Pub Date : 2026-01-12DOI: 10.1016/j.apsusc.2026.165913
Song Xu, Ling Zhao, Siran Hua, Mingzhe Che, Jiale Hou, Yuhui Liu, Huaijie Cao, Junxi Zhang
Galvanized steel usually presents limited service life under coastal or marine environment with high-salinity due to the corrosion susceptibility of zinc layer. Despite great efforts have been made to develop various protective coatings, it still remains a challenge in constructing inorganic and green coatings with active/passive protection capability. Herein, MgAl layered double hydroxide (LDH) nanosheets intercalated with MoO42− anions are incorporated in inorganic silica (SiO2) coating by electrodeposition process. Combined with ion-exchange of LDH and inhibition effect of MoO42−, the thin LDH@SiO2 composite coating can achieve active/passive protection on zinc. Impedance modulus at 0.01 Hz (|Z|0.01Hz) is improved by four orders of magnitude compared to Zn counterpart and the corrosion current density is reduced to 1.0195 × 10−8 A/cm2. After immersion tests for 30 days, the LDH@SiO2 composite coating still exhibits high corrosion resistance. Besides, the self-healing efficiency reaches 99.52%. The improved corrosion resistance is attributed to the physical barrier and labyrinth effect of the coating, while the release of MoO42− from MgAl LDH contributes to the self-healing process. This work proposes a new and green technology toward active/passive protection on zinc and sheds insights into understanding the protective mechanisms of LDH@SiO2 composite coating in marine environments.
{"title":"Electrodeposited MgAl LDH/SiO2 composite coating toward active/passive corrosion protection","authors":"Song Xu, Ling Zhao, Siran Hua, Mingzhe Che, Jiale Hou, Yuhui Liu, Huaijie Cao, Junxi Zhang","doi":"10.1016/j.apsusc.2026.165913","DOIUrl":"10.1016/j.apsusc.2026.165913","url":null,"abstract":"<div><div>Galvanized steel usually presents limited service life under coastal or marine environment with high-salinity due to the corrosion susceptibility of zinc layer. Despite great efforts have been made to develop various protective coatings, it still remains a challenge in constructing inorganic and green coatings with active/passive protection capability. Herein, MgAl layered double hydroxide (LDH) nanosheets intercalated with MoO<sub>4</sub><sup>2−</sup> anions are incorporated in inorganic silica (SiO<sub>2</sub>) coating by electrodeposition process. Combined with ion-exchange of LDH and inhibition effect of MoO<sub>4</sub><sup>2−</sup>, the thin LDH@SiO<sub>2</sub> composite coating can achieve active/passive protection on zinc. Impedance modulus at 0.01 Hz (|Z|<sub>0.01Hz</sub>) is improved by four orders of magnitude compared to Zn counterpart and the corrosion current density is reduced to 1.0195 × 10<sup>−8</sup> A/cm<sup>2</sup>. After immersion tests for 30 days, the LDH@SiO<sub>2</sub> composite coating still exhibits high corrosion resistance. Besides, the self-healing efficiency reaches 99.52%. The improved corrosion resistance is attributed to the physical barrier and labyrinth effect of the coating, while the release of MoO<sub>4</sub><sup>2−</sup> from MgAl LDH contributes to the self-healing process. This work proposes a new and green technology toward active/passive protection on zinc and sheds insights into understanding the protective mechanisms of LDH@SiO<sub>2</sub> composite coating in marine environments.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"726 ","pages":"Article 165913"},"PeriodicalIF":6.9,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956517","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}
Pub Date : 2026-01-11DOI: 10.1016/j.apsusc.2026.165889
Seok-Ho Lee , Sang Yun Kim , Byung Jin Lee , Myung-gi Seo , Geun-Ho Han , Kwan-Young Lee
Hydrogen peroxide (H2O2), generating only water and oxygen as byproducts, is a highly desirable green oxidant widely used in environmental remediation, pharmaceuticals, and fine chemicals. Among various production routes, direct synthesis from H2 and O2 (DSHP) offers a sustainable alternative to the traditional process. However, its practical deployment is limited by poor selectivity and rapid H2O2 degradation, highlighting the need for advanced catalyst design. This study presents a surface engineering strategy to precisely tune the hydrophobicity of Pd/SiO2 catalysts via chemical grafting of octadecyltrimethoxysilane ligands. Unlike conventional hydrophobic carbon supports that suffer from weak metal–support interaction and site blockage, the functionalized catalysts exhibited improved structural stability. Stepwise enhancement of surface hydrophobicity facilitated the diffusion of nonpolar reactants (H2, O2) and accelerated the desorption of hydrophilic H2O2, effectively suppressing its decomposition. Notably, a catalyst with moderate ligand density (10C18-Pd/SiO2) achieved an optimal balance, delivering 84.5% selectivity and a productivity of 2,754 mmol gPd−1·h−1—approximately 52% higher than the unmodified Pd/SiO2 catalyst. Excessive ligand coverage hindered access of the H3PO4 stabilizer to Pd active sites, thereby delineating a critical hydrophobicity window necessary for effective DSHP catalysis.
