ACS Omega最新文献

{"title":"Modeling Local Aerosol Surface Environments: Clustering of Pyruvic Acid Analogs, Water, and Na⁺, Cl^- Ions.","authors":"Georg Baadsgaard Trolle, Jakub Kubečka, Jonas Elm","doi":"10.1021/acsomega.4c09196","DOIUrl":"10.1021/acsomega.4c09196","url":null,"abstract":"<p><p>Pyruvic acid is an omnipresent compound in nature and is found both in the gas phase and in the particle phase of the atmosphere as well as in aqueous solution in the hydrosphere. Despite much literature on the photochemical degradation and stability of pyruvic acid in different chemical environments, the study of simultaneous interactions between gas-phase pyruvic acid or similar carboxylic acids with water and ions is not well-understood. Here, we present a study of microhydrated molecular clusters containing pyruvic acid and the structurally analogous carboxylic acids lactic acid, propionic acid, and 2,2-dihydroxypropanoic acid by probing geometries, binding free energies, hydrate distributions, as well as their infrared (IR) absorption spectra. We performed a meticulous configurational sampling protocol for the various hydrated clusters ranging from low level of theory to high level of theory to identify the lowest free energy structure. We find that cluster geometries and especially their water structure are highly sensitive to the presence and character of ions. We show that the hydration of the studied organic acids is thermodynamically unfavorable in the gas phase and ions are necessary for mediating interactions between organic acids and water thus stabilizing the clusters. Finally, we find a clear correlation between decreasing pyruvic acid carboxylic O-H stretching frequencies, increasing intensity when adding more water to the clusters, and a correlation between increasing redshifting of the O-H frequencies upon addition of ions to the clusters. The observations done in this study could pave the way to unravel the mechanisms behind the transitioning of organic acids from the gas phase to the particle phase.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 1","pages":"1470-1485"},"PeriodicalIF":3.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11740629/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996212","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Steric and Electronic Effects of Zirconocenealkyl-Borate Ion Pairs on Catalyst Activation: A Theoretical Study.","authors":"Wijitra Meelua, Tanchanok Wanjai, Julianna Oláh, Mikko Linnolahti, Jitrayut Jitonnom","doi":"10.1021/acsomega.4c08377","DOIUrl":"10.1021/acsomega.4c08377","url":null,"abstract":"<p><p>The effectiveness of metallocene catalysts in the cationic ring-opening polymerization (cationic ROP) of ε-caprolactone (CL) is influenced by the choice of metallocene/borate systems, particularly their bulkiness. Recent research examines this effect on the initiation and propagation stages of cationic ROP. We conducted a density functional theory study on the precatalyst activation of cationic CL ROP by zirconocene/borate catalysts, where four models of zirconocene precatalysts (Cp₂ZrMe₂ (<b>a</b>), (Me₅Cp)CpZrMe₂ (<b>b</b>), (Me₅Cp)₂ZrMe₂ (<b>c</b>), and Ind₂ZrMe₂ (<b>d</b>)) were combined with boron cocatalysts B(C₆F₅)₃ and [X⁺][B(C₆F₅)₄ ^-] (X⁺ = Ph₃C⁺ or PhMe₂NH⁺). We modeled and predicted their thermodynamic, steric, and electronic properties during ion-pair formation and separation. The calculated Gibbs energies of ion-pair formation correlated with the positive charge at the metal center and steric congestion of the catalyst. All catalyst precursors showed exothermic and exergonic insertion of CL, toluene solvent, and contact ion pairs; solvent-separated ion pairs were the preferred activation pathway. Catalyst <b>c</b> showed the most stable ion pair in precatalyst activation, with the lowest separation energy, aided by methyl group bulkiness and toluene solvent. We evaluated Cp'-based ligands using percent buried volume (%<i>V</i> _Bur) trends. Noncovalent interaction analysis indicated weak interactions at ion-pair contacts. This study enhances our understanding of cationic ROP and could aid in developing new polymerization catalysts for polyester synthesis.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 1","pages":"1082-1093"},"PeriodicalIF":3.