Xiaodong Jia, Lv Zhao, Jinpeng Cai, Peilun Shen, Dianwen Liu
{"title":"Microstructural characteristics and reaction mechanism of ammonium sulfate-promoted cuprite sulfidation","authors":"Xiaodong Jia, Lv Zhao, Jinpeng Cai, Peilun Shen, Dianwen Liu","doi":"10.1016/j.apsusc.2025.164851","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.164851","url":null,"abstract":"With the depletion of copper sulfide resources, efficient flotation technologies for low-grade copper oxides such as cuprite have garnered considerable attention. Due to the good hydrophobicity exhibited by copper sulfide, sulfidation is generally required for the flotation of cuprite. Meanwhile, ammonium sulfide ((NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>) has been widely used as an activator in the sulfidation flotation of cuprite. However, the mechanism through which (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> enhances the sulfidation effect remains to be systematically elucidated. The study of cuprite’s flotation behavior and surface wettability in this paper reveals that (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> reduces the depressant effect of excessive Na<sub>2</sub>S on cuprite and enhances its flotation efficiency. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis of sulfidation product ions (S<sub>2</sub><sup>−</sup>, S<sup>−</sup> and Cu<sub>2</sub>S<sup>+</sup>) verified the (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> enhancement of cuprite sulfidation. Microscopic morphology analysis indicates that cuprite surface roughness increased and sulfide products exhibited higher crystallinity and quantity following (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>-enhanced sulfidation. It was revealed by X-ray photoelectron spectroscopy (XPS) analyses that the sulfidation of cuprite was promoted by (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>, as demonstrated by the increase of hydrophobic S<sub>2</sub><sup>2−</sup> and S<sub>n</sub><sup>2−</sup> species on the cuprite surface; oxygen was also found to play a crucial role in this process. The main product of direct sulfidation was identified as Cu<sub>7.2</sub>S<sub>4</sub> by Grazing-Incidence X-ray Diffraction (GIXRD), and the main product of (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>-enhanced sulfidation was also identified as Cu<sub>7.2</sub>S<sub>4</sub> and Cu<sub>1.8</sub>S. Furthermore, it has been shown by studies on the solution components that [Cu(NH<sub>3</sub>)<sub>n</sub>]<sup>2+</sup> are formed through the combination of (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> with copper ions, thereby facilitating the dissolution of cuprite. Subsequently, [Cu(NH<sub>3</sub>)<sub>n</sub>]<sup>2+</sup> and HS<sup>−</sup> are caused to react, resulting in the generation of copper sulfide and the release of NH<sub>3</sub>. A significant enhancement in cuprite’s sulfidation, a strengthened adsorption of NaBX, and an improved flotation efficiency are all achieved through the oxygen-ammonium synergistic effect.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"10 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255341","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jianing Hu, Qingqing Han, Yanqi Liu, Yu Fan, Wen Xi, Youfang Zhang, Rui Wang, Huanwen Wang, Yansheng Gong, Jun Jin
{"title":"Interface engineering of Ni-MOF/NiCoFe-Prussian blue analogue composite with enhanced Na+ storage kinetics for high-performance hybrid capacitive deionization","authors":"Jianing Hu, Qingqing Han, Yanqi Liu, Yu Fan, Wen Xi, Youfang Zhang, Rui Wang, Huanwen Wang, Yansheng Gong, Jun Jin","doi":"10.1016/j.apsusc.2025.164854","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.164854","url":null,"abstract":"Prussian blue faces challenges, including a tendency for particle agglomeration and limited charge transfer, which limit their application in hybrid capacitive deionization (CDI) technology. Herein, we develop a Ni-MOF/NiCoFe-Prussian blue analogue (NiCoFe-PBA) heterostructure by employing an in-situ growth of NiCoFe-PBA on a 2D Ni-MOF substrate. The formation of this heterogeneous interface significantly enhances charge transfer efficiency. Additionally, the in-situ growth of PBA on the MOF surface effectively mitigates the stacking of 2D Ni-MOF sheets, thereby increasing the exposure of active sites. Furthermore, Ni improves the structural stability of the composite during Na<sup>+</sup> ion embedding/de-embedding, while Co doping introduces additional electrochemically active sites, significantly boosting the desalination capacity. Therefore, the Ni-MOF/NiCoFe-PBA composite exhibits an excellent desalination capacity of 63.19 mg g<sup>−1</sup> in a 500 μS cm<sup>−1</sup> NaCl solution, along with good cycling stability. The Na<sup>+</sup> ion storage mechanism of the Ni-MOF/NiCoFe-PBA composite is thoroughly investigated. This study provide a new approach for developing high-performance electrodes for hybrid CDI technology.