{"title":"Tuning surface hydrophobicity of palladium catalysts via alkyl ligand functionalization for direct synthesis of hydrogen peroxide","authors":"Seok-Ho Lee , Sang Yun Kim , Byung Jin Lee , Myung-gi Seo , Geun-Ho Han , Kwan-Young Lee","doi":"10.1016/j.apsusc.2026.165889","DOIUrl":"10.1016/j.apsusc.2026.165889","url":null,"abstract":"<div><div>Hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>), generating only water and oxygen as byproducts, is a highly desirable green oxidant widely used in environmental remediation, pharmaceuticals, and fine chemicals. Among various production routes, direct synthesis from H<sub>2</sub> and O<sub>2</sub> (DSHP) offers a sustainable alternative to the traditional process. However, its practical deployment is limited by poor selectivity and rapid H<sub>2</sub>O<sub>2</sub> degradation, highlighting the need for advanced catalyst design. This study presents a surface engineering strategy to precisely tune the hydrophobicity of Pd/SiO<sub>2</sub> catalysts via chemical grafting of octadecyltrimethoxysilane ligands. Unlike conventional hydrophobic carbon supports that suffer from weak metal–support interaction and site blockage, the functionalized catalysts exhibited improved structural stability. Stepwise enhancement of surface hydrophobicity facilitated the diffusion of nonpolar reactants (H<sub>2</sub>, O<sub>2</sub>) and accelerated the desorption of hydrophilic H<sub>2</sub>O<sub>2</sub>, effectively suppressing its decomposition. Notably, a catalyst with moderate ligand density (10C<sub>18</sub>-Pd/SiO<sub>2</sub>) achieved an optimal balance, delivering 84.5% selectivity and a productivity of 2,754 mmol g<sub>Pd</sub><sup>−1</sup>·h<sup>−1</sup>—approximately 52% higher than the unmodified Pd/SiO<sub>2</sub> catalyst. Excessive ligand coverage hindered access of the H<sub>3</sub>PO<sub>4</sub> stabilizer to Pd active sites, thereby delineating a critical hydrophobicity window necessary for effective DSHP catalysis.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"726 ","pages":"Article 165889"},"PeriodicalIF":6.9,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956539","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}
Pub Date : 2026-01-11DOI: 10.1016/j.apsusc.2026.165899
Teng Liu , Peirong Kuang , Wenchao Tong , Jinlong Cui , Wenyuan Zhao
A series of M2-L@OBC composites (M = Cu(II), Co(II), Fe(III); L = 5-Nitro-3-pyrazolecarboxylic acid; M:L molar ratio = 2:1; OBC = carboxylated bacterial cellulose) with 3D-networknet structure were successfully synthesized and utilized to improve the thermal decomposition of ammonium perchlorate (AP). The M2-L@OBC composites were characterized by IR, SEM, TEM, HRTEM, XPS and XRD, and the results indicate that the M2-L nanoparticles are evenly covered on cellulose fibers. The catalytic effects were investigated using the non-isothermal method, which shows that the Fe2-L@OBC composites exhibits excellent performance. The peak temperature of the high-temperature decomposition (HTD) stage of AP mixing 2 wt% Fe2-L@OBC advanced by 66 °C, the activation energy decreased by 56 kJ/mol, and the reaction rate constant increased by 1.1 times. Furthermore, online TG/FT-IR revealed that Fe2-L@OBC composites could significantly accelerate the consumption of HClO4 and NH3 to the conversion of N2O, NO, and NO2. This is attributed to the abundant active sites on the Fe2-L@OBC surface, which provide fresh active sites after decomposing into metal oxide nanoparticles, thereby promoting the electron transfer process in the HTD stage.