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11739944/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996274","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Study of Reinforced Cement Paste Properties with Woven Fabrics from Poly(ethylene Terephthalate) Bottle Yarn.","authors":"Montien O-Thongkham, Kiartiphum Duangsri, Nopporn Rattanachoung, Siriwun Duanghirun, Sujira Khojitmate","doi":"10.1021/acsomega.4c07140","DOIUrl":"https://doi.org/10.1021/acsomega.4c07140","url":null,"abstract":"<p><p>This study investigates the reinforcement of cement paste with woven fabrics made from recycled poly(ethylene terephthalate) (PET) bottle yarn, aiming to enhance its mechanical properties while addressing PET waste. PET bottles were transformed into yarn with a denier of 3,593.8, strength of 91.2 N, and 25.6% elongation before breaking. The yarns were woven into plain weave, twill weave, and basket weave fabrics, with the basket weave exhibiting the highest yarn density at 10 threads per inch and fabric weight of 277.08 g per square meter. Mechanical testing of cement paste samples, unreinforced, reinforced with PET fabrics, and reinforced with standard fiberglass fabric, demonstrated that the basket weave fabric reinforced samples exhibited superior compressive and flexural strengths of 31.99 and 1.53 N per square millimeter, respectively. This study highlights the potential of using PET bottle yarn woven fabrics, especially the basket weave pattern, as an effective and sustainable reinforcement material in cement paste. The findings offer a promising approach for PET waste valorization and the development of construction materials with improved performance. Environmental and economic assessments indicate that this approach can reduce CO₂ emissions by approximately 11% and achieve cost savings of 6.4% compared to traditional glass fiber reinforcement. These results demonstrate the potential for sustainable engineering solutions that combine environmental benefits with economic viability.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 1","pages":"599-608"},"PeriodicalIF":3.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11739945/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Conformationally Restricted Grp94-Selective Inhibitors.","authors":"Hao Xu, Kyler Pugh, Brian S J Blagg","doi":"10.1021/acsomega.4c06661","DOIUrl":"10.1021/acsomega.4c06661","url":null,"abstract":"<p><p>Selective inhibition of glucose regulated protein 94 (Grp94), the most structurally unique isoform of heat shock protein 90 (Hsp90), has been implicated in the treatment of various disease states, including primary open-angle glaucoma and metastatic cancer. In this study, nine analogues were designed and synthesized by conformationally restricting <b>KUNG65</b>, a second generation Grp94-selective inhibitor. Conformational constraints were applied to restrict the rotatable bonds and to bias the benzyl moiety into the Grp94 site 1 pocket as well as to reduce the entropic penalty paid upon binding. A fluorescence polarization assay demonstrated that lead compound <b>C6</b> exhibited an affinity of 5.52 μM for Grp94 and showed no affinity for Hsp90α, indicating its potential as a Grp94-selective inhibitor.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 1","pages":"449-455"},"PeriodicalIF":3.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11740130/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Microstructural Characteristics of Damaged Hot Dry Rock Flow Network Stimulated by Cryogenic Liquid Nitrogen Shock.","authors":"Yong Sun, Long Feng, Cheng Zhai, Yang Zhao, Xu Yu, Jizhao Xu, Yuzhou Cong, Hexiang Xu, Xinyu Zhu, Xianwei Xiang","doi":"10.1021/acsomega.4c08858","DOIUrl":"https://doi.org/10.1021/acsomega.4c08858","url":null,"abstract":"<p><p>Hot dry rock (HDR) geothermal development faces challenges due to the difficulty of stimulating fluid flow and heat-exchange fracture channels within deep, low-porosity, and low-permeability reservoirs. A liquid nitrogen cyclic cold shock method was proposed, using liquid nitrogen as a fracturing fluid. The large temperature difference between the liquid nitrogen and the hot rock induces thermal stress, forming a complex pore-fracture network. In this study, HDR samples at various temperatures were subjected to 5 cycles of liquid nitrogen cold