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"90 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuqing Sun , Pan Li , Jing He , Qingmin Ma , Man Shen , Zhixue Tian , Ying Liu
{"title":"Interface engineering of VSe2/LaFeO3 vertical heterostructures: modulation of magnetic and electronic properties","authors":"Yuqing Sun , Pan Li , Jing He , Qingmin Ma , Man Shen , Zhixue Tian , Ying Liu","doi":"10.1016/j.apsusc.2025.164845","DOIUrl":"10.1016/j.apsusc.2025.164845","url":null,"abstract":"<div><div>We performed first-principles calculations based on density functional theory to investigate the atomic structure, electronic properties, and magnetic behavior of monolayer and bilayer 1T- and H-VSe<sub>2</sub> adsorbed on the (001) surface of LaFeO<sub>3</sub> (LFO) with LaO and FeO<sub>2</sub> termination layers, respectively. Our findings reveal that both monolayer and bilayer VSe<sub>2</sub> can stably adhere to the LFO (001) surface. Monolayer 1T- and H-VSe<sub>2</sub> exhibit ferromagnetic (FM) characteristics, where the 1T phase is metallic and the H phase is semiconducting. Charge transfer from LFO to VSe<sub>2</sub> induces the reversal of the magnetic moments for specific V atoms in VSe<sub>2</sub>, leading to in-plane antiferromagnetic (AFM) properties. Monolayer 1T-VSe<sub>2</sub> on the LFO surface retains metallic, whereas monolayer H phase exhibits diverse behaviors: some configurations preserve their semiconducting properties, while others transition to metallic states. For bilayer VSe<sub>2</sub>/LFO heterostructures, both 1T- and H-bilayer VSe<sub>2</sub> exhibit interlayer AFM alignment and in-plane FM states. Bilayer 1T-VSe<sub>2</sub> maintains its metallic character, while bilayer H-VSe<sub>2</sub> with LaO termination exhibits half-metallic properties, and that with FeO<sub>2</sub> termination retains semiconducting, enabling tunable half-metal/semiconductor transitions via LFO substrate engineering. Finally, we explored the hydrogen evolution reaction (HER) catalytic performance of single-atom Pt-doped VSe<sub>2</sub> with and without the LFO (001) substrate. The results indicate that the presence of the LFO substrate significantly enhances the stability of single-atom Pt on VSe<sub>2</sub> and improves the HER catalytic efficiency for Pt-doped monolayer VSe<sub>2</sub>. Additionally, the monolayer H-VSe<sub>2</sub>/LFO heterostructure demonstrates potential for Z-scheme photocatalytic applications.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"717 ","pages":"Article 164845"},"PeriodicalIF":6.9,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145254900","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hao Lin , Changsheng Xiao , Shuang Liu , Jiaxiang Li , Shanshan Zhou , Hua Pan , Tang Fan , Xiaofeng Shen , Qingquan Xue
{"title":"Design and mechanistic insight into a Na-C3N4/Bi4O5Br2 S-scheme heterojunction for efficient antibiotic degradation via low concentration peroxymonosulfate activation","authors":"Hao Lin , Changsheng Xiao , Shuang Liu , Jiaxiang Li , Shanshan Zhou , Hua Pan , Tang Fan , Xiaofeng Shen , Qingquan Xue","doi":"10.1016/j.apsusc.2025.164809","DOIUrl":"10.1016/j.apsusc.2025.164809","url":null,"abstract":"<div><div>Advances in medical biotechnology have driven the widespread use of antibiotics, leading to their environmental persistence and associated threats to human health. In this work, a Na-modified S-scheme heterojunction Na-C<sub>3</sub>N<sub>4</sub>/Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> was fabricated for photocatalytic activation of PMS to degrade tetracycline (TC). The Na ions are embedded into the heptazine ring of C<sub>3</sub>N<sub>4</sub>, which alters the symmetrical structure of C<sub>3</sub>N<sub>4</sub>. Importantly, Na-C<sub>3</sub>N<sub>4</sub>/Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> activated