{"title":"3D framework energetic composites: an efficient catalyst for ammonium perchlorate thermal decomposition","authors":"Teng Liu , Peirong Kuang , Wenchao Tong , Jinlong Cui , Wenyuan Zhao","doi":"10.1016/j.apsusc.2026.165899","DOIUrl":"10.1016/j.apsusc.2026.165899","url":null,"abstract":"<div><div>A series of M<sub>2</sub>-L@OBC composites (M = Cu(II), Co(II), Fe(III); L = 5-Nitro-3-pyrazolecarboxylic acid; M:L molar ratio = 2:1; OBC = carboxylated bacterial cellulose) with 3D-networknet structure were successfully synthesized and utilized to improve the thermal decomposition of ammonium perchlorate (AP). The M<sub>2</sub>-L@OBC composites were characterized by IR, SEM, TEM, HRTEM, XPS and XRD, and the results indicate that the M<sub>2</sub>-L nanoparticles are evenly covered on cellulose fibers. The catalytic effects were investigated using the non-isothermal method, which shows that the Fe<sub>2</sub>-L@OBC composites exhibits excellent performance. The peak temperature of the high-temperature decomposition (HTD) stage of AP mixing 2 wt% Fe<sub>2</sub>-L@OBC advanced by 66 °C, the activation energy decreased by 56 kJ/mol, and the reaction rate constant increased by 1.1 times. Furthermore, online TG/FT-IR revealed that Fe<sub>2</sub>-L@OBC composites could significantly accelerate the consumption of HClO<sub>4</sub> and NH<sub>3</sub> to the conversion of N<sub>2</sub>O, NO, and NO<sub>2</sub>. This is attributed to the abundant active sites on the Fe<sub>2</sub>-L@OBC surface, which provide fresh active sites after decomposing into metal oxide nanoparticles, thereby promoting the electron transfer process in the HTD stage.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"726 ","pages":"Article 165899"},"PeriodicalIF":6.9,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947512","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}
Against the backdrop of green and sustainable mining, efficient separation of ilmenite from forsterite remains challenging, mainly due to the high reagent dosage, high pulp residue, and water pollution caused by conventional collectors. Herein, a novel unsaturated short-chain hydroxamate, sodium trans-2-octenyl hydroxamate (NaOHA-II), was designed and synthesized to enhance ilmenite flotation. Its collecting capability was compared with octyl hydroxamic acid (NaOHA-I) via flotation experiments, modern analytical techniques and molecular dynamics simulations. Micro-flotation tests showed that 84.80% ilmenite recovery and only 5.02% forsterite recovery with 50 mg/L NaOHA-II. In actual ore flotation, compared with the application of 500 g/t NaOHA-I, the use of 300 g/t NaOHA-II enhances the TiO2 grade and recovery of the rough concentrate by 3.15% and 38.59%, respectively. Meanwhile, this reagent cuts the dosage by 40%, reduces pulp residues and provides non-toxic certification to meet green separation. Mechanistic analyses indicated that double bonds of NaOHA-II boost polar groups electron density (enhancing electrostatic and hydrogen bonding). Moreover, the enhanced electronegativity of the hydroxamic acid active group makes it easier to donate electrons and form chemical bonds, thereby enhancing selective chemisorption on ilmenite surface, highlighting its potential as an effective collector for the flotation of ilmenite from forsterite
{"title":"New insight into the implications of unsaturated hydroxamic acid collector for the flotation separation between ilmenite and forsterite: electronic effect supplied by double bonds to improve the selective adsorption","authors":"Huaiyao Zhang, Tingting Chen, Xiaoman Wang, Yijun Cao, Jingchao Li, Guosheng Li, Junwei Huang, Shuling Gao, Fanfan Zhang, Guixia Fan","doi":"10.1016/j.apsusc.2026.165908","DOIUrl":"https://doi.org/10.1016/j.apsusc.2026.165908","url":null,"abstract":"Against the backdrop of green and sustainable mining, efficient separation of ilmenite from forsterite remains challenging, mainly due to the high reagent dosage, high pulp residue, and water pollution caused by conventional collectors. Herein, a novel unsaturated short-chain hydroxamate, sodium <ce:italic>trans</ce:italic>-2-octenyl hydroxamate (NaOHA-II), was designed and synthesized to enhance ilmenite flotation. Its collecting capability was compared with octyl hydroxamic acid (NaOHA-I) via flotation experiments, modern analytical techniques and molecular dynamics simulations. Micro-flotation tests showed that 84.80% ilmenite recovery and only 5.02% forsterite recovery with 50 mg/L NaOHA-II. In actual ore flotation, compared with the application of 500 g/t NaOHA-I, the use of 300 g/t NaOHA-II enhances the TiO<ce:inf loc=\"post\">2</ce:inf> grade and recovery of the rough concentrate by 3.15% and 38.59%, respectively. Meanwhile, this reagent cuts the dosage by 40%, reduces pulp residues and provides non-toxic certification to meet green separation. Mechanistic analyses indicated that double bonds of NaOHA-II boost polar groups electron density (enhancing electrostatic and hydrogen bonding). Moreover, the enhanced electronegativity of the hydroxamic acid active group makes it easier to donate electrons and form chemical bonds, thereby enhancing selective chemisorption on ilmenite surface, highlighting its potential as an effective collector for the flotation of ilmenite from forsterite","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"53 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956523","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}
