Alumina aerogels have attracted great interest for extreme thermal insulation. However, traditional alumina aerogels inevitably undergo severe structural degradation above 1000 °C due to the metastable-to-α phase transformation, which fundamentally limits their ultrahigh-temperature applications. In nature, red coral constructs its robust porous skeleton directly from calcite, the thermodynamically stable polymorph of CaCO3, thereby achieving exceptional long-term structural durability. Inspired by this “thermodynamically stable-phase construction” wisdom, we herein propose a thermodynamically stable-phase core-shell (TSC) strategy that employs thermodynamically stable α-Al2O3 nanoparticles as building blocks. The in situ sol-gel growth of a methyl-containing SiO2 shell on the nanoparticle surfaces directly yields three-dimensional continuous α-Al2O3@SiO2 core-shell aerogels (SAAs). The resulting SAAs exhibit outstanding ultrahigh-temperature thermal stability, retaining a non-collapsed porous skeleton with a high specific surface area retention of 23.6% after calcination at 1500 °C in air for 2 h. They also display excellent superhydrophobicity, with a water contact angle as high as 163.0° and a rolling angle as low as 2.9°. Furthermore, the SAAs deliver remarkable thermal insulation performance, exhibiting a room-temperature thermal conductivity of only 0.0394 W·m−1·K−1. When exposed to a 1300 °C butane torch flame for 120 s, a merely 4-mm-thick SAAs plate registers a cold-side temperature rise of only 141 °C. Molecular dynamics simulations reveal that the SiO2 shell acts as an efficient physical and diffusion barrier, effectively suppressing sintering neck formation and atomic diffusion between particles, thereby preserving the nanostructure at extreme temperatures. This work not only provides a coral-inspired stable-phase construction pathway toward lightweight ceramic aerogels for extreme environments but also establishes a general approach for constructing sintering-resistant nanostructures based on thermodynamically stable-phase nanoparticles via core-shell engineering.
{"title":"Coral-Inspired Thermodynamically Stable-Phase Core-Shell Strategy Enables α-Al2O3@SiO2 Aerogels with Thermal Stability up to 1500 °C and Superhydrophobicity","authors":"Zhendong Jiang,Yonggang Jiang,Mengyao Zhao,Junzong Feng,Yijie Hu,Jian Feng","doi":"10.1021/acsami.6c16249","DOIUrl":"https://doi.org/10.1021/acsami.6c16249","url":null,"abstract":"Alumina aerogels have attracted great interest for extreme thermal insulation. However, traditional alumina aerogels inevitably undergo severe structural degradation above 1000 °C due to the metastable-to-α phase transformation, which fundamentally limits their ultrahigh-temperature applications. In nature, red coral constructs its robust porous skeleton directly from calcite, the thermodynamically stable polymorph of CaCO3, thereby achieving exceptional long-term structural durability. Inspired by this “thermodynamically stable-phase construction” wisdom, we herein propose a thermodynamically stable-phase core-shell (TSC) strategy that employs thermodynamically stable α-Al2O3 nanoparticles as building blocks. The in situ sol-gel growth of a methyl-containing SiO2 shell on the nanoparticle surfaces directly yields three-dimensional continuous α-Al2O3@SiO2 core-shell aerogels (SAAs). The resulting SAAs exhibit outstanding ultrahigh-temperature thermal stability, retaining a non-collapsed porous skeleton with a high specific surface area retention of 23.6% after calcination at 1500 °C in air for 2 h. They also display excellent superhydrophobicity, with a water contact angle as high as 163.0° and a rolling angle as low as 2.9°. Furthermore, the SAAs deliver remarkable thermal insulation performance, exhibiting a room-temperature thermal conductivity of only 0.0394 W·m−1·K−1. When exposed to a 1300 °C butane torch flame for 120 s, a merely 4-mm-thick SAAs plate registers a cold-side temperature rise of only 141 °C. Molecular dynamics simulations reveal that the SiO2 shell acts as an efficient physical and diffusion barrier, effectively suppressing sintering neck formation and atomic diffusion between particles, thereby preserving the nanostructure at extreme temperatures. This work not only provides a coral-inspired stable-phase construction pathway toward lightweight ceramic aerogels for extreme environments but also establishes a general approach for constructing sintering-resistant nanostructures based on thermodynamically stable-phase nanoparticles via core-shell engineering.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"22 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250812","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}
Organic charge-transfer cocrystals have emerged as promising candidates for photothermal conversion, yet current design strategies predominantly focus on intermolecular charge-transfer interactions or nonradiative decay pathways, with less attention paid to the fundamental prerequisite of absorbance. Here, we propose a high-extinction-coefficient donor engineering strategy to boost photothermal conversion. A charge-transfer cocrystal (BNQ) was constructed from DtBuCzB—a donor with a high molar extinction coefficient (5.81 × 104 L mol–1 cm–1)—and the classical acceptor TCNQ. The BNQ cocrystal exhibits a well-ordered 2:1 alternating columnar packing structure with close π–π interactions and C–H···N hydrogen bonds, leading to a narrow optical bandgap of 1.04 eV and broad-spectrum absorption extending to 1198 nm. Under 808 nm laser irradiation, BNQ achieves an outstanding photothermal conversion efficiency of 95.1% and an ultrafast heating rate (130 °C within 10 s), substantially outperforming previously reported TCNQ-based cocrystals. As a practical demonstration, BNQ-incorporated polyurethane foam delivers an average solar-driven water evaporation rate of 1.84 ± 0.03 kg m–2 h–1 under 1-sun illumination with excellent operational stability. This work establishes donor extinction coefficient engineering as a simple yet powerful design strategy for developing next-generation photothermal cocrystals and provides a design parameter for the rational screening of component monomers.
