Hydrogen (H2) has emerged as a pivotal clean energy carrier due to its zero-carbon emissions and high energy density, while seawater electrolysis presents a promising route for H2 production. However, the complex ionic environment of seawater poses significant challenges for stable and efficient catalytic electrodes. Herein, we develop a spin-state engineering strategy that stabilizes low-spin metallic Ni centers within N-doped graphitic carbon through H2-assisted pyrolysis (Ni/CN-AH). Density functional theory (DFT) reveals graphitization and low-spin Ni synergistically downshift the d-band center by 0.69 eV, achieving optimal H* adsorption while weakening chlorine binding. The strong d-p hybridization at the interface and charge delocalization from low-spin Ni to carbon enhances reaction kinetics. The catalyst exhibits outstanding HER activity and durability in both 1 M KOH and alkaline seawater, while simultaneously suppressing Cl− adsorption and preventing Ca2+/Mg2+ precipitation. This work establishes a new pathway for developing durable seawater-splitting catalysts through atomic-scale spin control and nanoscale carbon engineering.
氢（H2）因其零碳排放和高能量密度而成为关键的清洁能源载体，而海水电解是一种很有前途的制氢途径。然而，海水复杂的离子环境对稳定高效的催化电极提出了重大挑战。在此，我们开发了一种自旋态工程策略，通过h2辅助热解（Ni/CN-AH）稳定n掺杂石墨碳中的低自旋金属Ni中心。密度泛函理论（DFT）表明，石墨化和低自旋Ni协同作用使d带中心下移0.69 eV，实现了最佳的H*吸附，同时减弱了氯的结合。界面处强的d-p杂化和低自旋Ni向碳的电荷离域增强了反应动力学。该催化剂在1 M KOH和碱性海水中均表现出优异的HER活性和耐久性，同时抑制Cl -吸附和阻止Ca2+/Mg2+沉淀。本研究通过原子尺度的自旋控制和纳米尺度的碳工程为开发耐用的海水分解催化剂开辟了一条新的途径。
{"title":"Spin-state engineering of low-spin nickel on highly graphitized carbon enables efficient and stable seawater electrolysis","authors":"Xiaoyu Hao, Kewei Tang, Meirong Gu, Tianyi Zhang, Jingyu Kang, Jinglun Guo, Wen Xiao, Xiaolei Huang, Xuqing Liu","doi":"10.1016/j.jmst.2026.01.017","DOIUrl":"https://doi.org/10.1016/j.jmst.2026.01.017","url":null,"abstract":"Hydrogen (H<sub>2</sub>) has emerged as a pivotal clean energy carrier due to its zero-carbon emissions and high energy density, while seawater electrolysis presents a promising route for H<sub>2</sub> production. However, the complex ionic environment of seawater poses significant challenges for stable and efficient catalytic electrodes. Herein, we develop a spin-state engineering strategy that stabilizes low-spin metallic Ni centers within N-doped graphitic carbon through H<sub>2</sub>-assisted pyrolysis (Ni/CN-AH). Density functional theory (DFT) reveals graphitization and low-spin Ni synergistically downshift the d-band center by 0.69 eV, achieving optimal H* adsorption while weakening chlorine binding. The strong d-p hybridization at the interface and charge delocalization from low-spin Ni to carbon enhances reaction kinetics. The catalyst exhibits outstanding HER activity and durability in both 1 M KOH and alkaline seawater, while simultaneously suppressing Cl<sup>−</sup> adsorption and preventing Ca<sup>2+</sup>/Mg<sup>2+</sup> precipitation. This work establishes a new pathway for developing durable seawater-splitting catalysts through atomic-scale spin control and nanoscale carbon engineering.","PeriodicalId":16154,"journal":{"name":"Journal of Materials Science & Technology","volume":"86 1","pages":""},"PeriodicalIF":10.9,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146000618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lithium-ion batteries (LIBs) have become an integral part of electrical energy storage systems; however, the high price leads to a search for alternatives to LIBs. Sodium-ion batteries stand out because sodium is unlimited in the Earth’s crust and sea. Similar to LIBs, layered transition metal oxides are the optimal choice for practical application by virtue of good ion conductivity, high energy density, and facile synthesis. However, the air sensitivity will lead to the degradation of layered oxides, corresponding with poor electrochemical performance. For instance, capacity losses of 20%–50% after exposure to air with ∼50% relative humidity for 1 day to 30 days, accompanied by surface carbonate coverage exceeding 20% in many cases. It is also regrettable that the air sensitivity has plagued the commercialization of layered oxides for a long time, resulting in huge cost needs to be spent on storage and transportation. Hence, in this work, recent strategies on air stability are reviewed, and the comprehensive chemical evolution mechanisms of air-exposure are introduced that H2O and CO2 have the greatest impact on the structural degradation of layered oxides. In addition, the design principles of layered oxides that choose elements with higher electrochemical potential, increasing the cation competition coefficient, increasing the particle size, surface coating layer modification, and controlling exposed active facets for better air stability are given out. It is hoped that the attention of researchers to air stability can be aroused, and more studies about air stability will be done to address the problem of air sensitivity.