Pub Date : 2026-01-11DOI: 10.1016/j.apsusc.2026.165890
Si Chen , Wenyu Huang , Zhihua Xia , Qi Qin , Muzi Yang , Li Gong , Hongyan Chen , Dai-Bin Kuang , Fangyan Xie , Jian Chen
Photocatalysts have attracted significant attention for their unique ability to convert light energy into chemical energy. Accurate determination of the key electronic structure parameters − including the Fermi level, work function (WF), and valence band maximum (VBM) etc.- is crucial for understanding the charge separation mechanism and rationally designing high-performance photocatalysts. Ultraviolet photoelectron spectroscopy (UPS) is widely recognized in the determination of these parameters due to its high precision. However, there is a lack of detailed and practical guidelines for UPS characterization methods in the field of photocatalysis, resulting in widespread misinterpretation of results in the literature. Therefore, this paper systematically summarizes common pitfalls and misconceptions in UPS analysis of photocatalysts. We further present a validated and detailed operating protocol (taking CsPbBr3 perovskite photocatalyst as an example) to accurately determine the energy level arrangement of the photocatalyst, covering the entire process of sample preparation, measurement and data analysis. By establishing a clear and rigorous UPS characterization methodology, this work aims to reduce misunderstandings of the photocatalytic mechanism caused by inaccurate electronic structure determination, and to provide practical guidance for the research community of photocatalysts.
{"title":"Toward accurate UPS characterization of photocatalysts: common pitfalls and a validated protocol using CsPbBr3 perovskite","authors":"Si Chen , Wenyu Huang , Zhihua Xia , Qi Qin , Muzi Yang , Li Gong , Hongyan Chen , Dai-Bin Kuang , Fangyan Xie , Jian Chen","doi":"10.1016/j.apsusc.2026.165890","DOIUrl":"10.1016/j.apsusc.2026.165890","url":null,"abstract":"<div><div>Photocatalysts have attracted significant attention for their unique ability to convert light energy into chemical energy. Accurate determination of the key electronic structure parameters − including the Fermi level, work function (WF), and valence band maximum (VBM) etc.- is crucial for understanding the charge separation mechanism and rationally designing high-performance photocatalysts. Ultraviolet photoelectron spectroscopy (UPS) is widely recognized in the determination of these parameters due to its high precision. However, there is a lack of detailed and practical guidelines for UPS characterization methods in the field of photocatalysis, resulting in widespread misinterpretation of results in the literature. Therefore, this paper systematically summarizes common pitfalls and misconceptions in UPS analysis of photocatalysts. We further present a validated and detailed operating protocol (taking CsPbBr<sub>3</sub> perovskite photocatalyst as an example) to accurately determine the energy level arrangement of the photocatalyst, covering the entire process of sample preparation, measurement and data analysis. By establishing a clear and rigorous UPS characterization methodology, this work aims to reduce misunderstandings of the photocatalytic mechanism caused by inaccurate electronic structure determination, and to provide practical guidance for the research community of photocatalysts.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"726 ","pages":"Article 165890"},"PeriodicalIF":6.9,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947511","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}
Pub Date : 2026-01-11DOI: 10.1016/j.apsusc.2026.165901
Zhiling Huang, Xiaoge Peng, Di Liu, Yue Meng
This study focuses on the promising electrochromic material tungsten oxide. A WO3·0.33H2O film with a controllable microstructure was successfully synthesized using a surfactant-assisted hydrothermal method. Compared with the WO3-SDS films regulated by the ionic surfactant sodium dodecyl sulfate (SDS) and the pure-phase WO3·0.33H2O films (Marked as WO3 films), this study used non-ionic polyethylene glycol (PEG) as a structure-directing agent to successfully fabricate high-crystallinity WO3-PEG films with preferred (220) crystal plane orientation. Scanning electron microscopy (SEM) analysis shows that the film exhibits uniform particle morphology, with tightly packed particles forming interparticle channels, creating layered ion diffusion paths. Electrochemical tests showed that the WO3-PEG film exhibited excellent electrochromic performance: the Li+ diffusion coefficient (5.094 × 10−13 cm2/s) was significantly improved, 1.71 times higher than that of pure WO3 (2.971 × 10−13 cm2/s). The response time was fast ((tc/tb = 4.73 s/4.57 s), and the optical modulation amplitude was high (ΔT of 61.50% at 600 nm wavelength). By optimizing the synergistic effect of crystallinity and engineered ion channel structure, synchronous electron transfer and ion insertion are achieved, providing a new approach for the design of high-performance electrochromic materials.