有机电荷转移共晶已经成为光热转换的有希望的候选者，但目前的设计策略主要集中在分子间电荷转移相互作用或非辐射衰变途径上，很少关注吸收的基本先决条件。在这里，我们提出了一个高消光系数供体工程策略来提高光热转换。以高摩尔消光系数（5.81 × 104 L mol-1 cm-1）的给体dtbuczb和经典受体TCNQ构建了电荷转移共晶（BNQ）。BNQ共晶具有有序的2:1交替柱状填充结构，具有紧密的π -π相互作用和C-H··N氢键，具有1.04 eV的窄带隙和1198 nm的广谱吸收。在808 nm激光照射下，BNQ实现了95.1%的光热转换效率和超快的升温速率（10 s内130°C），大大优于先前报道的基于tcnq的共晶。作为实际演示，bnq -加入的聚氨酯泡沫在1太阳光照下的平均太阳能驱动水蒸发速率为1.84±0.03 kg m-2 h-1，具有出色的运行稳定性。本研究建立了供体消光系数工程作为开发下一代光热共晶的一种简单而有效的设计策略，并为合理筛选组分单体提供了设计参数。
{"title":"High-Extinction-Coefficient Donor Engineering Enables High-Performance Photothermal Cocrystals","authors":"Zhuanbian Yang,Ting Huang,Chengjian Li,Qing Zhang,Xuan Zhang,Yujian Zhang","doi":"10.1021/acsami.6c11937","DOIUrl":"https://doi.org/10.1021/acsami.6c11937","url":null,"abstract":"Organic charge-transfer cocrystals have emerged as promising candidates for photothermal conversion, yet current design strategies predominantly focus on intermolecular charge-transfer interactions or nonradiative decay pathways, with less attention paid to the fundamental prerequisite of absorbance. Here, we propose a high-extinction-coefficient donor engineering strategy to boost photothermal conversion. A charge-transfer cocrystal (BNQ) was constructed from DtBuCzB—a donor with a high molar extinction coefficient (5.81 × 104 L mol–1 cm–1)—and the classical acceptor TCNQ. The BNQ cocrystal exhibits a well-ordered 2:1 alternating columnar packing structure with close π–π interactions and C–H···N hydrogen bonds, leading to a narrow optical bandgap of 1.04 eV and broad-spectrum absorption extending to 1198 nm. Under 808 nm laser irradiation, BNQ achieves an outstanding photothermal conversion efficiency of 95.1% and an ultrafast heating rate (130 °C within 10 s), substantially outperforming previously reported TCNQ-based cocrystals. As a practical demonstration, BNQ-incorporated polyurethane foam delivers an average solar-driven water evaporation rate of 1.84 ± 0.03 kg m–2 h–1 under 1-sun illumination with excellent operational stability. This work establishes donor extinction coefficient engineering as a simple yet powerful design strategy for developing next-generation photothermal cocrystals and provides a design parameter for the rational screening of component monomers.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"98 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248550","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}
Poly(ethylene oxide) (PEO) is a promising solid-state polymer electrolyte (SPE), but its room-temperature crystallization leads to low ionic conductivity, limiting its application. Semi-interpenetrating networks (semi-IPNs) represent an effective strategy for suppressing PEO crystallization. Previous studies have overlooked the influence of crosslinking temperature on the network topology. Here, we report a crosslinking temperature-regulated topological confinement of amorphous PEO electrolyte achieved by initiating the photopolymerization of ethoxylated trimethylolpropane triacrylate (ETPTA) at 80 °C. The resulting homogeneous network effectively confines the amorphous phase of PEO while retaining local freedom for Na+ transport. When the mass ratio of PEO to ETPTA is 60:40 (P-E40H), the material exhibits optimal comprehensive electrochemical performance, demonstrating a high room-temperature ionic conductivity of 0.173 mS cm–1, a high Na+ transference number of 0.59, high voltage stability of 4.72 V, and an elongation at break of 160.05%. Molecular dynamics simulations indicate that the uniform network allows Na+ to adopt a solvation structure dominated purely by PEO. The capacity retention ratios of Na3V2(PO4)3|P-E40H|Na cell are 92.9% (1 C, 400 cycles) and exhibits a specific capacity of 64.05 mAh g–1 at 5 C. This work demonstrates that crosslinking temperature is an effective processing parameter for tuning the network topology of semi-IPN electrolytes, offering a simple and efficient structural regulation strategy for high-performance solid-state sodium-metal batteries.