{"title":"Air sensitivity of layered oxides for practical sodium-ion batteries","authors":"Xin-Yang Zhou, Zhi-Xiong Huang, Xin-Yao Liu, Ben-Jian Xin, Miao Du, Dai-Huo Liu, Dong-Mei Dai, Xing-Long Wu","doi":"10.1016/j.jmst.2025.12.056","DOIUrl":"https://doi.org/10.1016/j.jmst.2025.12.056","url":null,"abstract":"Lithium-ion batteries (LIBs) have become an integral part of electrical energy storage systems; however, the high price leads to a search for alternatives to LIBs. Sodium-ion batteries stand out because sodium is unlimited in the Earth’s crust and sea. Similar to LIBs, layered transition metal oxides are the optimal choice for practical application by virtue of good ion conductivity, high energy density, and facile synthesis. However, the air sensitivity will lead to the degradation of layered oxides, corresponding with poor electrochemical performance. For instance, capacity losses of 20%–50% after exposure to air with ∼50% relative humidity for 1 day to 30 days, accompanied by surface carbonate coverage exceeding 20% in many cases. It is also regrettable that the air sensitivity has plagued the commercialization of layered oxides for a long time, resulting in huge cost needs to be spent on storage and transportation. Hence, in this work, recent strategies on air stability are reviewed, and the comprehensive chemical evolution mechanisms of air-exposure are introduced that H<sub>2</sub>O and CO<sub>2</sub> have the greatest impact on the structural degradation of layered oxides. In addition, the design principles of layered oxides that choose elements with higher electrochemical potential, increasing the cation competition coefficient, increasing the particle size, surface coating layer modification, and controlling exposed active facets for better air stability are given out. It is hoped that the attention of researchers to air stability can be aroused, and more studies about air stability will be done to address the problem of air sensitivity.","PeriodicalId":16154,"journal":{"name":"Journal of Materials Science & Technology","volume":"31 1","pages":""},"PeriodicalIF":10.9,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-19DOI: 10.1016/j.jmst.2026.01.016
Oleksandr Lypchanskyi, Nikolaos Rigas, Łukasz Rogal, Karol Janus, Lidia Litynska-Dobrzynska, Grzegorz Korpała, Thomas Lampke, Marion Merklein, Ulrich Prahl
This study investigates the microstructural evolution of Al-Mg-Si-Mn alloys, focusing on the influence of Si content on mechanical properties, deformation mechanisms, and precipitate evolution during high-temperature tensile testing. Tensile tests were performed at 200, 250, 300, and 350°C with strain rates of 0.1, 1, and 10%/s, showing significant variations in mechanical response as a function of Si content. Microstructural characterization was performed using electron backscatter diffraction, energy-dispersive X-ray spectrometry, and a transmission electron microscope to analyze deformation mechanisms, precipitate evolution, and texture formation. The results show a progressive decrease in tensile strength and yield strength with increasing deformation temperature, with the most pronounced reduction occurring at 350°C in alloys with higher Si content. This increased Si level promotes the strengthening of the Copper texture while progressively suppressing the Cube texture during deformation at elevated temperatures. At 200°C, deformation bands are formed primarily by interaction with dislocations, while precipitates drive deformation band formation by effectively impeding dislocation motion. Resolved shear stress analysis indicates a direct influence on the initiation and progression of discontinuous dynamic recrystallization (DDRX), with higher Si levels promoting more pronounced DDRX. Deformation at elevated temperatures of 300 and 350°C enhances dynamic recrystallization and accelerates continuous dynamic recrystallization, leading to increased grain boundary formation and a reduction in deformation band density. Furthermore, the evolution of β′, B′, and U1 phases at 300°C and 0.1%/s strain rate highlights the heterogeneous nucleation and growth mechanisms of precipitates. These results underscore the critical role of Si content in controlling the mechanical response and microstructural evolution of Al-Mg-Si-Mn alloys, providing valuable insights for optimizing alloy design and performance at elevated temperatures.
