β-Ag₂MoO₄(110), and α-Ag₂WO₄(100), whereas the opposite trend is observed on β-Ag₂MoO₄(111) and α-Ag₂WO₄(001).Electronic structure analyses corroborate this surface-dependent behavior.These results reconcile contrasting views on the role of H₂O by demonstrating its critical dependence on surface structure andintrinsic reactivity, providing crucial insights for the rationaldesign and optimization of Ag-based semiconductor photocatalysts throughcontrolled surface exposure or humidity management.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13701–13711"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Oxygen Reduction Reaction on N-Doped Graphene under Acidic Conditions: Integrating N-Dopant Site Structure Changes with Competing Elementary Reaction Steps","authors":"Spand Mehta,&nbsp;Aishwarya Rao,&nbsp;Aravind Asthagiri","doi":"10.1021/acs.jpcc.6c04248","DOIUrl":"10.1021/acs.jpcc.6c04248","url":null,"abstract":"<p>Nitrogen-doped carbon(CN_<em>x</em>) catalystsare promising alternatives to replace Pt for the electrochemical oxygenreduction reaction (ORR) in proton-exchange-membrane fuel cells. Todate, there remains an ongoing debate regarding the nature of activesites on CN_<em>x</em>. Experimental half-cell ORRactivity studies of CN_<em>x</em> catalysts correlatethe fraction of pyridinic sites (characterized ex situ by X-ray photoelectronspectroscopy) to ORR activity. In contrast, density functional theory(DFT) studies using the chemical hydrogen electrode (CHE) approachpredominantly show quaternary/oxide sites to have higher activitythan that of pyridinic sites. In this work, we integrate the initialthermodynamic stability analysis of the N-dopant structure at 1.23V-RHE with subsequent competing ORR elementary steps as a functionof applied potential. In contrast to earlier studies, our integratedapproach predicts high activity for pyridinic sites, with a majorityof quaternary sites, except basal quaternary, which show low activity.This enhanced activity occurs through an initial oxidation of thepyridinic sites via H₂O that converts the pyridinic sitesto pyridinic oxide structures at 1.23 V-RHE (before the start of ORR).Subsequent ORR steps on this structure result in a stable 4 proton–electroncycle of elementary steps that yield high ORR DFT thermodynamic limitingpotentials. Therefore, the DFT-CHE results suggest that pyridinicsites are indeed active for ORR but first must convert to an oxidizedstructure that mediates the ORR mechanism. Our findings suggest apotential mechanism to reconcile the ongoing debate on the natureof active sites and provide fundamental insights into the ORR activityof CN_<em>x</em> catalysts.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"130 40","pages":"13720–13733"},"PeriodicalIF":3.4,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}