Applied Surface Science最新文献_第10页

Physicochemical properties of cholesterol micelles with embedded flame-made metal oxide nanoparticles: potential lipid-lowering effects using in vitro and in vivo evaluation 嵌入火焰制造的金属氧化物纳米颗粒的胆固醇胶束的物理化学性质：使用体外和体内评估的潜在降脂效果

IF 6.9 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science

Pub Date : 2026-01-12 DOI: 10.1016/j.apsusc.2026.165912

Chaikarn Liewhiran , Mameaseng Siriwalai , Anurat Wisitsoraat , Thanthakan Saithong , Kornwalai Tunkaew , Jakkapong Inchai , Chutima S. Vaddhanaphuti

Flame-made metal oxide nanoparticles (MOX-NPs) including ZnO, SnO₂, In₂O₃, and WO₃ were embedded into cholesterol micelles to assess their possible medical application in hypercholesterolemia treatment. Material analysis by X-ray spectroscopy and electron microscopy demonstrated the inclusion of stoichiometric hexagonal-ZnO, tetragonal-SnO₂, cubic-In₂O₃, and monoclinic-WO₃ nanoparticles with 5–30 nm in diameter within cholesterol micelles. Dynamic light scattering data revealed that the micellar size increased 4.6-fold, 4.5-fold, 3.4-fold, and 1.3-fold after incorporating ZnO-NPs, SnO₂-NPs, and In₂O₃-NPs, respectively. Zeta potential of MOX-NPs shifted negatively upon embedding into the micelle, indicating improved colloidal stability. From In vitro experiments using human colorectal adenocarcinoma (Caco-2) cells, all MOX-NPs significantly reduced cholesterol uptake to levels similar to ezetimibe (EZ). However, the in vivo assessment using [³H]-cholesterol micelles in Wistar rats revealed insignificant alterations in plasma cholesterol levels. Nevertheless, ZnO-NPs remarkably lowered cholesterol accumulated in intestinal and hepatic tissues when SnO₂-NPs only decreased hepatic cholesterol deposition. In contrast, In₂O₃-NPs and WO₃-NPs insignificantly affected cholesterol deposition. Overall, ZnO-NPs provided the highest cholesterol-lowering effect, suggesting their potential for hypercholesterolemia treatment. Nonetheless, the in vivo lipid-lowering efficiencies in tissues were relatively low compared with EZ. Thus, improvements and safety assessments must be made before applying them to real medical applications.

火焰制备的金属氧化物纳米颗粒（MOX-NPs）包括ZnO、SnO2、In2O3和WO3嵌入胆固醇胶束中，以评估其在高胆固醇血症治疗中的潜在医学应用。通过x射线光谱学和电子显微镜对材料进行分析，发现在胆固醇胶束中包含了直径为5-30 nm的六边形zno、四边形sno2、立方in2o3和单斜wo3纳米颗粒。动态光散射数据显示，加入ZnO-NPs、SnO2-NPs和In2O3-NPs后，胶束尺寸分别增加了4.6倍、4.5倍、3.4倍和1.3倍。MOX-NPs嵌入胶团后Zeta电位发生负移动，表明胶体稳定性得到改善。使用人结直肠癌（Caco-2）细胞进行的体外实验显示，所有MOX-NPs均可显著降低胆固醇摄取，其水平与依折替米贝（eztimibe）相似。然而，在Wistar大鼠中使用[3H]-胆固醇胶束的体内评估显示血浆胆固醇水平没有明显变化。然而，ZnO-NPs显著降低了肠道和肝脏组织中积累的胆固醇，而SnO2-NPs仅降低了肝脏胆固醇沉积。相比之下，In2O3-NPs和WO3-NPs对胆固醇沉积影响不显著。总的来说，ZnO-NPs提供了最高的降胆固醇效果，表明它们具有治疗高胆固醇血症的潜力。然而，与EZ相比，体内组织降脂效率相对较低。因此，在将其应用于实际医疗应用之前，必须进行改进和安全性评估。

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引用次数: 0

A green, inhibitor-free CMP slurry enabled by synergistic surfactant design for cobalt-based copper interconnects 一种绿色、无抑制剂的CMP浆液，采用协同表面活性剂设计，可用于钴基铜互连

IF 6.9 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science

Pub Date : 2026-01-12 DOI: 10.1016/j.apsusc.2026.165909

Jiahui Li , Chao He , Xinhuan Niu , Jiakai Zhou , Changxin Dong , Xinjie Li , Zheng Wu , Bin Hu