shock. Pore-fracture structures of the damaged cores were tested by low-field nuclear magnetic resonance and X-ray microscopy. Results showed temperature-dependent changes in porosity: at 200 and 300 °C, small-size pores rose, with maximum porosities of 3.13% and 3.37%; at 400-500 °C, large-size pores rose, with porosities reaching 4.59% and 12.76%. Different pore types exhibited distinct responses: mesopores are the most sensitive to temperature shock, micropores responded to the early damage stage, and macropores only responded under high-temperature differences and multiple cycles. Multifractal analysis revealed increased heterogeneity and concentration in pore distribution with damage escalation. The slice porosity, fractal box dimension, and probability entropy demonstrated exponential growth. Results indicate that temperature difference is the main controlling factor of pore damage in HDR, and cyclic shock can also contribute to continuous pore development. There is a high correlation between pore-fracture parameters and multifractal parameters, allowing the multifractal to reflect a more complex pore-fracture structure quantitatively.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 1","pages":"1261-1278"},"PeriodicalIF":3.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11739976/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996209","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Prediction of the Topologically Nontrivial Phase in Three-Dimensional ABX Zintl Compounds.","authors":"Ina Marie R Verzola, Rovi Angelo B Villaos, Zhi-Quan Huang, Hsin Lin, Feng-Chuan Chuang","doi":"10.1021/acsomega.4c08153","DOIUrl":"10.1021/acsomega.4c08153","url":null,"abstract":"<p><p>Zintl compounds have garnered research interest due to their diverse technological applications. Utilizing first-principles calculations, we performed a systematic study of ABX (A = Li, Na, K, Rb, or Cs; B = Si, Ge, Sn, or Pb; and X = P, As, Sb, or Bi) Zintl materials with the <i>P</i>6₃ <i>mc</i> KSnSb-type structure. Notably, six ABX Zintl compounds (RbSiBi, CsSiBi, LiGeBi, KGeBi, RbGeBi, and CsGeBi) were found to have topologically nontrivial phases, as demonstrated by the <i>Z</i> ₂ invariant computed using the hybrid functional HSE06. Among them, RbGeBi and CsGeBi were identified as topological insulators with nontrivial bandgaps of 28 and 116 meV, respectively. The topological phase transition arises as a result of spin-orbit coupling, as demonstrated in the representative material, CsGeBi. Additionally, the existence of gapless surface states further confirmed the topologically nontrivial phases of the six materials. Moreover, phonon spectra and formation energy calculations verified that all identified nontrivial materials under the hybrid functional are dynamically and structurally stable, except LiGeBi which exhibited imaginary phonon frequencies. Finally, the thermodynamic stability of the representative material CsGeBi was verified through elastic constants and ab initio molecular dynamics simulations. These results provide foundational insights that could drive further experimental research and synthesis, potentially enabling the application of ABX Zintl compounds in electronic technologies such as quantum computing or spintronics.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 1","pages":"964-971"},"PeriodicalIF":3.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11740378/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996160","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical Monitoring of Vitamins B₉ and C in Environmental Matrices with an Oligo Diaminotriazole Electrode.","authors":"Veeramani Mangala Gowri, Krishnamoorthy Shanmugaraj, Theelada Panleam, Tanawat Imboon, Jeerawan Khumphon, Dusadee Khamboonrueang, Pongthep Prajongtat, Chaisak Issro, Sirikanjana Thongmee","doi":"10.1021/acsomega.4c07588","DOIUrl":"10.1021/acsomega.4c07588","url":null,"abstract":"<p><p>Chemical polymerization/oligomerization opens numerous opportunities, from fundamental materials research to practical applications in catalysis, energy, sensing, and medicine. The electrochemical detection of vitamins B₉ (folic acid) and C (ascorbic acid) requires new approaches because of low selectivity, electrode fouling, and interference from other chemicals. As an excellent material