{"title":"Synergistic construction of preferential growth of WO3 and ion channels induced by non-ionic polyethylene glycol to enhance electrochromic performance","authors":"Zhiling Huang, Xiaoge Peng, Di Liu, Yue Meng","doi":"10.1016/j.apsusc.2026.165901","DOIUrl":"10.1016/j.apsusc.2026.165901","url":null,"abstract":"<div><div>This study focuses on the promising electrochromic material tungsten oxide. A WO<sub>3</sub>·0.33H<sub>2</sub>O film with a controllable microstructure was successfully synthesized using a surfactant-assisted hydrothermal method. Compared with the WO<sub>3</sub>-SDS films regulated by the ionic surfactant sodium dodecyl sulfate (SDS) and the pure-phase WO<sub>3</sub>·0.33H<sub>2</sub>O films (Marked as WO<sub>3</sub> films), this study used non-ionic polyethylene glycol (PEG) as a structure-directing agent to successfully fabricate high-crystallinity WO<sub>3</sub>-PEG films with preferred (220) crystal plane orientation. Scanning electron microscopy (SEM) analysis shows that the film exhibits uniform particle morphology, with tightly packed particles forming interparticle channels, creating layered ion diffusion paths. Electrochemical tests showed that the WO<sub>3</sub>-PEG film exhibited excellent electrochromic performance: the Li<sup>+</sup> diffusion coefficient (5.094 × 10<sup>−13</sup> cm<sup>2</sup>/s) was significantly improved, 1.71 times higher than that of pure WO<sub>3</sub> (2.971 × 10<sup>−13</sup> cm<sup>2</sup>/s). The response time was fast ((t<sub>c</sub>/t<sub>b</sub> = 4.73 s/4.57 s), and the optical modulation amplitude was high (ΔT of 61.50% at 600 nm wavelength). By optimizing the synergistic effect of crystallinity and engineered ion channel structure, synchronous electron transfer and ion insertion are achieved, providing a new approach for the design of high-performance electrochromic materials.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"726 ","pages":"Article 165901"},"PeriodicalIF":6.9,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956522","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}
Pub Date : 2026-01-11DOI: 10.1016/j.apsusc.2026.165886
Bicai Li, Yaxi Xiao, Yingjie Tan, Hongrui Zhao, Yi Huang, Guowen He
Landfill leachate, a complex refractory wastewater rich in high-concentration dissolved organic matter (DOM), resists conventional biochemical treatment and threatens aquatic ecosystems and human health. Developing efficient, stable DOM remediation technologies remains urgent. Herein, four ZnO photocatalysts with distinct morphologies (rod-like ZnO-1, flower-like ZnO-2, needle-like ZnO-3, rod-like arrayed ZnO-4) were synthesised via magnetron sputtering pretreatment combined with hydrothermal reaction. Characterisations showed ZnO-1 had a high oxygen vacancy density (62.05 %) and efficient photogenerated electron-hole separation. After 90 min of photocatalysis, ZnO-1 achieved the highest TOC (36.84 %) and DOM (63.16 %) degradation efficiencies, outperforming other samples. All catalysts preferred fulvic-like substance degradation over protein-like ones. Hydroxyl radicals (·OH) were the primary active species, synergising with superoxide radicals (·O2–) and photogenerated holes (h+) to degrade DOM via C=C cleavage, aromatic ring opening and mineralisation. ZnO-1 retained >30 % activity after four cycles. This work provides a high-performance catalyst for refractory DOM remediation and guides morphology-controlled semiconductor catalyst design for complex wastewater treatment.