As device feature sizes scale down to 14 nm, cobalt (Co) has been identified as a suitable barrier layer material for advanced copper (Cu) interconnects in integrated circuits. In chemical mechanical polishing (CMP) of Cu films in Co-based Cu interconnect structures, achieving a high Cu-to-Co removal rate selectivity is essential to prevent barrier layer degradation and ensure process fidelity. Here, we report the rational design of an inhibitor-free CMP slurry based on a co-surfactant system composed of dodecylbenzenesulphonic acid (DBSA) and dodecyl dimethyl betaine (BS-12). The optimized formulation achieves a removal rate selectivity exceeding 107:1, while simultaneously delivering low surface roughness for both Cu (Sq = 1.49 nm) and cobalt (Sq = 1.07 nm). Electrochemical characterization reveals that the DBSA + BS-12 system forms a compact, passivating interfacial film that effectively mitigates electrochemical corrosion. Finally, density functional theory (DFT) calculations further reveal the enhanced molecular reactivity and optimal reactive sites of the synergistic DBSA-BS + 12 system, providing atomic-level insight into its superior inhibition performance. This study establishes a green, dual-function co-surfactant strategy that eliminates the need for toxic azole-based inhibitors, streamlines slurry composition, and provides a scalable solution for next-generation CMP processes in advanced interconnect technology.

随着器件特征尺寸缩小到14 nm，钴（Co）已被确定为集成电路中高级铜（Cu）互连的合适阻挡层材料。在化学机械抛光（CMP） co基Cu互连结构中的Cu膜中，实现高Cu- co去除率是防止阻挡层降解和保证工艺保真度的关键。本文报道了基于十二烷基苯磺酸（DBSA）和十二烷基二甲基甜菜碱（BS-12）组成的助表面活性剂体系的无抑制剂CMP浆料的合理设计。优化后的配方对铜（Sq = 1.49 nm）和钴（Sq = 1.07 nm）的去除率超过107:1，同时具有较低的表面粗糙度。电化学表征表明，DBSA + BS-12体系形成致密的钝化界面膜，有效减轻了电化学腐蚀。最后，密度泛函理论（DFT）计算进一步揭示了增效DBSA-BS + 12体系的增强分子反应性和最佳反应位点，为其优越的抑制性能提供了原子水平的见解。该研究建立了一种绿色、双功能的助表面活性剂策略，消除了对有毒的唑基抑制剂的需求，简化了浆液组成，并为先进互连技术中的下一代CMP工艺提供了可扩展的解决方案。

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引用次数: 0

Electrodeposited MgAl LDH/SiO2 composite coating toward active/passive corrosion protection 电沉积MgAl LDH/SiO2复合镀层用于主动/被动防腐

IF 6.9 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science

Pub Date : 2026-01-12 DOI: 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.

由于锌层易腐蚀，镀锌钢在高盐度的沿海或海洋环境中使用寿命有限。尽管人们在开发各种防护涂料方面做出了巨大的努力，但构建具有主动/被动防护能力的无机和绿色涂料仍然是一个挑战。本文采用电沉积法将嵌入MoO42−阴离子的MgAl层状双氢氧化物（LDH）纳米片掺入到无机二氧化硅（SiO2）涂层中。结合LDH的离子交换和MoO42−的抑制作用，薄LDH@SiO2复合涂层可以实现对锌的主动/被动保护。在0.01 Hz （|Z|0.01Hz）处的阻抗模量比Zn提高了4个数量级，腐蚀电流密度降低到1.0195 × 10−8 A/cm2。经过30 天的浸渍试验，LDH@SiO2复合涂层仍然具有较高的耐腐蚀性。自愈效率达99.52%。涂层的物理屏障和迷宫效应提高了涂层的耐蚀性，而MgAl LDH中MoO42−的释放有助于自修复过程。本研究提出了一种新型的绿色锌主动/被动防护技术，为理解LDH@SiO2复合涂层在海洋环境中的保护机制提供了新的思路。

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引用次数: 0

Tuning surface hydrophobicity of palladium catalysts via alkyl ligand functionalization for direct synthesis of hydrogen peroxide 烷基配体功能化对过氧化氢直接合成钯催化剂表面疏水性的调节

IF 6.9 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science

Pub Date : 2026-01-11 DOI: 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 g_Pd⁻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.

