Xiaojing Yu, Zeyu Ren, Yuyang Wu, Taisen Yan, Andrei A. Eliseev, Li-Zhi Zhang
Hydrogel-based evaporative cooling has emerged as a promising passive strategy for thermal management in photovoltaic (PV) systems. However, conventional bulk hydrogels suffer from severe structural deformation and limited water storage capacity, hindering their long-term performance in practical applications. Herein, we developed a polyacrylamide microparticle-assembled hydrogel (MPH) formed through the self-assembly of dehydrated microparticles triggered by water absorption. The as-reconstructed hydrogels establish dynamic interparticle interfaces via physical entanglements, facilitating rapid polymer chain mobility and local structural reorganization during hydration and dehydration. The flexible structure of the MPH mitigates drying-induced stress and reduces undesirable inhomogeneous deformation, ensuring sustained thermal contact between the hydrogel and the PV panel throughout evaporation. Meanwhile, the dynamic network enhances water molecule mobility and improves the water absorption capacity. Leveraging the fast water uptake of the MPH, we engineered a water-fed cooling system integrating a capillary-driven layer for a continuous water supply. The system achieved a significant temperature drop of 26 °C under an intense heat flux of 1000 W/m2 and demonstrated sustained cooling performance compared to natural convection. This work presents a novel material strategy for efficient and durable thermal management in solar energy applications.
{"title":"Polyacrylamide Microparticles-Assembled Hydrogel with Mitigated Inhomogeneous Deformation for Efficient Photovoltaic Cooling","authors":"Xiaojing Yu, Zeyu Ren, Yuyang Wu, Taisen Yan, Andrei A. Eliseev, Li-Zhi Zhang","doi":"10.1021/acsami.5c17512","DOIUrl":"https://doi.org/10.1021/acsami.5c17512","url":null,"abstract":"Hydrogel-based evaporative cooling has emerged as a promising passive strategy for thermal management in photovoltaic (PV) systems. However, conventional bulk hydrogels suffer from severe structural deformation and limited water storage capacity, hindering their long-term performance in practical applications. Herein, we developed a polyacrylamide microparticle-assembled hydrogel (MPH) formed through the self-assembly of dehydrated microparticles triggered by water absorption. The as-reconstructed hydrogels establish dynamic interparticle interfaces via physical entanglements, facilitating rapid polymer chain mobility and local structural reorganization during hydration and dehydration. The flexible structure of the MPH mitigates drying-induced stress and reduces undesirable inhomogeneous deformation, ensuring sustained thermal contact between the hydrogel and the PV panel throughout evaporation. Meanwhile, the dynamic network enhances water molecule mobility and improves the water absorption capacity. Leveraging the fast water uptake of the MPH, we engineered a water-fed cooling system integrating a capillary-driven layer for a continuous water supply. The system achieved a significant temperature drop of 26 °C under an intense heat flux of 1000 W/m<sup>2</sup> and demonstrated sustained cooling performance compared to natural convection. This work presents a novel material strategy for efficient and durable thermal management in solar energy applications.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"33 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729215","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}
Developing advanced halide solid-state electrolytes (SSEs) with both high ionic conductivity and high-voltage stability is crucial for high-energy all-solid-state batteries (ASSBs). However, conventional strategies such as simple cation substitution or anion engineering for achieving these properties simultaneously often require compromising one for the other. Herein, a high-entropy strategy is employed to design and synthesize Li3–4xIn1–6xFexYxZr2xHf2xCl6 (0 ≤ x ≤ 0.05) through multication substitution in Li3InCl6 (LIC). Li2.92In0.88Fe0.02Y0.02Zr0.04Hf0.04Cl6 (HE-LIC) featuring moderate lattice distortion achieves the highest ionic conductivity of 1.136 mS cm–1 at 25 °C and improved high-voltage stability. Based on theoretical calculations and experimental findings, the tailored distortion elongates Li1–Cl bonds (2.6616 vs 2.6531 Å in LIC) to facilitate Li+ conduction, while confining Cl– distribution to inhibit oxidation. ASSBs with HE-LIC and LiCoO2 cathode deliver a discharge capacity of 151.13 mAh g–1 and 81.17% capacity retention after 100 cycles at 0.5 C under 4.5 V. Even at 4.6 V, a discharge capacity of 165.98 mAh g–1 with 80.63% retention after 50 cycles at 0.5 C is achieved. These findings demonstrate the potential of high-entropy-driven moderate lattice distortion for advanced SSEs in high-voltage ASSBs.