{"title":"Boosting selective degradation of refractory dissolved organic matter in landfill leachate: Morphology-tunable ZnO via magnetron sputtering-hydrothermal synthesis","authors":"Bicai Li, Yaxi Xiao, Yingjie Tan, Hongrui Zhao, Yi Huang, Guowen He","doi":"10.1016/j.apsusc.2026.165886","DOIUrl":"https://doi.org/10.1016/j.apsusc.2026.165886","url":null,"abstract":"Landfill leachate, a complex refractory wastewater rich in high-concentration dissolved organic matter (DOM), resists conventional biochemical treatment and threatens aquatic ecosystems and human health. Developing efficient, stable DOM remediation technologies remains urgent. Herein, four ZnO photocatalysts with distinct morphologies (rod-like ZnO-1, flower-like ZnO-2, needle-like ZnO-3, rod-like arrayed ZnO-4) were synthesised via magnetron sputtering pretreatment combined with hydrothermal reaction. Characterisations showed ZnO-1 had a high oxygen vacancy density (62.05 %) and efficient photogenerated electron-hole separation. After 90 min of photocatalysis, ZnO-1 achieved the highest TOC (36.84 %) and DOM (63.16 %) degradation efficiencies, outperforming other samples. All catalysts preferred fulvic-like substance degradation over protein-like ones. Hydroxyl radicals (·OH) were the primary active species, synergising with superoxide radicals (·O<sub>2</sub><sup>–</sup>) and photogenerated holes (<em>h</em><sup>+</sup>) to degrade DOM via C=C cleavage, aromatic ring opening and mineralisation. ZnO-1 retained >30 % activity after four cycles. This work provides a high-performance catalyst for refractory DOM remediation and guides morphology-controlled semiconductor catalyst design for complex wastewater treatment.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"84 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947515","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}
Pub Date : 2026-01-11DOI: 10.1016/j.apsusc.2026.165884
Ruey-Chi Wang , Yu-Kai Chen , Hsiu-Cheng Chen , Shu-Jen Chen , Yi-Ti Lin , Jing-Ya Gong
Contact-electro-catalysis (CEC) has attracted attention for using commercial plastics as catalysts, yet the most effective CEC polymers are costly fluorinated materials with poor high-temperature performance. In this study, poly(methyl methacrylate) (PMMA) was surface-treated with real-time generated plasma-activated water (PAW), exhibiting excellent CEC performance that outperforms mainstream fluorinated ethylene propylene (FEP) under elevated-temperature conditions. According to water contact angle measurements, the hydrophilicity of PMMA continuously increases with longer PAW treatment durations. FTIR analysis reveals a decrease in C=O, C–O–C, C–C, and –CH3 bond content, while XPS analysis indicates a continuous increase in –OH functional groups on the surface of PMMA. Furthermore, CEC testing shows that PMMA treated with an appropriate duration of PAW exhibits the best CEC performance. This enhancement is attributed to the reaction between highly active hydroxyl radicals (•OH) in PAW and the PMMA molecular chains, resulting in a significant increase in the electron-withdrawing capacity of the PMMA. Besides, KPFM measurements reveal that powders with more negative surface potential promote more efficient electron transfer from water. This study offers a new route to develop efficient, low-cost, high-temperature-resistant, fluorine-free CEC polymers and advance their use in pollutant degradation and environmental remediation.