聚环氧乙烷（PEO）是一种很有前途的固态聚合物电解质（SPE），但其室温结晶导致离子电导率低，限制了其应用。半互穿网络（semi-IPNs）是抑制PEO结晶的有效策略。以往的研究忽略了交联温度对网络拓扑结构的影响。在这里，我们报道了一种交联温度调节的无定形PEO电解质的拓扑限制，通过在80°C下引发乙氧基化三甲基丙烷三丙烯酸酯（ETPTA）的光聚合。由此产生的均匀网络有效地限制了PEO的非晶相，同时保留了Na+输运的局部自由。当PEO与ETPTA的质量比为60:40 （P-E40H）时，该材料的综合电化学性能最佳，室温离子电导率为0.173 mS cm-1， Na+转移数为0.59，电压稳定性为4.72 V，断裂伸长率为160.05%。分子动力学模拟表明，均匀的网络使得Na+采用纯PEO主导的溶剂化结构。Na3V2(PO4)3|P-E40H|钠电池的容量保持率为92.9%（1℃，400次循环），在5℃时的比容量为64.05 mAh g-1。本研究表明，交联温度是调节半ipn电解质网络拓扑结构的有效工艺参数，为高性能固态钠金属电池提供了一种简单有效的结构调节策略。
{"title":"Crosslinking Temperature-Regulated Topological Confinement of Amorphous PEO Electrolytes for High-Performance Sodium-Metal Batteries","authors":"Bolin Li,Hu Fu,Yuping Wu,Zhirong Chen,Haichen Li,Qinran Zhang,Hongming Zhou","doi":"10.1021/acsami.6c21141","DOIUrl":"https://doi.org/10.1021/acsami.6c21141","url":null,"abstract":"Poly(ethylene oxide) (PEO) is a promising solid-state polymer electrolyte (SPE), but its room-temperature crystallization leads to low ionic conductivity, limiting its application. Semi-interpenetrating networks (semi-IPNs) represent an effective strategy for suppressing PEO crystallization. Previous studies have overlooked the influence of crosslinking temperature on the network topology. Here, we report a crosslinking temperature-regulated topological confinement of amorphous PEO electrolyte achieved by initiating the photopolymerization of ethoxylated trimethylolpropane triacrylate (ETPTA) at 80 °C. The resulting homogeneous network effectively confines the amorphous phase of PEO while retaining local freedom for Na+ transport. When the mass ratio of PEO to ETPTA is 60:40 (P-E40H), the material exhibits optimal comprehensive electrochemical performance, demonstrating a high room-temperature ionic conductivity of 0.173 mS cm–1, a high Na+ transference number of 0.59, high voltage stability of 4.72 V, and an elongation at break of 160.05%. Molecular dynamics simulations indicate that the uniform network allows Na+ to adopt a solvation structure dominated purely by PEO. The capacity retention ratios of Na3V2(PO4)3|P-E40H|Na cell are 92.9% (1 C, 400 cycles) and exhibits a specific capacity of 64.05 mAh g–1 at 5 C. This work demonstrates that crosslinking temperature is an effective processing parameter for tuning the network topology of semi-IPN electrolytes, offering a simple and efficient structural regulation strategy for high-performance solid-state sodium-metal batteries.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"82 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250811","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}
Controlling the in-plane orientation of two-dimensional nanosheets during repeated forming remains challenging because deformation can become nonuniform through the film thickness. Here, alternating 60 and 80 wt % boron nitride nanosheet/thermoplastic polyurethane (BNNS/TPU) layers were used to introduce a moderate modulus contrast during water-based stack pressing and were compared with homogeneous 70 wt % films having the same nominal average filler content. Repeated pressing increased BNNS alignment in both architectures, while the binary film exhibited a slightly narrower SEM-derived angular distribution after six total pressing operations. The binary film reached an in-plane thermal conductivity of 17.85 W m–1·K–1, a through-plane thermal conductivity of 0.22 W m–1 K–1, a tensile strength of 17.48 MPa, and a thermal anisotropy ratio of approximately 81. Under the present point-heating configuration, its hotspot temperature was 5.7 °C lower than that of the unitary film at 60 s. Idealized linear-elastic finite-element analysis qualitatively illustrates modulus-dependent stress and strain partitioning but does not model interfacial damage or nanosheet rotation. Fabrication of 400 × 400 mm films further demonstrates large-area batch-processing feasibility.