for long-term vitamin detection, oligo 3,5-diamino-1,2,4-triazole (oligo DAT) enhances the sensitivity, selectivity, and stability of sensors by creating a stable, conductive layer that facilitates electron transfer and reduces interference from common substances like glucose or uric acid. This work investigates the electrochemical sensing properties of oligo DAT, utilizing hydrogen tetrachloroaurate (III) (HAuCl₄) as an oxidizing agent at ambient temperature for the concurrent and sensitive detection of vitamins B₉ and C. The oligo DAT was carefully characterized by spectroscopic and microscopic techniques to confirm its structure and properties. The GC electrode was subsequently connected to the oligo DAT by a potentiodynamic technique. The oligo DAT-modified electrode exhibited higher catalytic activity than the unmodified GC electrode for the oxidation of vitamins B₉ and C. This led to the determination of the sensitivity levels for both vitamins; the lowest measured concentration for vitamin C was 1 × 10^-11 M with a theoretical limit of detection (LOD) of 1.9 × 10^-11 M, and for vitamin B₉, the lowest measured concentration was 1 × 10^-11 M with a theoretical LOD of 3.5 × 10^-11 M. The practical efficacy of this straightforward method was proven by the quantification of vitamins B₉ and C in human plasma samples.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 2","pages":"1954-1965"},"PeriodicalIF":3.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11755172/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044880","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Novel Decellularization Scheme for Preparing Acellular Fish Scale Scaffolds for Bone Tissue Engineering.","authors":"Shilong Su, Ruideng Wang, Jinwu Bai, Zhengyang Chen, Fang Zhou","doi":"10.1021/acsomega.4c05096","DOIUrl":"10.1021/acsomega.4c05096","url":null,"abstract":"<p><p>In bone tissue engineering, a suitable scaffold is the key. Due to their similar composition to bone tissue, special structure, good mechanical properties, and osteogenic properties, acellular fish scale scaffolds are potential scaffolds for bone tissue engineering. At present, the fish scale decellularization scheme mostly uses a combination of sodium dodecyl sulfate and ethylenediamine tetraacetic acid (EDTA), but this method has problems. We optimized this method using a combined method of Triton X-100, EDTA, and nuclease. In this study, the optimal scheme was screened with respect to the decellularization effect, extracellular matrix composition and structure retention, mechanical properties, cell biocompatibility, and osteogenic differentiation ability. The results showed that the optimal scheme was as follows: the native fish scales were incubated in 0.1% EDTA for 24 h, and then the cellular components were removed with 1% Triton X-100 for 4 days, followed by nuclease digestion for 24 h. On that basis, we proposed a novel and more suitable fish scale decellularization scheme, and the acellular fish scale scaffold prepared by this decellularization scheme may have great potential in bone tissue engineering.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 1","pages":"230-238"},"PeriodicalIF":3.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11740628/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996171","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT Investigation of the Stereoselectivity of the Lewis-Acid-Catalyzed Diels-Alder Reaction between 2,5-Dimethylfuran and Acrolein.","authors":"Mohamed Chellegui, Mahmoud Trabelsi, Benoît Champagne, Vincent Liégeois","doi":"10.1021/acsomega.4c07888","DOIUrl":"10.1021/acsomega.4c07888","url":null,"abstract":"<p><p>Density functional theory (DFT) has been enacted to study the Diels-Alder reaction between 2,5-dimethylfuran (2,5-DMF), a direct product of biomass transformation, and acrolein and to analyze its thermodynamics, kinetics, and mechanism when catalyzed by a Lewis acid (LA), in comparison to the uncatalyzed reaction. The uncatalyzed reaction occurs via a typical one-step asynchronous process, corresponding to a normal electron demand (NED) mechanism, where acrolein is an electrophile whereas 2,5-DMF is a nucleophile. The small endo selectivity in solvents of low dielectric constants is replaced by a small exo selectivity in solvents