开发具有高离子电导率和高电压稳定性的先进卤化物固态电解质对于高能全固态电池（assb）至关重要。然而，传统的策略，如简单的阳离子取代或阴离子工程，以同时实现这些性质往往需要牺牲一个为另一个。本文采用高熵策略设计合成Li3-4xIn1-6xFexYxZr2xHf2xCl6（0≤x≤0.05）。具有中等晶格畸变的Li2.92In0.88Fe0.02Y0.02Zr0.04Hf0.04Cl6 （HE-LIC）在25℃时离子电导率最高，为1.136 mS cm-1，提高了高压稳定性。基于理论计算和实验结果，量身定制的畸变延长了Li1-Cl键（在LIC中为2.6616 vs 2.6531 Å），促进了Li+的传导，同时限制了Cl -的分布以抑制氧化。采用HE-LIC和LiCoO2阴极的assb在4.5 V、0.5 C、100次循环后的放电容量为151.13 mAh g-1，容量保持率为81.17%。即使在4.6 V下，放电容量为165.98 mAh g-1, 0.5 C下50次循环后保持率为80.63%。这些发现证明了高熵驱动的中等晶格畸变在高压assb中用于高级ssi的潜力。
{"title":"High-Entropy-Driven Moderate Lattice Distortion Improves Ionic Conductivity and High-Voltage Stability of Halide Solid-State Electrolytes","authors":"Qian Zhao, Weizong Wang, Cheng Ruan, Zhengping Ding, Peng Wei, Xiangqun Zhuge, Yurong Ren","doi":"10.1021/acsami.5c19063","DOIUrl":"https://doi.org/10.1021/acsami.5c19063","url":null,"abstract":"Developing advanced halide solid-state electrolytes (SSEs) with both high ionic conductivity and high-voltage stability is crucial for high-energy all-solid-state batteries (ASSBs). However, conventional strategies such as simple cation substitution or anion engineering for achieving these properties simultaneously often require compromising one for the other. Herein, a high-entropy strategy is employed to design and synthesize Li<sub>3–4<i>x</i></sub>In<sub>1–6<i>x</i></sub>Fe<sub><i>x</i></sub>Y<sub><i>x</i></sub>Zr<sub>2<i>x</i></sub>Hf<sub>2<i>x</i></sub>Cl<sub>6</sub> (0 ≤ <i>x</i> ≤ 0.05) through multication substitution in Li<sub>3</sub>InCl<sub>6</sub> (LIC). Li<sub>2.92</sub>In<sub>0.88</sub>Fe<sub>0.02</sub>Y<sub>0.02</sub>Zr<sub>0.04</sub>Hf<sub>0.04</sub>Cl<sub>6</sub> (HE-LIC) featuring moderate lattice distortion achieves the highest ionic conductivity of 1.136 mS cm<sup>–1</sup> at 25 °C and improved high-voltage stability. Based on theoretical calculations and experimental findings, the tailored distortion elongates Li1–Cl bonds (2.6616 vs 2.6531 Å in LIC) to facilitate Li<sup>+</sup> conduction, while confining Cl<sup>–</sup> distribution to inhibit oxidation. ASSBs with HE-LIC and LiCoO<sub>2</sub> cathode deliver a discharge capacity of 151.13 mAh g<sup>–1</sup> and 81.17% capacity retention after 100 cycles at 0.5 C under 4.5 V. Even at 4.6 V, a discharge capacity of 165.98 mAh g<sup>–1</sup> with 80.63% retention after 50 cycles at 0.5 C is achieved. These findings demonstrate the potential of high-entropy-driven moderate lattice distortion for advanced SSEs in high-voltage ASSBs.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"29 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732090","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}
Andrea Mantovani, Annagioia Mastrolorenzo, Edoardo Marchini, Paola Manini, Mirco Natali
Dye-sensitized photoelectrochemical cells (DSPECs) are currently at the forefront of solar-to-chemical energy conversion technologies. Although water oxidation to dioxygen has long been the preferred reaction at the photoanodic compartment, recent research has increasingly focused on oxidation processes for the synthesis of value-added organic compounds. Quite surprisingly, within this framework, cyclometalated iridium(III) complexes have received negligible attention as photoactive components in DSPEC photoanodes, in spite of their intriguing photophysical and electrochemical properties. With the aim of filling this gap, this work