在重复成形过程中，控制二维纳米片的面内取向仍然是一个挑战，因为变形会随着薄膜厚度的变化而变得不均匀。在这里，60和80 wt %氮化硼纳米片/热塑性聚氨酯（BNNS/TPU）层交替使用，以在水基堆压过程中引入适度的模量对比，并与具有相同标称平均填料含量的70 wt %均匀薄膜进行比较。在这两种结构中，重复的压制增加了BNNS的取向，而在总共六次压制操作后，二元薄膜的sem衍生角分布略窄。二元膜的面内导热系数为17.85 W m-1·K-1，通面导热系数为0.22 W m-1 K-1，抗拉强度为17.48 MPa，热各向异性比约为81。在当前点加热结构下，其热点温度在60 s时比单一膜低5.7℃。理想的线弹性有限元分析定性地说明了模量依赖的应力和应变分配，但不模拟界面损伤或纳米片旋转。400 × 400毫米薄膜的制备进一步证明了大面积批量加工的可行性。
{"title":"Green Manufacturing of High-Performance Multilayered Boron Nitride Composites via Modulus-Contrast-Assisted Stack Pressing","authors":"Peiyao Ran,Youxing Shu,Fangzheng Zhen,Siyuan Ding,Yu Du,Yueni Zhong,Qixuan Deng,Miheng Dong,Song Huang,Zhijun Guo,Weiren Fan,Ruiping Zou,Aibing Yu,Ling Qiu,Minsu Liu","doi":"10.1021/acsami.6c17025","DOIUrl":"https://doi.org/10.1021/acsami.6c17025","url":null,"abstract":"Controlling the in-plane orientation of two-dimensional nanosheets during repeated forming remains challenging because deformation can become nonuniform through the film thickness. Here, alternating 60 and 80 wt % boron nitride nanosheet/thermoplastic polyurethane (BNNS/TPU) layers were used to introduce a moderate modulus contrast during water-based stack pressing and were compared with homogeneous 70 wt % films having the same nominal average filler content. Repeated pressing increased BNNS alignment in both architectures, while the binary film exhibited a slightly narrower SEM-derived angular distribution after six total pressing operations. The binary film reached an in-plane thermal conductivity of 17.85 W m–1·K–1, a through-plane thermal conductivity of 0.22 W m–1 K–1, a tensile strength of 17.48 MPa, and a thermal anisotropy ratio of approximately 81. Under the present point-heating configuration, its hotspot temperature was 5.7 °C lower than that of the unitary film at 60 s. Idealized linear-elastic finite-element analysis qualitatively illustrates modulus-dependent stress and strain partitioning but does not model interfacial damage or nanosheet rotation. Fabrication of 400 × 400 mm films further demonstrates large-area batch-processing feasibility.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"166 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248541","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}
Yantao Deng,Songkun Zeng,Yufeng Xie,Wenbin Huang,Zikai He
Achieving deep-blue electroluminescence with high efficiency and color purity that meets the BT.2020 standard remains a major challenge for organic light-emitting diodes. Here, we report two D–π–A emitters, SFIA-1 and SFIA-2, based on a spiro-fluorene-imidazole acceptor (A) and a 10H-spiro(acridine-9,9′-fluorene) donor (D). By strategically introducing a para-phenylene bridge, the molecules adopt highly twisted conformations. Experimental and theoretical analyses further reveal CT-dominated, hybridized local-excited and charge-transfer states. Both emitters exhibit wide optical band gaps (>3.3 eV). A negligible singlet–triplet energy gap of 0.01 eV, combined with a moderate spin–orbit coupling, activates an efficient high-lying reverse intersystem crossing “hot exciton” channel. As a result, the SFIA-1-doped device achieves a maximum external quantum efficiency (EQE) of 7.53% with an electroluminescence peak at 425 nm, while SFIA-2 delivers an electroluminescence peak at 420 nm with Commission Internationale de l'Éclairage coordinates of (0.159, 0.043), closely aligned with the BT.2020 blue light standard. Furthermore, the non-doped devices based on SFIA-1 and SFIA-2 exhibit maximum EQEs of 6.29 and 10.89%, respectively. Therefore, SFIA-2 was utilized as a host for PO-01-TB, tCzphB-Ph, and Ir(mphmq)2(tmd) emitters, yielding maximum EQEs of 30.47, 24.09, and 15.57%, respectively. These results demonstrate a molecular design strategy for ultra-deep-blue hot-exciton materials and high-performance hosts that reconciles the trade-off between exciton utilization efficiency and color purity.
实现符合BT.2020标准的高效率和色纯度的深蓝色电致发光仍然是有机发光二极管的主要挑战。在这里，我们报道了两个D -π-A发射体，SFIA-1和SFIA-2，基于一个螺-芴-咪唑受体(a)和一个10h -螺（吖啶-9,9 ' -芴）供体(D)。通过巧妙地引入对苯基桥，分子采用高度扭曲的构象。实验和理论分析进一步揭示了ct主导、杂化的局部激发态和电荷转移态。两个发射体都表现出较宽的光学带隙（>3.3 eV）。一个可以忽略不计的0.01 eV的单重态-三重态能隙，加上适度的自旋-轨道耦合，激活了一个高效的高空反向系统间穿越“热激子”通道。结果表明，sfia -1掺杂器件的最大外量子效率（EQE）为7.53%，电致发光峰值为425 nm，而SFIA-2的电致发光峰值为420 nm，国际委员会（Commission Internationale del 'Éclairage）坐标为（0.159,0.043），与BT.2020蓝光标准密切相关。此外，基于SFIA-1和SFIA-2的未掺杂器件的最大EQEs分别为6.29%和10.89%。因此，利用SFIA-2作为PO-01-TB、tCzphB-Ph和Ir(mphmq)2（tmd）发射体的宿主，获得的最大EQEs分别为30.47%、24.09和15.57%。这些结果证明了一种超深蓝色热激子材料和高性能宿主的分子设计策略，该策略可以协调激子利用效率和颜色纯度之间的权衡。
{"title":"Deep-Blue Hot Exciton Emitters Approaching the BT.2020 Standard: Spiro-Fluoreno-Imidazole Acceptors with Twisted D–π–A Architectures","authors":"Yantao Deng,Songkun Zeng,Yufeng Xie,Wenbin Huang,Zikai He","doi":"10.1021/acsami.6c16895","DOIUrl":"https://doi.org/10.1021/acsami.6c16895","url":null,"abstract":"Achieving deep-blue electroluminescence with high efficiency and color purity that meets the BT.2020 standard remains a major challenge for organic light-emitting diodes. Here, we report two D–π–A emitters, SFIA-1 and SFIA-2, based on a spiro-fluorene-imidazole acceptor (A) and a 10H-spiro(acridine-9,9′-fluorene) donor (D). By strategically introducing a para-phenylene bridge, the molecules adopt highly twisted conformations. Experimental and theoretical analyses further reveal CT-dominated, hybridized local-excited and charge-transfer states. Both emitters exhibit wide optical band gaps (>3.3 eV). A negligible singlet–triplet energy gap of 0.01 eV, combined with a moderate spin–orbit coupling, activates an efficient high-lying reverse intersystem crossing “hot exciton” channel. As a result, the SFIA-1-doped device achieves a maximum external quantum efficiency (EQE) of 7.53% with an electroluminescence peak at 425 nm, while SFIA-2 delivers an electroluminescence peak at 420 nm with Commission Internationale de l'Éclairage coordinates of (0.159, 0.043), closely aligned with the BT.2020 blue light standard. Furthermore, the non-doped devices based on SFIA-1 and SFIA-2 exhibit maximum EQEs of 6.29 and 10.89%, respectively. Therefore, SFIA-2 was utilized as a host for PO-01-TB, tCzphB-Ph, and Ir(mphmq)2(tmd) emitters, yielding maximum EQEs of 30.47, 24.09, and 15.57%, respectively. These results demonstrate a molecular design strategy for ultra-deep-blue hot-exciton materials and high-performance hosts that reconciles the trade-off between exciton utilization efficiency and color purity.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"1 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250809","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}