过氧化氢（H2O2）副产物仅为水和氧，是一种非常理想的绿色氧化剂，广泛应用于环境修复、制药和精细化工等领域。在各种生产路线中，H2和O2直接合成（DSHP）提供了传统工艺的可持续替代方案。然而，它的实际应用受到选择性差和H2O2快速降解的限制，这突出了对先进催化剂设计的需求。本研究提出了一种表面工程策略，通过化学接枝十八烷基三甲氧基硅烷配体来精确调整Pd/SiO2催化剂的疏水性。与传统疏水碳载体遭受弱金属载体相互作用和位点堵塞不同，功能化催化剂表现出更好的结构稳定性。表面疏水性的逐步增强有利于非极性反应物（H2、O2）的扩散，加速亲水性H2O2的解吸，有效抑制其分解。值得注意的是，配体密度中等（10C18-Pd/SiO2）的催化剂达到了最佳平衡，选择性为84.5%，产率为2,754 mmol gPd−1·h−1，比未修饰的Pd/SiO2催化剂高约52%。过量的配体覆盖阻碍了H3PO4稳定剂接近Pd活性位点，从而划定了有效DSHP催化所必需的临界疏水性窗口。

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引用次数: 0

3D framework energetic composites: an efficient catalyst for ammonium perchlorate thermal decomposition 三维框架含能复合材料：高氯酸铵热分解的高效催化剂

IF 6.9 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science

Pub Date : 2026-01-11 DOI: 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.

一系列M2-L@OBC复合材料(M = Cu(II), Co(II), Fe(III)；L = 5-硝基-3-吡唑羧酸；M:L摩尔比 = 2:1；成功合成了三维网络结构的OBC = 羧化细菌纤维素（carboxyylated bacterial cellulose），并将其用于高氯酸铵（AP）的热分解。对M2-L@OBC复合材料进行了IR、SEM、TEM、HRTEM、XPS和XRD表征，结果表明，纳米M2-L均匀覆盖在纤维素纤维上。采用非等温法对其催化效果进行了研究，结果表明Fe2-L@OBC复合材料具有优异的催化性能。AP混合2 wt% Fe2-L@OBC的高温分解（HTD）阶段峰值温度提高了66 ℃，活化能降低了56 kJ/mol，反应速率常数提高了1.1倍。此外，在线TG/FT-IR显示Fe2-L@OBC复合材料可以显著加速HClO4和NH3的消耗，转化为N2O、NO和NO2。这是由于Fe2-L@OBC表面丰富的活性位点在分解成金属氧化物纳米颗粒后提供了新鲜的活性位点，从而促进了HTD阶段的电子转移过程。

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引用次数: 0

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 不饱和羟肟酸捕收剂对钛铁矿和橄榄石浮选分离的新认识：双键提供电子效应以提高选择性吸附

IF 6.7 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science

Pub Date : 2026-01-11 DOI: 10.1016/j.apsusc.2026.165908

Huaiyao Zhang, Tingting Chen, Xiaoman Wang, Yijun Cao, Jingchao Li, Guosheng Li, Junwei Huang, Shuling Gao, Fanfan Zhang, Guixia Fan

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

在绿色和可持续开采的背景下，钛铁矿和橄榄石的高效分离仍然是一个挑战，主要是由于药剂用量大、矿浆残留高以及传统捕收剂造成的水污染。本文设计并合成了一种新型不饱和短链羟酸酯反式-2-辛烯基羟酸钠（NaOHA-II），以增强钛铁矿的浮选性能。通过浮选实验、现代分析技术和分子动力学模拟，比较了其与辛羟肟酸（naoha - 1）的捕收性能。微浮选试验表明，当NaOHA-II用量为50 mg/L时，钛铁矿回收率为84.80%，橄榄石回收率仅为5.02%。在实际浮选中，与500 g/t NaOHA-I相比，300 g/t NaOHA-II可使粗精矿TiO2品位和回收率分别提高3.15%和38.59%。同时，该试剂用量减少40%，减少纸浆残留，并提供无毒认证，满足绿色分离。机理分析表明，NaOHA-II的双键提高了极性基团的电子密度（增强了静电和氢键）。此外，羟肟酸活性基团的电负性增强，使其更容易给电子和形成化学键，从而增强了钛铁矿表面的选择性化学吸附，突出了其作为钛铁矿浮选的有效捕收剂的潜力

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引用次数: 0

Toward accurate UPS characterization of photocatalysts: common pitfalls and a validated protocol using CsPbBr3 perovskite 对光催化剂的准确UPS表征：使用CsPbBr3钙钛矿的常见缺陷和经过验证的协议

IF 6.9 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science

Pub Date : 2026-01-11 DOI: 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.