接触电催化（CEC）是一种利用商业塑料作为催化剂的技术，但目前最有效的接触电催化聚合物是价格昂贵且高温性能差的氟化材料。在本研究中，用实时生成的等离子体活化水（PAW）对聚甲基丙烯酸甲酯（PMMA）进行表面处理，在高温条件下表现出优异的CEC性能，优于主流的氟化乙丙烯（FEP）。根据水接触角的测量，PMMA的亲水性随着PAW处理时间的延长而不断增加。FTIR分析显示，PMMA表面的C=O、C - O - C、C - C和-CH3键含量减少，而XPS分析显示，PMMA表面的-OH官能团含量持续增加。此外，CEC测试表明，经过适当时间的PAW处理的PMMA具有最佳的CEC性能。这种增强是由于PAW中高活性羟基自由基（•OH）与PMMA分子链之间的反应，导致PMMA的吸电子能力显著增加。此外，KPFM测量表明，具有更多负表面电位的粉末促进更有效的电子从水中转移。本研究为开发高效、低成本、耐高温、无氟的CEC聚合物，推进其在污染物降解和环境修复中的应用提供了新的途径。
{"title":"Excellent contact-electro-catalysis performance from fluorine-free polymers modified by real-time generated plasma-activated water","authors":"Ruey-Chi Wang , Yu-Kai Chen , Hsiu-Cheng Chen , Shu-Jen Chen , Yi-Ti Lin , Jing-Ya Gong","doi":"10.1016/j.apsusc.2026.165884","DOIUrl":"10.1016/j.apsusc.2026.165884","url":null,"abstract":"<div><div>Contact-electro-catalysis (CEC) has attracted attention for using commercial plastics as catalysts, yet the most effective CEC polymers are costly fluorinated materials with poor high-temperature performance. In this study, poly(methyl methacrylate) (PMMA) was surface-treated with real-time generated plasma-activated water (PAW), exhibiting excellent CEC performance that outperforms mainstream fluorinated ethylene propylene (FEP) under elevated-temperature conditions. According to water contact angle measurements, the hydrophilicity of PMMA continuously increases with longer PAW treatment durations. FTIR analysis reveals a decrease in C=O, C–O–C, C–C, and –CH<sub>3</sub> bond content, while XPS analysis indicates a continuous increase in –OH functional groups on the surface of PMMA. Furthermore, CEC testing shows that PMMA treated with an appropriate duration of PAW exhibits the best CEC performance. This enhancement is attributed to the reaction between highly active hydroxyl radicals (•OH) in PAW and the PMMA molecular chains, resulting in a significant increase in the electron-withdrawing capacity of the PMMA. Besides, KPFM measurements reveal that powders with more negative surface potential promote more efficient electron transfer from water. This study offers a new route to develop efficient, low-cost, high-temperature-resistant, fluorine-free CEC polymers and advance their use in pollutant degradation and environmental remediation.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"726 ","pages":"Article 165884"},"PeriodicalIF":6.9,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947513","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}
Pub Date : 2026-01-11DOI: 10.1016/j.apsusc.2026.165904
Jinhu Fan , Jinkun Wang , Huai Zheng , Liyi Li , Yiying Zhu
Highly (111)-oriented nanotwinned Cu is widely considered the optimal microstructure for Cu–Cu low-temperature bonding, attributed to its rapid surface diffusion kinetics. In this study, systematic investigations are conducted into the atomic mechanism during Cu–Cu bonding by adjusting grain characteristics at the interface using molecular dynamics simulations. The findings highlight the critical role of plastic deformation rather than the conventional surface diffusion-driven perspective. The (111)-oriented bonding interface does not show a clear advantage and, in some cases, performs even worse. Bonding kinetics are mainly governed by localized plastic deformation under stress, with grain boundary density playing a crucial role in determining the void closure rate. Grain boundaries act as high-diffusivity pathways that enable mass transport, localized recrystallization, and stress relaxation. Furthermore, typical polycrystalline Cu demonstrates enhanced stress accommodation via grain rotation, resulting in the fastest void closure rate among samples with comparable grain boundary densities. Overall, this study provides atomic-level insights into the Cu–Cu low-temperature bonding mechanism, emphasizing the importance of optimizing grain boundary density and promoting grain rotation for enhancing bonding efficiency. The advantage of highly (111)-oriented nanotwinned Cu likely comes from the process robustness of high surface grain boundary densities rather than intrinsic atomic bonding mechanisms.