Tianhao Xu,Xuemeng Fu,Liquan Wang,Liangshun Zhang,Jiaping Lin
Optimizing the properties of thermosetting polymers presents an inherent challenge due to the high-dimensional formulation-processing parameter space and the trade-offs between thermomechanical properties. In this contribution, we propose a hierarchical Monte Carlo tree search (MCTS)-guided Bayesian optimization (BO) framework to enable the simultaneous design of both the composition and curing protocols of epoxy resins as a major class of thermosetting polymers. A sigmoid-based weighting strategy is introduced to encode application-driven performance thresholds into the objective function, guiding the optimization toward coordinated multi-property improvement. With only 30 experiments across four iterative rounds, the framework optimizes both the formulation and curing protocols to yield a performance-enhanced epoxy resin that simultaneously meets all four target thresholds. This balanced performance cannot be achieved by any of the initial samples, an equal-weight baseline, or commercial and literature-reported systems. Furthermore, interpretable machine learning analysis combined with targeted experimental validation quantitatively resolves the relative importance of formulation and processing parameters, indicating that composition variables dominate overall property trends while their synergistic interactions produce non-linear effects on glass transition temperature. The findings demonstrate that the hierarchical MCTS-guided BO framework offers an efficient strategy for navigating complex formulation-processing spaces, and the interpretable analysis provides a quantitative basis for understanding structure–property relationships in thermosetting polymers.
{"title":"Hierarchical MCTS-Guided Bayesian Optimization for Co-designing Formulation and Processing of Thermosetting Polymers with Balanced Performance","authors":"Tianhao Xu,Xuemeng Fu,Liquan Wang,Liangshun Zhang,Jiaping Lin","doi":"10.1021/acsami.6c18158","DOIUrl":"https://doi.org/10.1021/acsami.6c18158","url":null,"abstract":"Optimizing the properties of thermosetting polymers presents an inherent challenge due to the high-dimensional formulation-processing parameter space and the trade-offs between thermomechanical properties. In this contribution, we propose a hierarchical Monte Carlo tree search (MCTS)-guided Bayesian optimization (BO) framework to enable the simultaneous design of both the composition and curing protocols of epoxy resins as a major class of thermosetting polymers. A sigmoid-based weighting strategy is introduced to encode application-driven performance thresholds into the objective function, guiding the optimization toward coordinated multi-property improvement. With only 30 experiments across four iterative rounds, the framework optimizes both the formulation and curing protocols to yield a performance-enhanced epoxy resin that simultaneously meets all four target thresholds. This balanced performance cannot be achieved by any of the initial samples, an equal-weight baseline, or commercial and literature-reported systems. Furthermore, interpretable machine learning analysis combined with targeted experimental validation quantitatively resolves the relative importance of formulation and processing parameters, indicating that composition variables dominate overall property trends while their synergistic interactions produce non-linear effects on glass transition temperature. The findings demonstrate that the hierarchical MCTS-guided BO framework offers an efficient strategy for navigating complex formulation-processing spaces, and the interpretable analysis provides a quantitative basis for understanding structure–property relationships in thermosetting polymers.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"10 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250810","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}
Jingkun Gu,Haojie Han,Zihao Zheng,Tianyi Liu,Zongqi Xu,Jinming Guo,Jing Ma
SrTiO3 (STO), a typical quantum paraelectric material, has been extensively investigated for the stabilization of ferroelectric order through external perturbations. However, conventional approaches typically rely on epitaxial strain or external field excitation, limiting their suitability for epitaxial-strain-free and low-stress device architectures. Here, we demonstrate an epitaxial-strain-independent route to robust ferroelectricity in STO enabled by interfacial oxygen-vacancy engineering. By introducing a La0.5Sr0.5MnO3 (LSMO) bottom electrode with strong oxygen affinity, interfacial oxygen redistribution is promoted during epitaxial growth, resulting in significant oxygen-vacancy accumulation in the adjacent STO layer. The engineered oxygen vacancies drive local symmetry breaking and stabilize polar nanoregions in fully relaxed STO epitaxial films. Consequently, STO grown on the LSMO buffer layer exhibits robust room-temperature ferroelectricity with a remanent polarization of 14 μC/cm2, achieved without conventional epitaxial strain engineering. These findings establish interfacial oxygen-vacancy engineering as a viable strategy for inducing ferroelectricity in STO-based heterostructures and provide a possible route for designing emergent functionalities.