{"title":"Strain-induced microstructural and precipitation behavior of Al-Mg-Si-Mn alloys: Effects of Si content under controlled thermomechanical conditions","authors":"Oleksandr Lypchanskyi, Nikolaos Rigas, Łukasz Rogal, Karol Janus, Lidia Litynska-Dobrzynska, Grzegorz Korpała, Thomas Lampke, Marion Merklein, Ulrich Prahl","doi":"10.1016/j.jmst.2026.01.016","DOIUrl":"https://doi.org/10.1016/j.jmst.2026.01.016","url":null,"abstract":"This study investigates the microstructural evolution of Al-Mg-Si-Mn alloys, focusing on the influence of Si content on mechanical properties, deformation mechanisms, and precipitate evolution during high-temperature tensile testing. Tensile tests were performed at 200, 250, 300, and 350°C with strain rates of 0.1, 1, and 10%/s, showing significant variations in mechanical response as a function of Si content. Microstructural characterization was performed using electron backscatter diffraction, energy-dispersive X-ray spectrometry, and a transmission electron microscope to analyze deformation mechanisms, precipitate evolution, and texture formation. The results show a progressive decrease in tensile strength and yield strength with increasing deformation temperature, with the most pronounced reduction occurring at 350°C in alloys with higher Si content. This increased Si level promotes the strengthening of the Copper texture while progressively suppressing the Cube texture during deformation at elevated temperatures. At 200°C, deformation bands are formed primarily by interaction with dislocations, while precipitates drive deformation band formation by effectively impeding dislocation motion. Resolved shear stress analysis indicates a direct influence on the initiation and progression of discontinuous dynamic recrystallization (DDRX), with higher Si levels promoting more pronounced DDRX. Deformation at elevated temperatures of 300 and 350°C enhances dynamic recrystallization and accelerates continuous dynamic recrystallization, leading to increased grain boundary formation and a reduction in deformation band density. Furthermore, the evolution of β′, B′, and U1 phases at 300°C and 0.1%/s strain rate highlights the heterogeneous nucleation and growth mechanisms of precipitates. These results underscore the critical role of Si content in controlling the mechanical response and microstructural evolution of Al-Mg-Si-Mn alloys, providing valuable insights for optimizing alloy design and performance at elevated temperatures.","PeriodicalId":16154,"journal":{"name":"Journal of Materials Science & Technology","volume":"11 1","pages":""},"PeriodicalIF":10.9,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146000620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hydrogen-driven porosity is a major barrier to high-strength Al-Cu parts produced by wire-arc additive manufacturing (WAAM). We introduced 1.5 wt.% nano-TiC particles into Al-6.3Cu filler wire and calculated, from first principles, a hydrogen-trapping energy of 1.55 eV per H atom—three times that at θ′/Al interfaces. WAAM walls printed with this wire exhibited an average porosity of 0.015% versus 3.05% in the TiC-free reference, and an equiaxed grain size refined from 41 to 12 µm. After identical T6 treatment, the TiC-bearing alloy delivered yield and ultimate tensile strengths of 328 and 433 MPa, increases of 56% and 24%, respectively, while anisotropy improved to 0.96. Moreover, 90% of these strengths were retained after 100 h at 200°C. These results provide the first quantitative evidence that TiC nanoparticles concurrently suppress processing and heat-treatment pores in WAAM Al-Cu and offer an immediately applicable pore-control route for high-performance Al additive manufacturing.