{"title":"Atomic mechanisms of Cu–Cu low-temperature bonding dominated by plastic deformation","authors":"Jinhu Fan , Jinkun Wang , Huai Zheng , Liyi Li , Yiying Zhu","doi":"10.1016/j.apsusc.2026.165904","DOIUrl":"10.1016/j.apsusc.2026.165904","url":null,"abstract":"<div><div>Highly (111)-oriented nanotwinned Cu is widely considered the optimal microstructure for Cu–Cu low-temperature bonding, attributed to its rapid surface diffusion kinetics. In this study, systematic investigations are conducted into the atomic mechanism during Cu–Cu bonding by adjusting grain characteristics at the interface using molecular dynamics simulations. The findings highlight the critical role of plastic deformation rather than the conventional surface diffusion-driven perspective. The (111)-oriented bonding interface does not show a clear advantage and, in some cases, performs even worse. Bonding kinetics are mainly governed by localized plastic deformation under stress, with grain boundary density playing a crucial role in determining the void closure rate. Grain boundaries act as high-diffusivity pathways that enable mass transport, localized recrystallization, and stress relaxation. Furthermore, typical polycrystalline Cu demonstrates enhanced stress accommodation via grain rotation, resulting in the fastest void closure rate among samples with comparable grain boundary densities. Overall, this study provides atomic-level insights into the Cu–Cu low-temperature bonding mechanism, emphasizing the importance of optimizing grain boundary density and promoting grain rotation for enhancing bonding efficiency. The advantage of highly (111)-oriented nanotwinned Cu likely comes from the process robustness of high surface grain boundary densities rather than intrinsic atomic bonding mechanisms.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"726 ","pages":"Article 165904"},"PeriodicalIF":6.9,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955021","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}
Pub Date : 2026-01-11DOI: 10.1016/j.apsusc.2026.165883
Honghong Wang , Shaodong Sun , Xiaozhe Zhang , Wenshao Lin , Shuhua Liang , Jie Cui
The construction of oxygen vacancies (OVs) is an effective means of catalyst modification, as they can modulate the energy band structure of the catalyst and enhance its ability for visible light absorption. In this study, the organic solvent ethylene glycol (EG) was employed in the hydrothermal synthesis to introduce OVs into the crystal structure of (BiO)2CO3. The photocatalytic capacity of the (BiO)2CO3 with OVs (BC20EG) was evaluated by degrading TC-HCl under visible light irradiation. Experimental results indicated that the photodegradation efficiency of BC20EG for TC-HCl could reach 92.4 % within 60 min, and its degradation rate constant k value was 8.4 times higher than that of the pristine (BiO)2CO3 (BC0EG). From theoretical calculations combined with characterizations of photoelectric properties and active radicals, it was proved that the excellent photocatalytic activity of BC20EG derived from the defective energy levels formed by OVs in its energy band structure, effectively facilitating the separation of photogenerated charges and enhancing the photo-responsiveness. The findings of this study reveal the potential advantages of the catalyst BC20EG in the removal of antibiotics for the purification of water resources.
{"title":"Mechanism insight into photocatalytic degradation of tetracycline hydrochloride by oxygen-vacancy modified (BiO)2CO3","authors":"Honghong Wang , Shaodong Sun , Xiaozhe Zhang , Wenshao Lin , Shuhua Liang , Jie Cui","doi":"10.1016/j.apsusc.2026.165883","DOIUrl":"10.1016/j.apsusc.2026.165883","url":null,"abstract":"<div><div>The construction of oxygen vacancies (OVs) is an effective means of catalyst modification, as they can modulate the energy band structure of the catalyst and enhance its ability for visible light absorption. In this study, the organic solvent ethylene glycol (EG) was employed in the hydrothermal synthesis to introduce OVs into the crystal structure of (BiO)<sub>2</sub>CO<sub>3</sub>. The photocatalytic capacity of the (BiO)<sub>2</sub>CO<sub>3</sub> with OVs (BC<sub>20EG</sub>) was evaluated by degrading TC-HCl under visible light irradiation. Experimental results indicated that the photodegradation efficiency of BC<sub>20EG</sub> for TC-HCl could reach 92.4 % within 60 min, and its degradation rate constant k value was 8.4 times higher than that of the pristine (BiO)<sub>2</sub>CO<sub>3</sub> (BC<sub>0EG</sub>). From theoretical calculations combined with characterizations of photoelectric properties and active radicals, it was proved that the excellent photocatalytic activity of BC<sub>20EG</sub> derived from the defective energy levels formed by OVs in its energy band structure, effectively facilitating the separation of photogenerated charges and enhancing the photo-responsiveness. The findings of this study reveal the potential advantages of the catalyst BC<sub>20EG</sub> in the removal of antibiotics for the purification of water resources.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"726 ","pages":"Article 165883"},"PeriodicalIF":6.9,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956546","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号