a low PMS dosage (5 mg) to generate reactive oxygen species, achieving rapid tetracycline degradation (91 % in 10 min). This superior performance stems from the synergistic effects of efficient charge separation and the strong redox capacity of the heterojunction. <em>In-situ</em> XPS analysis revealed the electron transfer pathway within the Na-C<sub>3</sub>N<sub>4</sub>/Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> composite under both dark and illuminated conditions. Combined with DFT calculations, these results support an S-scheme mechanism for PMS activation in TC degradation. Upon light irradiation, electrons in the CB of Na-C<sub>3</sub>N<sub>4</sub> preferentially migrate to the VB of Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub>, while the remaining electrons in the CB of Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> and holes in the VB of Na-C<sub>3</sub>N<sub>4</sub> react with OH<sup>−</sup>, O<sub>2</sub>, and PMS to generate reactive species. This study proposed a reasonable design for an ionic-doped S-scheme heterojunction used for degradation of organic wastewater through photocatalysis and advanced oxidation technology.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"717 ","pages":"Article 164809"},"PeriodicalIF":6.9,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145254904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Temperature-adaptive MoN-Ag coatings under operando tribology: multiscale Ag diffusion-oxidation coupling","authors":"Yong Cheng , Yupeng Zhang , Yiqun Feng, Meiqi Zhang, Aiying Wang, Zhenyu Wang","doi":"10.1016/j.apsusc.2025.164842","DOIUrl":"10.1016/j.apsusc.2025.164842","url":null,"abstract":"<div><div>The development of temperature-adaptive lubricant coatings for foil air bearings remains a major challenge. Here, dense MoN–Ag nanocomposite coatings with varying Ag contents (0–22.8 at.%) were deposited by HiPIMS–DCMS. The coatings exhibited low residual stress, strong adhesion, and high mechanical performance. Tribological tests showed that the coefficient of friction (COF) decreased with Ag addition at 350 °C and 500 °C, reaching 0.389 and 0.223, respectively, for the 22.8 at.% Ag coating. At 600 °C, however, the COF increased with Ag content, while the 13.4 at.% Ag coating displayed the lowest wear rate of 2.84 × 10<sup>-5</sup> mm<sup>3</sup>N<sup>-1</sup>m<sup>−1</sup>. Under simulated service conditions, the 13.4 at.% Ag coating demonstrated a reduction in COF from ∼ 0.4 to 0.26 across 25–600 °C, evidencing self-adaptive lubrication. This behavior is ascribed to the formation of a low-shear-strength surface layer, where Ag diffusion and the generation of MoO<sub>x</sub>, Ag<sub>2</sub>MoO<sub>4</sub>, and Ag<sub>2</sub>Mo<sub>4</sub>O<sub>13</sub> promote facile slip along crystal planes, thereby enhancing lubricity.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"717 ","pages":"Article 164842"},"PeriodicalIF":6.9,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255349","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Viacheslav Kalinovych, Anastasiia Deineko, Sascha L. Mehl, Lesia Piliai, Kevin C. Prince, Iva Matolínová, Tomáš Skála, Nataliya Tsud
{"title":"Functionalization of the polycrystalline cerium oxide with phenylphosphonic acid molecules","authors":"Viacheslav Kalinovych, Anastasiia Deineko, Sascha L. Mehl, Lesia Piliai, Kevin C. Prince, Iva Matolínová, Tomáš Skála, Nataliya Tsud","doi":"10.1016/j.apsusc.2025.164834","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.164834","url":null,"abstract":"This work reports a study of the functionalization of polycrystalline cerium oxide (pCeO<sub>2</sub>) films by the phenylphosphonic acid (PPA) molecules deposited either in vacuum or from aqueous solution. The systems are characterized using synchrotron-based techniques, including core-level and valence-band photoelectron spectroscopy, resonant photoemission and near-edge X-ray absorption spectroscopy. PPA binds strongly to the pCeO<sub>2</sub> surface via the phosphonate group in a tridentate geometry, accompanied by deprotonation of the P–OH groups and the formation of surface hydroxyl groups. The binding configuration is independent of molecular deposition technique and oxide surface morphology. Thermal stability analysis reveals that low coverage PPA adlayers (0.07 ML) are prone to desorption and decomposition upon heating. In contrast, high coverage adlayers (0.17 ML), particularly those formed in the presence of water, exhibit higher thermal stability as no molecular decomposition was observed up to 400 °C. The deposition of PPA from aqueous solution is found to protect the surface of pCeO<sub>2</sub> films from reduction. The results contribute to the understanding of phosphonate–cerium oxide interactions by highlighting the influence of the deposition environment and surface morphology on molecular bonding and stability.