{"title":"Oxygen-Vacancy-Engineered Robust Ferroelectricity in Epitaxial-Strain-Free SrTiO3 Films","authors":"Jingkun Gu,Haojie Han,Zihao Zheng,Tianyi Liu,Zongqi Xu,Jinming Guo,Jing Ma","doi":"10.1021/acsami.6c12589","DOIUrl":"https://doi.org/10.1021/acsami.6c12589","url":null,"abstract":"SrTiO3 (STO), a typical quantum paraelectric material, has been extensively investigated for the stabilization of ferroelectric order through external perturbations. However, conventional approaches typically rely on epitaxial strain or external field excitation, limiting their suitability for epitaxial-strain-free and low-stress device architectures. Here, we demonstrate an epitaxial-strain-independent route to robust ferroelectricity in STO enabled by interfacial oxygen-vacancy engineering. By introducing a La0.5Sr0.5MnO3 (LSMO) bottom electrode with strong oxygen affinity, interfacial oxygen redistribution is promoted during epitaxial growth, resulting in significant oxygen-vacancy accumulation in the adjacent STO layer. The engineered oxygen vacancies drive local symmetry breaking and stabilize polar nanoregions in fully relaxed STO epitaxial films. Consequently, STO grown on the LSMO buffer layer exhibits robust room-temperature ferroelectricity with a remanent polarization of 14 μC/cm2, achieved without conventional epitaxial strain engineering. These findings establish interfacial oxygen-vacancy engineering as a viable strategy for inducing ferroelectricity in STO-based heterostructures and provide a possible route for designing emergent functionalities.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"13 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248548","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}
Controlling the flow of electricity in metallic circuits with light is a key goal for future optoelectronics. In this work, we demonstrate all-optical generation and directional control of non-thermal drift photocurrents driven by the transfer of spin optical angular momentum to the electron gas of a plasmonic gold wire. We attribute this phenomenon to the Inverse Faraday Effect and show that the current's direction can be precisely reversed at a subwavelength scale by tailoring the incident light's polarization or laser beam position. A bespoke polarization modulation technique is employed to unambiguously separate ultrafast drift currents from the ubiquitous photothermal background. We further reveal a collaborative mechanism where macroscopic thermal gradients, acting as a driving force, are used to extract and remotely detect the locally-generated nanoscale photocurrents. This robust control and detection scheme paves the way for reconfigurable, all-optical nanocircuitry capable of ultrafast on-chip processing.
{"title":"Directional Control of Nonthermal Photocurrents Driven by Optical Spin Angular Momentum","authors":"Roméo Zapata,Diana Singh,Obren Markovic,Chantal Hareau,Xingyu Yang,Ye Mou,Bruno Gallas,Maria Sanz-Paz,Gérard Colas-des-Francs,Alexandre Bouhelier,Mathieu Mivelle","doi":"10.1021/acsami.6c07175","DOIUrl":"https://doi.org/10.1021/acsami.6c07175","url":null,"abstract":"Controlling the flow of electricity in metallic circuits with light is a key goal for future optoelectronics. In this work, we demonstrate all-optical generation and directional control of non-thermal drift photocurrents driven by the transfer of spin optical angular momentum to the electron gas of a plasmonic gold wire. We attribute this phenomenon to the Inverse Faraday Effect and show that the current's direction can be precisely reversed at a subwavelength scale by tailoring the incident light's polarization or laser beam position. A bespoke polarization modulation technique is employed to unambiguously separate ultrafast drift currents from the ubiquitous photothermal background. We further reveal a collaborative mechanism where macroscopic thermal gradients, acting as a driving force, are used to extract and remotely detect the locally-generated nanoscale photocurrents. This robust control and detection scheme paves the way for reconfigurable, all-optical nanocircuitry capable of ultrafast on-chip processing.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"1 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250917","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}
Metal-organic terephthalates composed of earth-abundant elements are promising low-cost and structurally tuneable anodes for sodium-ion batteries, yet their electrochemical behavior, particularly in newly developed compounds, remains insufficiently understood. We report monoclinic nanocrystalline ZnC8H4O4 (ZnTP-2), prepared through the controlled thermal transformation of a hydrated zinc terephthalate precursor, ZnC8H6O5 (ZnTP-1), containing residual terephthalic acid (ZnTP-1@TPA). This transformation involves TPA sublimation and framework dehydration, producing ZnTP-2 with fine crystals of approximately 50–150 nm, increased surface area, and a higher concentration of oxygen-related defect sites compared with ZnTP-1@TPA. ZnTP-2 delivers a reversible Na-ion storage capacity of 222.7 mAh g–1 after 80 cycles at 50 mA g–1, approaching its theoretical capacity and indicating highly efficient utilization of the terephthalate redox framework. It also retains 110 mAh g–1 after 500 cycles at 1000 mA g–1, with a relatively low charge-transfer resistance of 11.5 Ω, demonstrating improved electrochemical stability and rate performance compared with conventional metal-organic terephthalate anodes. Electrochemical kinetic analyses reveal Na-ion diffusion coefficients between 10–14 and 10–12 cm2 s–1, with the differences discussed in terms of apparent, Warburg-related and bulk/chemical diffusion processes. UV–vis analysis reveals a lower optical band gap for ZnTP-2 (2.74 eV) than for ZnTP-1@TPA (3.36 eV), with DFT calculations on idealized molecular models of hydrated and dehydrated zinc terephthalates supporting a similar trend. Full-cell examination provides proof of concept for its applicability.