with larger dielectric constants, such as DMSO. In the catalyzed process, the LA interacts with acrolein, forming a O-LA coordinating bond, that enhances its electron-acceptor character, further favoring the NED mechanism and reducing the activation energy. When AlCl₃ and GaCl₃ catalyze the reaction, the bond formations of both the endo and exo pathways occur via a two-step asynchronous process. Thus, these processes involve the formation of two transition states and a stable intermediate. The second transition state is the critical one and it dictates the increase of the exo selectivity, in comparison to the uncatalyzed reaction. The DFT calculations have also unraveled that the LA plays additional roles, i.e. it forms stable complexes with the carbonyl group of acrolein while AlCl₃ and GaCl₃ form dimers, which also impact the different equilibria.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 1","pages":"833-847"},"PeriodicalIF":3.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11739960/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Transient Kinetic QXAFS Approach for Understanding the RDE-MEA Gap in Fuel Cell (Oxygen Reduction Reaction) Performances of Pt-Based Electrocatalysts.","authors":"Takefumi Yoshida, Shinobu Takao, Hiroko Ariga-Miwa, Xiao Zhao, Gabor Samjeské, Takuma Kaneko, Tomoya Uruga, Yasuhiro Iwasawa","doi":"10.1021/acsomega.4c07787","DOIUrl":"10.1021/acsomega.4c07787","url":null,"abstract":"<p><p>There is a large gap between the performances indicated by rotating disk electrode (RDE) results in acidic media and the actual performances obtained in membrane-electrode assemblies (MEAs) composed of the same electrocatalysts. It is unclear whether the intrinsic kinetic reactivity of the available surface Pt sites of Pt-based cathode electrocatalysts is similar or different at RDE and in MEA. To address this, we used an operando element-selective time-resolved Pt L_III-edge quick X-ray absorption fine structure (QXAFS) technique to determine transient response profiles and rate constants, <i>k</i> _d(WL), <i>k</i> _{d(CN_Pt-O)}, and <i>k</i> _{d(CN_Pt-Pt)}, corresponding to changes in the oxidation states [white line (WL) intensity] and local structures (coordination numbers of Pt-O and Pt-Pt bonds) at Pt sites for nine representative Pt-based cathode electrocatalysts under transient voltage operations, aiming to understand the oxygen reduction reaction (ORR) performance gap between RDE and MEA. For the first time, the transient kinetics and reactivity of electrocatalyst themselves in MEA, characterized by the operando QXAFS analysis technique, were systematically compared with the electrochemical activity [mass activity (<i>I</i> _mass) and surface specific activity (<i>I</i> _specific)] of the electrocatalysts in MEA and at RDE. The operando time-resolved QXAFS analysis revealed that the ORR activities of available surface Pt sites at RDEs of the electrocatalysts, including notably structured electrocatalysts (concave octahedral PtNi _<i>x</i> /C and Pt nanowire/C), were kinetically reflected at good levels of <i>k</i> _d(WL) and <i>k</i> _{d(CN_Pt-O)} in MEA performances, despite large RDE-MEA gaps observed in the electrochemically determined <i>I</i> _mass and <i>I</i> _specific. As the <i>I</i> _mass and <i>I</i> _specific of MEA increased, the relaxation time <i>k</i> _{d(CN_Pt-Pt)} ^-1, which indicates long-term durability, decreased, reflecting a dilemma in the development of remarkable Pt-based electrocatalysts, while the <i>k</i> _{d(CN_Pt-Pt)} ^-1 was almost independent of ECSA. The differences and similarities in the kinetic reactivity and durability of the Pt surface between RDE and MEA were examined using operando QXAFS transient kinetics and electrochemical performance measurements to elucidate the underlying factors contributing to the performance gap between RDE and MEA. The insights gained aim to support the development of next-generation polymer electrolyte fuel cells with enhanced performance and durability by leveraging the operando time-resolved QXAFS technique under the transient kinetic-response operation.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 1","pages":"796-808"},"PeriodicalIF":3.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11739974/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}