光催化剂以其将光能转化为化学能的独特能力引起了人们的广泛关注。准确测定费米能级、功函数（WF）、价带最大值（VBM）等关键电子结构参数，对于理解电荷分离机理和合理设计高性能光催化剂至关重要。紫外光电子能谱（UPS）因其高精度而在这些参数的测定中得到广泛认可。然而，在光催化领域缺乏详细和实用的UPS表征方法指南，导致文献中对结果的广泛误解。因此，本文系统地总结了光催化剂UPS分析中常见的陷阱和误区。我们进一步提出了一个经过验证且详细的操作方案（以CsPbBr3钙钛矿光催化剂为例），以准确确定光催化剂的能级排列，涵盖了样品制备、测量和数据分析的整个过程。本工作旨在通过建立清晰严谨的UPS表征方法，减少因电子结构测定不准确而导致的光催化机理误解，为光催化剂研究提供实践指导。

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引用次数: 0

Synergistic construction of preferential growth of WO3 and ion channels induced by non-ionic polyethylene glycol to enhance electrochromic performance WO3与非离子型聚乙二醇诱导的离子通道协同构建优先生长以提高电致变色性能

IF 6.9 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science

Pub Date : 2026-01-11 DOI: 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 ((t_c/t_b = 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.

本文重点研究了一种很有前途的电致变色材料氧化钨。采用表面活性剂辅助水热法制备了微观结构可控的WO3·0.33H2O薄膜。与离子表面活性剂十二烷基硫酸钠（SDS）调控的WO3-SDS膜和纯相WO3·0.33H2O膜（标记为WO3膜）相比，本研究采用非离子型聚乙二醇（PEG）作为结构导向剂，成功制备了具有优选（220）晶面取向的高结晶度WO3-PEG膜。扫描电镜（SEM）分析表明，该膜具有均匀的颗粒形态，颗粒紧密堆积形成颗粒间通道，形成层状离子扩散路径。电化学测试表明，WO3- peg薄膜具有优异的电致变色性能，其Li+扩散系数（5.094 × 10−13 cm2/s）显著提高，是纯WO3（2.971 × 10−13 cm2/s）的1.71倍。响应时间快（tc/tb = 4.73 s/4.57 s），光调制幅度高（在600 nm波长处ΔT为61.50%）。通过优化结晶度和工程离子通道结构的协同效应，实现了同步电子转移和离子插入，为高性能电致变色材料的设计提供了新的途径。

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引用次数: 0

Excellent contact-electro-catalysis performance from fluorine-free polymers modified by real-time generated plasma-activated water 实时生成的等离子体活化水修饰的无氟聚合物具有优异的接触电催化性能

IF 6.9 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science

Pub Date : 2026-01-11 DOI: 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。

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引用次数: 0

Boosting selective degradation of refractory dissolved organic matter in landfill leachate: Morphology-tunable ZnO via magnetron sputtering-hydrothermal synthesis 促进垃圾渗滤液中难降解溶解有机物的选择性降解：磁控溅射-水热合成形貌可调ZnO

IF 6.9 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science

Pub Date : 2026-01-11 DOI: 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.

垃圾渗滤液是一种富含高浓度溶解有机物（DOM）的复杂难处理废水，难以进行常规生化处理，对水生生态系统和人类健康构成威胁。开发高效、稳定的DOM修复技术仍然是当务之急。本文采用磁控溅射预处理和水热反应相结合的方法合成了四种不同形貌的ZnO光催化剂（棒状ZnO-1、花状ZnO-2、针状ZnO-3、棒状排列ZnO-4）。表征表明ZnO-1具有较高的氧空位密度（62.05 %）和高效的光电子空穴分离。光催化90 min后，ZnO-1对TOC（36.84 %）和DOM（63.16 %）的降解效率最高，优于其他样品。所有的催化剂都倾向于类黄腐酸物质而不是类蛋白质物质的降解。羟基自由基（·OH）是主要活性物质，它与超氧自由基（·O2 -）和光生空穴（h+）协同作用，通过C=C解理、芳环打开和矿化作用降解DOM。四个循环后，ZnO-1的活性保持在30% %。本研究为难降解DOM修复提供了一种高性能催化剂，并指导了复杂废水处理中形态控制半导体催化剂的设计。

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