金属-有机对苯二甲酸盐是一种很有前途的低成本、结构可调的钠离子电池阳极，但其电化学行为，特别是在新开发的化合物中，仍未得到充分的了解。我们报道了单斜纳米晶ZnC8H4O4 (ZnTP-2)，通过水合对苯二甲酸锌前驱体ZnC8H6O5 （ZnTP-1）的受控热转化制备，含有残留的对苯二甲酸（ZnTP-1@TPA）。这种转变包括TPA升华和框架脱水，产生的ZnTP-2具有约50-150 nm的细晶，比ZnTP-1@TPA表面积增加，氧相关缺陷位点浓度更高。ZnTP-2在50 mA g-1下循环80次后可提供222.7 mAh g-1的可逆钠离子存储容量，接近其理论容量，表明对苯二甲酸盐氧化还原框架的高效利用。在1000 mA g-1下循环500次后，它还能保持110 mAh g-1，电荷转移电阻相对较低，为11.5 Ω，与传统的金属有机对苯二甲酸盐阳极相比，显示出更好的电化学稳定性和速率性能。电化学动力学分析表明，na离子扩散系数在10-14和10-12 cm2 s-1之间，并从表观扩散、warburg相关扩散和体/化学扩散过程中讨论了差异。UV-vis分析显示ZnTP-2的光学带隙（2.74 eV）比ZnTP-1@TPA （3.36 eV）低，水合和脱水对苯二甲酸锌的理想分子模型的DFT计算也支持类似的趋势。全细胞检查为其适用性提供了概念证明。
{"title":"Thermally Transformed ZnC8H4O4 Nanocrystals for Enhanced Sodium-Ion Storage","authors":"Yunan Liu,Ali Reza Kamali","doi":"10.1021/acsami.6c16944","DOIUrl":"https://doi.org/10.1021/acsami.6c16944","url":null,"abstract":"Metal-organic terephthalates composed of earth-abundant elements are promising low-cost and structurally tuneable anodes for sodium-ion batteries, yet their electrochemical behavior, particularly in newly developed compounds, remains insufficiently understood. We report monoclinic nanocrystalline ZnC8H4O4 (ZnTP-2), prepared through the controlled thermal transformation of a hydrated zinc terephthalate precursor, ZnC8H6O5 (ZnTP-1), containing residual terephthalic acid (ZnTP-1@TPA). This transformation involves TPA sublimation and framework dehydration, producing ZnTP-2 with fine crystals of approximately 50–150 nm, increased surface area, and a higher concentration of oxygen-related defect sites compared with ZnTP-1@TPA. ZnTP-2 delivers a reversible Na-ion storage capacity of 222.7 mAh g–1 after 80 cycles at 50 mA g–1, approaching its theoretical capacity and indicating highly efficient utilization of the terephthalate redox framework. It also retains 110 mAh g–1 after 500 cycles at 1000 mA g–1, with a relatively low charge-transfer resistance of 11.5 Ω, demonstrating improved electrochemical stability and rate performance compared with conventional metal-organic terephthalate anodes. Electrochemical kinetic analyses reveal Na-ion diffusion coefficients between 10–14 and 10–12 cm2 s–1, with the differences discussed in terms of apparent, Warburg-related and bulk/chemical diffusion processes. UV–vis analysis reveals a lower optical band gap for ZnTP-2 (2.74 eV) than for ZnTP-1@TPA (3.36 eV), with DFT calculations on idealized molecular models of hydrated and dehydrated zinc terephthalates supporting a similar trend. Full-cell examination provides proof of concept for its applicability.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"79 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248542","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}
Akhtar Gul,Kshitij Sharma,Nihad Ahmadli,Jirameth Tarnsangpradit,Rongguan Yin,Masiuddin M. Mohammed,Michael R. Bockstaller,Krzysztof Matyjaszewski,Jack F. Douglas,Alamgir Karim
While polymer-grafted nanoparticle (PGNP) mixtures having brush layers with different chemistry undergo phase separation as in ordinary homopolymer blends, knowledge of the underlying phase behavior of such “hybrid” blends currently does not exist theoretically or even empirically. Entropic effects in PGNPs arising from the chain-end tethering constraints of the brush layers reduce the number of configurational states of the polymer segments, compared to their corresponding free chain homopolymer blend, greatly reducing the gain in entropic free energy of mixing (–TΔSmix). However, the enthalpic driving force for phase separation for χ(Τ) > 0, ΔHmix ∼ χ(Τ), is also lowered by reduced unfavorable segmental brush/brush physical contacts, a situation that makes estimation of the overall free energy of mixing, ΔG = ΔHmix – TΔSmix, difficult. The phase stability of miscible polymer blends is normally dominated by a large enthalpic (relative to entropic) contribution to ΔG, so that observations of competitive entropy/enthalpy effects on blend phase behavior are limited to systems having relatively small ΔHmix, i.e., 0 < χ(Τ) Ν < 2. With this general thermodynamic relationship in view, we designed a binary PGNP blend system comprising end-grafted polymer brush layers on silica nanoparticles having nearly balanced entropic/enthalpic interactions. Specifically, we synthesized poly(methyl methacrylate-silica) (PMMA-SiO2) and poly(styrene-acrylonitrile (AN-14%)-silica (PSAN-SiO2) PGNPs and cast blend films that exhibited a reversible and compositionally tunable U-shaped lower critical solution temperature (LCST) phase behavior. In contrast, the corresponding free chain PMMA/PSAN homopolymer blend films under the same conditions were fully miscible. As in a phase-separating homopolymer blend, phase separation in the PGNP blend film leads to spontaneous (spinodal) surface pattern formation, wherein the ratio of the in-plane to out-of-plane phase separation scale, λ/h, is constant. Furthermore, a shift in miscibility based on an asymmetry in the grafted chain length ratio of PGNPs can be compensated by an equivalent asymmetry in the PGNP blend ratio. Practical properties relevant to colloidal paints and coatings, including gloss (sheen) and dielectric breakdown strength (EBD) for capacitive energy storage, are measured. Single-phase PGNPs show high gloss (sheen) and high EBD, while the phase-separated PGNP blend films have low gloss and low EBD, effects that could be exploited for the design of numerous optical and flexible solid-state electrical power devices.
{"title":"Entropy-Driven Phase Transition in Polymer-Grafted Nanoparticle Blend Films and Associated Gloss and Dielectric Breakdown Strength","authors":"Akhtar Gul,Kshitij Sharma,Nihad Ahmadli,Jirameth Tarnsangpradit,Rongguan Yin,Masiuddin M. Mohammed,Michael R. Bockstaller,Krzysztof Matyjaszewski,Jack F. Douglas,Alamgir Karim","doi":"10.1021/acsami.6c13966","DOIUrl":"https://doi.org/10.1021/acsami.6c13966","url":null,"abstract":"While polymer-grafted nanoparticle (PGNP) mixtures having brush layers with different chemistry undergo phase separation as in ordinary homopolymer blends, knowledge of the underlying phase behavior of such “hybrid” blends currently does not exist theoretically or even empirically. Entropic effects in PGNPs arising from the chain-end tethering constraints of the brush layers reduce the number of configurational states of the polymer segments, compared to their corresponding free chain homopolymer blend, greatly reducing the gain in entropic free energy of mixing (–TΔSmix). However, the enthalpic driving force for phase separation for χ(Τ) > 0, ΔHmix ∼ χ(Τ), is also lowered by reduced unfavorable segmental brush/brush physical contacts, a situation that makes estimation of the overall free energy of mixing, ΔG = ΔHmix – TΔSmix, difficult. The phase stability of miscible polymer blends is normally dominated by a large enthalpic (relative to entropic) contribution to ΔG, so that observations of competitive entropy/enthalpy effects on blend phase behavior are limited to systems having relatively small ΔHmix, i.e., 0 < χ(Τ) Ν < 2. With this general thermodynamic relationship in view, we designed a binary PGNP blend system comprising end-grafted polymer brush layers on silica nanoparticles having nearly balanced entropic/enthalpic interactions. Specifically, we synthesized poly(methyl methacrylate-silica) (PMMA-SiO2) and poly(styrene-acrylonitrile (AN-14%)-silica (PSAN-SiO2) PGNPs and cast blend films that exhibited a reversible and compositionally tunable U-shaped lower critical solution temperature (LCST) phase behavior. In contrast, the corresponding free chain PMMA/PSAN homopolymer blend films under the same conditions were fully miscible. As in a phase-separating homopolymer blend, phase separation in the PGNP blend film leads to spontaneous (spinodal) surface pattern formation, wherein the ratio of the in-plane to out-of-plane phase separation scale, λ/h, is constant. Furthermore, a shift in miscibility based on an asymmetry in the grafted chain length ratio of PGNPs can be compensated by an equivalent asymmetry in the PGNP blend ratio. Practical properties relevant to colloidal paints and coatings, including gloss (sheen) and dielectric breakdown strength (EBD) for capacitive energy storage, are measured. Single-phase PGNPs show high gloss (sheen) and high EBD, while the phase-separated PGNP blend films have low gloss and low EBD, effects that could be exploited for the design of numerous optical and flexible solid-state electrical power devices.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"90 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149269123","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}
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