explores the application of two iridium(III) complexes (Ir1 and Ir2), differing in the presence of fluorinated substituents, as light-harvesting sensitizers anchored onto mesoporous TiO2 photoelectrodes. These systems were employed to drive two relevant oxidation processes: the TEMPO-mediated oxidation of benzyl alcohol (BzOH) to benzaldehyde and the radical cation Diels-Alder reaction between trans-anethole (TA) and isoprene (ISO). In the oxidation of BzOH to benzaldehyde, maximum photocurrent densities on the order of 0.5-0.7 mA·cm-2 were recorded, but the photoelectrodes proved substantially inefficient (APCE between 2.2% and 2.4%). Under operative conditions, low Faradaic efficiencies (FEs) for benzaldehyde formation were also registered (42% and 32% for Ir1 and Ir2, respectively), associated with a rapid decrease in photocurrent densities, particularly in the case of the fluorinated complex. In contrast, the DSPEC system operating without a redox mediator exhibits markedly improved performances (photocurrent densities on the order of 0.7 mA·cm-2, APCE up to 19%), with quantitative conversion of the TA substrate under bulk electrolysis conditions. Interestingly, for this latter reaction, the enhanced oxidative power of the fluorinated sensitizer contributes to the increased reactivity. A combination of photoelectrochemical and transient absorption spectroscopy studies has been performed to rationalize the observed behavior. The results highlight how the molecular design and electronic properties of the dye component in DSPECs should be rationally engineered to align with the thermodynamic and kinetic requirements of the targeted chemical transformation.
{"title":"Exploring the Boundaries of Cyclometalated Iridium(III) Sensitizers in Photoelectrochemical Organic Transformations.","authors":"Andrea Mantovani, Annagioia Mastrolorenzo, Edoardo Marchini, Paola Manini, Mirco Natali","doi":"10.1021/acsami.5c20212","DOIUrl":"https://doi.org/10.1021/acsami.5c20212","url":null,"abstract":"<p><p>Dye-sensitized photoelectrochemical cells (DSPECs) are currently at the forefront of solar-to-chemical energy conversion technologies. Although water oxidation to dioxygen has long been the preferred reaction at the photoanodic compartment, recent research has increasingly focused on oxidation processes for the synthesis of value-added organic compounds. Quite surprisingly, within this framework, cyclometalated iridium(III) complexes have received negligible attention as photoactive components in DSPEC photoanodes, in spite of their intriguing photophysical and electrochemical properties. With the aim of filling this gap, this work explores the application of two iridium(III) complexes (<b>Ir1</b> and <b>Ir2</b>), differing in the presence of fluorinated substituents, as light-harvesting sensitizers anchored onto mesoporous TiO<sub>2</sub> photoelectrodes. These systems were employed to drive two relevant oxidation processes: the TEMPO-mediated oxidation of benzyl alcohol (BzOH) to benzaldehyde and the radical cation Diels-Alder reaction between <i>trans</i>-anethole (TA) and isoprene (ISO). In the oxidation of BzOH to benzaldehyde, maximum photocurrent densities on the order of 0.5-0.7 mA·cm<sup>-2</sup> were recorded, but the photoelectrodes proved substantially inefficient (APCE between 2.2% and 2.4%). Under operative conditions, low