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"357 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mei Hang Lei, Ding Ling Gao, Ya Yuan Zhang, Na Qin, Peng Xiang, Xiong Huang, Li Nan Xu, Jian Hua Chen, Qian Yang
{"title":"Efficient separation of phosphate ions from water across a wide pH range using a triphenylamine-p-phenylenediamine/TMC composite membrane","authors":"Mei Hang Lei, Ding Ling Gao, Ya Yuan Zhang, Na Qin, Peng Xiang, Xiong Huang, Li Nan Xu, Jian Hua Chen, Qian Yang","doi":"10.1016/j.apsusc.2025.164855","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.164855","url":null,"abstract":"The persistent accumulation of phosphate ions in wastewater, which leads to eutrophication, has garnered substantial attention within the scientific community. Nanofiltration (NF) membranes are widely used for water treatment due to their simplicity, effective multivalent ion rejection, and absence of phase change; however, their practical application is limited by the “trade-off effect” and poor antifouling performance. Therefore, the development of membrane materials that simultaneously enhance rejection efficiency, flux, and anti-fouling performance is of great practical significance. In this study, polyaniline (Ani) and <em>para</em>-phenylenediamine (pPD) were polymerized in situ on a polyethersulfone (PES) support using ammonium persulfate as the oxidant to synthesize PAPD. Subsequently, PAPD was integrated with trimesoyl chloride through interfacial polymerization, thereby fabricating a PAPD/PES composite nanofiltration membrane specifically designed for phosphate separation. The membrane surface featured protruding structures with nanoscale particulate characteristics. At ambient temperature, under an operational pressure of 2.5 bar, with a solution pH of 9 and an initial phosphate concentration of 10 mg L<sup>–1</sup>, the membrane flux reached 58.15 L m<sup>–2</sup>h<sup>−1</sup> bar<sup>−1</sup>, with a phosphate rejection of 81.86 %. Stability tests confirmed excellent structural durability. In real wastewater containing 1.03 mg P L<sup>–</sup>1, the membrane reduced phosphate to 0.51 mg P L<sup>–</sup>1, meeting China’s Grade B discharge standard (1.0 mg P L<sup>–</sup>1). This work demonstrates that the PAPD/PES composite membrane, modified with Ani and pPD, provides enhanced phosphate rejection, high flux, and robust antifouling performance, offering a promising strategy for efficient water treatment and potential industrial-scale applications.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"36 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255294","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Iva Šarić Janković, Robert Peter, Ivna Kavre Piltaver, Harun Hano, Karlo Veličan, Antonio Borzatti, Mato Knez, Mladen Petravić
{"title":"Controlled reduction and development of in-gap states in anatase TiO2 under low-energy hydrogen bombardment","authors":"Iva Šarić Janković, Robert Peter, Ivna Kavre Piltaver, Harun Hano, Karlo Veličan, Antonio Borzatti, Mato Knez, Mladen Petravić","doi":"10.1016/j.apsusc.2025.164853","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.164853","url":null,"abstract":"In this study, we investigate the reduction mechanism and modifications of the electronic structure of anatase TiO<sub>2</sub> thin films induced by low-energy H<sub>2</sub><sup>+</sup> ion bombardment at room temperature, focusing on hydrogen-induced changes in the oxidation states of Ti atoms, local chemical bonding of oxygen and the formation of defect states within the band gap. During the initial stages of bombardment, the energetic hydrogen reacts with lattice oxygen to form hydroxyl groups, followed by the reduction of Ti<sup>4+</sup> to Ti<sup>3+</sup>. For the higher doses, the formation of H − O − H bridge bonds causes splitting of O − Ti bonds and formation of H<sub>2</sub>O gas molecules, accompanied by a reduction of Ti<sup>3+</sup> and Ti<sup>4+</sup> states to Ti<sup>2+</sup>. At the same time, the reduction of Ti<sup>4+</sup> to lower oxidation states introduces some defect states within the band gap of TiO<sub>2</sub>, associated with Ti<sup>3+</sup> defects or the formation of double-oxygen-vacancy clusters at Ti<sup>2+</sup> sites.