{"title":"Mitigating micro-pores in wire-arc additive manufactured Al alloys via nano-TiC dispersoids: From fundamentals to validation","authors":"Jiqiang Chen, Yuxiang Gong, Jiale Miao, Yong Jiang","doi":"10.1016/j.jmst.2025.12.057","DOIUrl":"https://doi.org/10.1016/j.jmst.2025.12.057","url":null,"abstract":"Hydrogen-driven porosity is a major barrier to high-strength Al-Cu parts produced by wire-arc additive manufacturing (WAAM). We introduced 1.5 wt.% nano-TiC particles into Al-6.3Cu filler wire and calculated, from first principles, a hydrogen-trapping energy of 1.55 eV per H atom—three times that at θ′/Al interfaces. WAAM walls printed with this wire exhibited an average porosity of 0.015% versus 3.05% in the TiC-free reference, and an equiaxed grain size refined from 41 to 12 µm. After identical T6 treatment, the TiC-bearing alloy delivered yield and ultimate tensile strengths of 328 and 433 MPa, increases of 56% and 24%, respectively, while anisotropy improved to 0.96. Moreover, 90% of these strengths were retained after 100 h at 200°C. These results provide the first quantitative evidence that TiC nanoparticles concurrently suppress processing and heat-treatment pores in WAAM Al-Cu and offer an immediately applicable pore-control route for high-performance Al additive manufacturing.","PeriodicalId":16154,"journal":{"name":"Journal of Materials Science & Technology","volume":"37 1","pages":""},"PeriodicalIF":10.9,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146000623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-16DOI: 10.1016/j.jmst.2025.12.055
Tongjun Zhao, Shasha Yang, Zehao Chen, Yao Du, Jinlong Wang, Minghui Chen, Shenglong Zhu, Fuhui Wang
The degradation of protective performance at elevated temperatures remains a major limitation for application of organic coatings. In this study, for the first time, submicron low-melting glass (LMG) was combined with active nano-Ti powder to develop a novel oxidation-resistant silicone composite coating for protecting Ti-6Al-4V alloy at 650°C. Compared with a control coating containing inert nano-TiO2 (S-TO), the coating reinforced by nano-Ti powder (S-Ti) exhibited superior oxidation resistance. The nano-Ti powder functioned as an active pigment, consuming oxygen through oxidation and producing TiO2 with a 73% volumetric expansion. This expansion synergized with the viscous LMG-derived glass phase, enabling the in-situ repair of holes formed by the submicron LMG particles, thereby enhancing the coating density. Consequently, the S-Ti coating achieved lower porosity (6.1% vs. 14.0%), reduced oxygen diffusion flux, and suppressed substrate oxidation kinetics (rate constant: 5.4 × 10−7 mg2 cm−4 s−1 vs. 8.9 × 10−7 mg2 cm−4 s−1 for S-TO). After oxidation for 300 h, no oxide scale was observed on the substrate surface (detection limit: 1 μm).
高温下防护性能的退化仍然是有机涂层应用的主要限制。本研究首次将亚微米低熔点玻璃（LMG）与活性纳米ti粉结合，制备了一种新型抗氧化硅复合涂层，用于650℃下保护Ti-6Al-4V合金。与含有惰性纳米tio2 （S-TO）的对照涂层相比，纳米ti粉（S-Ti）增强涂层具有更好的抗氧化性能。纳米钛粉作为活性颜料，通过氧化消耗氧气，生成体积膨胀率为73%的TiO2。这种膨胀与黏性LMG衍生的玻璃相协同作用，使亚微米LMG颗粒形成的孔洞能够就地修复，从而提高涂层密度。因此，s - ti涂层实现了更低的孔隙率（6.1% vs. 14.0%），降低了氧扩散通量，抑制了底物氧化动力学（速率常数：5.4 × 10−7 mg2 cm−4 s−1 vs. 8.9 × 10−7 mg2 cm−4 s−1）。氧化300 h后，衬底表面未见氧化皮（检出限为1 μm）。
{"title":"Mechanistic insight into synergistic reinforcement of oxidation resistance in silicone coatings via submicron low-melting glass and active nano-pigments","authors":"Tongjun Zhao, Shasha Yang, Zehao Chen, Yao Du, Jinlong Wang, Minghui Chen, Shenglong Zhu, Fuhui Wang","doi":"10.1016/j.jmst.2025.12.055","DOIUrl":"https://doi.org/10.1016/j.jmst.2025.12.055","url":null,"abstract":"The degradation of protective performance at elevated temperatures remains a major limitation for application of organic coatings. In this study, for the first time, submicron low-melting glass (LMG) was combined with active nano-Ti powder to develop a novel oxidation-resistant silicone composite coating for protecting Ti-6Al-4V alloy at 650°C. Compared with a control coating containing inert nano-TiO<sub>2</sub> (S-TO), the coating reinforced by nano-Ti powder (S-Ti) exhibited superior oxidation resistance. The nano-Ti powder functioned as an active pigment, consuming oxygen through oxidation and producing TiO<sub>2</sub> with a 73% volumetric expansion. This expansion synergized with the viscous LMG-derived glass phase, enabling the in-situ repair of holes formed by the submicron LMG particles, thereby enhancing the coating density. Consequently, the S-Ti coating achieved lower porosity (6.1% vs. 14.0%), reduced oxygen diffusion flux, and suppressed substrate oxidation kinetics (rate constant: 5.4 × 10<sup>−7</sup> mg<sup>2</sup> cm<sup>−4</sup> s<sup>−1</sup> vs. 8.9 × 10<sup>−7</sup> mg<sup>2</sup> cm<sup>−4</sup> s<sup>−1</sup> for S-TO). After oxidation for 300 h, no oxide scale was observed on the substrate surface (detection limit: 1 μm).","PeriodicalId":16154,"journal":{"name":"Journal of Materials Science & Technology","volume":"42 1","pages":""},"PeriodicalIF":10.9,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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