Faradaic efficiencies (FEs) for benzaldehyde formation were also registered (42% and 32% for <b>Ir1</b> and <b>Ir2</b>, respectively), associated with a rapid decrease in photocurrent densities, particularly in the case of the fluorinated complex. In contrast, the DSPEC system operating without a redox mediator exhibits markedly improved performances (photocurrent densities on the order of 0.7 mA·cm<sup>-2</sup>, APCE up to 19%), with quantitative conversion of the TA substrate under bulk electrolysis conditions. Interestingly, for this latter reaction, the enhanced oxidative power of the fluorinated sensitizer contributes to the increased reactivity. A combination of photoelectrochemical and transient absorption spectroscopy studies has been performed to rationalize the observed behavior. The results highlight how the molecular design and electronic properties of the dye component in DSPECs should be rationally engineered to align with the thermodynamic and kinetic requirements of the targeted chemical transformation.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145740029","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}
Rafael R M Madrid,Angelina Angelova,Borislav Angelov,Gouranga Manna,Patrick D Mathews,Omar Mertins
Designing advanced functional materials capable of passing through complex biological environments requires a deep understanding of their dynamic structural behavior in situ. We investigate pH-responsive core-shell cubosomes for oral drug delivery applications. These nanoparticles comprise a lipid-based core of cubic Im3m liquid crystalline structure and are coated with a chitosan-N-arginine/alginate polyelectrolyte shell (PS). The cubosomes encapsulate varying concentrations (0-30% w/w) of Aloe vera-derived acemannan, an immunomodulatory macromolecular drug. Utilizing synchrotron small-angle X-ray scattering and cryogenic transmission electron microscopy, we performed an advanced spatiotemporal analysis, which focused on their nanoscale structural evolution under simulated gastric (pH 2.5) and intestinal (pH 7.4) conditions. The interactions with key individual gastrointestinal components, including mucins, pepsin, bile salts, and pancreatin, were systematically examined. Our results demonstrate that acemannan incorporation and environmental pH significantly modulate cubosome structure and heterogeneity (phase coexistence) during disassembly. The pH-responsive polyelectrolyte shell imparts notable structural stability against pepsin and mucins at pH 2.5, ensuring functional gastric protection. However, under intestinal conditions (pH 7.4), bile salt-mediated solubilization caused complete disassembly. Pancreatic lipase-induced digestion triggered a remarkable time-dependent phase transition from a cubic (Im3m) to an inverted hexagonal (HII) topology in PS-cubosomes containing 30% acemannan. A simulated duodenum mixture induced lamellar phases at pH 2.5 for acemannan-loaded systems but led to complete disassembly at pH 7.4, primarily driven by bile salts. Deconvoluting these structural responses over time provides crucial insights into their mechanistic nature. It clarifies pH-dependent stability and component-specific disassembly pathways. The achieved understanding is crucial for designing advanced stimuli-responsive lipid/biopolymer nanomaterials that facilitate efficient oral delivery.