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"15 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255345","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dzaki Ahmad Syaifullah , Muhammad Arkan Nuruzzahran , Rizky Dio Idhola , Nadhratun Naiim Mobarak , Hamad AlMohamadi , Shashikant Patole , Sasfan Arman Wella , Fiki Taufik Akbar , Jenny Rizkiana , Ni Luh Wulan Septiani , Adhitya Gandaryus Saputro
{"title":"Tuning oxygen evolution activity via transition metal doping in bimetallic nickel phosphates","authors":"Dzaki Ahmad Syaifullah , Muhammad Arkan Nuruzzahran , Rizky Dio Idhola , Nadhratun Naiim Mobarak , Hamad AlMohamadi , Shashikant Patole , Sasfan Arman Wella , Fiki Taufik Akbar , Jenny Rizkiana , Ni Luh Wulan Septiani , Adhitya Gandaryus Saputro","doi":"10.1016/j.apsusc.2025.164846","DOIUrl":"10.1016/j.apsusc.2025.164846","url":null,"abstract":"<div><div>The oxygen evolution reaction (OER) activity of transition metal-doped bimetallic nickel phosphate (NiMPO-X; M = Mn, Fe, Co; dopant X = Mn, Fe, Co, Cu) has been explored based on density functional theory (DFT) calculations combined with the computational hydrogen electrode (CHE) method and microkinetic simulations. Our findings showed that transition metal doping significantly affects the OER activity of bimetallic nickel phosphates by altering the local <em>d</em>-band center and optimizing the *O binding strength at the surface active site. Among NiMPO-X systems, the best OER performance was achieved by NiFePO-Co with a minimum overpotential of 0.26 V, followed by NiMnPO-Fe (0.27 V) and NiFePO-Mn (0.28 V), outperforming the undoped bimetal NiMPO. These findings highlight the importance of dopant selection to maximize the OER activity of bimetallic nickel phosphate-based catalysts.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"717 ","pages":"Article 164846"},"PeriodicalIF":6.9,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Oxygen exchange kinetics of BaFeO3–δ modified with Ce and/or Y: oxygen isotope exchange and pressure relaxation","authors":"A.V. Khodimchuk , D.M. Zakharov , E.V. Gordeev , I.V. Svishch , N.M. Porotnikova , A.D. Koryakov , A.M. Shalamova , A.Yu. Suntsov","doi":"10.1016/j.apsusc.2025.164823","DOIUrl":"10.1016/j.apsusc.2025.164823","url":null,"abstract":"<div><div>The kinetics of surface oxygen exchange between the gas phase and new, highly efficient electrode materials based on doped barium ferrite oxide with triple H<sup>+</sup>/O<sup>2–</sup>/e<sup>–</sup> conductivity were studied by two independent methods. The oxygen chemical surface exchange coefficients (<em>k<sup>δ</sup></em>) for BaFe<sub>0.9</sub>Ce<sub>0.1</sub>O<sub>3–</sub><em><sub>δ</sub></em>, BaFe<sub>0.9</sub>Y<sub>0.1</sub>O<sub>3–</sub><em><sub>δ</sub></em> and BaFe<sub>0.8</sub>Ce<sub>0.1</sub>Y<sub>0.1</sub>O<sub>3–</sub><em><sub>δ</sub></em> dense samples have been measured by oxygen pressure relaxation (OPR) method under non-equilibrium conditions at <em>ΔT</em> = 600–800 °C and <em>Δp</em>O<sub>2</sub> = 0.1–3.5 kPa. A correlation was found between the chemical surface oxygen exchange coefficient and the oxygen content of the oxides. The mechanism of surface oxygen exchange in the gaseous oxygen – oxide system was determined by the method of pulsed isotope exchange (PIE) under conditions of adsorption–desorption equilibrium on oxide powders at <em>ΔT</em> = 350–600 °C and a partial pressure of oxygen <em>p</em>O<sub>2</sub> = 21.3 kPa. The values of the rates of oxygen heterogenous surface exchange (<em>r<sub>H</sub></em>) and the rates of elementary steps of oxygen exchange were calculated, and the effective activation energies of these processes were determined. The influence of the temperature, the oxygen pressure and the cationic composition of the material on the change in the kinetic characteristics of oxygen exchange was discussed.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"717 ","pages":"Article 164823"},"PeriodicalIF":6.9,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}