{"title":"Dynamic Self-Assembly and Stimuli-Responsive Disassembly of Bioactive-Loaded Cubosomes in Biomimetic Media Traced by Real-Time Small-Angle X-ray Scattering and Cryogenic Transmission Electron Microscopy.","authors":"Rafael R M Madrid,Angelina Angelova,Borislav Angelov,Gouranga Manna,Patrick D Mathews,Omar Mertins","doi":"10.1021/acsami.5c18735","DOIUrl":"https://doi.org/10.1021/acsami.5c18735","url":null,"abstract":"Designing advanced functional materials capable of passing through complex biological environments requires a deep understanding of their dynamic structural behavior in situ. We investigate pH-responsive core-shell cubosomes for oral drug delivery applications. These nanoparticles comprise a lipid-based core of cubic Im3m liquid crystalline structure and are coated with a chitosan-N-arginine/alginate polyelectrolyte shell (PS). The cubosomes encapsulate varying concentrations (0-30% w/w) of Aloe vera-derived acemannan, an immunomodulatory macromolecular drug. Utilizing synchrotron small-angle X-ray scattering and cryogenic transmission electron microscopy, we performed an advanced spatiotemporal analysis, which focused on their nanoscale structural evolution under simulated gastric (pH 2.5) and intestinal (pH 7.4) conditions. The interactions with key individual gastrointestinal components, including mucins, pepsin, bile salts, and pancreatin, were systematically examined. Our results demonstrate that acemannan incorporation and environmental pH significantly modulate cubosome structure and heterogeneity (phase coexistence) during disassembly. The pH-responsive polyelectrolyte shell imparts notable structural stability against pepsin and mucins at pH 2.5, ensuring functional gastric protection. However, under intestinal conditions (pH 7.4), bile salt-mediated solubilization caused complete disassembly. Pancreatic lipase-induced digestion triggered a remarkable time-dependent phase transition from a cubic (Im3m) to an inverted hexagonal (HII) topology in PS-cubosomes containing 30% acemannan. A simulated duodenum mixture induced lamellar phases at pH 2.5 for acemannan-loaded systems but led to complete disassembly at pH 7.4, primarily driven by bile salts. Deconvoluting these structural responses over time provides crucial insights into their mechanistic nature. It clarifies pH-dependent stability and component-specific disassembly pathways. The achieved understanding is crucial for designing advanced stimuli-responsive lipid/biopolymer nanomaterials that facilitate efficient oral delivery.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"7 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728629","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}
Changqing Shen, Yunxia Zhou, Xiong Li, Yang Liu, Renyan Zhang, Xiangang Luo
Molybdenum disulfide (MoS2) monolayers are promising candidates for next-generation nanoelectronics, yet ultraviolet (UV) irradiation during device fabrication induces surface defects that compromise device reliability. This study systematically investigates the wavelength-dependent effects of 365 nm (UV-365) and 193 nm (UV-193) irradiation on the strain and doping characteristics of chemical vapor deposition (CVD)-grown monolayer MoS2. Raman spectroscopy analysis reveals that UV-365 irradiation (1000–3000 mJ) consistently induces ∼0.1% tensile strain with minimal variation in doping levels (Δn ∼ −1 × 1012 cm–2). In contrast, UV-193 irradiation at identical energies generates compressive strain (∼0.2–0.3%) and pronounced p-type doping, with carrier density reaching Δn ∼ −3.5 × 1012 cm–2 at 3000 mJ. X-ray photoelectron spectroscopy (XPS) elucidates distinct mechanisms: UV-365 promotes oxygen adsorption via photothermal effects, inducing tensile strain and weak p-type doping, and UV-193 (photon energy > Mo–S bond energy) cleaves Mo–S bonds, enabling oxygen passivation of sulfur vacancies to form MoO3. This process causes lattice compression (compressive strain) and enhances p-type doping through defect-mediated charge transfer. These findings underscore that UV-193 irradiation significantly alters critical electrical parameters (strain and doping), whereas UV-365 irradiation primarily modulates the strain. Mitigating such wavelength-specific surface modifications is essential for enhancing the reliability of wafer-scale MoS2 field-effect transistors.
{"title":"Effect of Ultraviolet Irradiation on Surface Doping and Strain Properties of Chemical Vapor Deposition-Grown MoS2","authors":"Changqing Shen, Yunxia Zhou, Xiong Li, Yang Liu, Renyan Zhang, Xiangang Luo","doi":"10.1021/acsami.5c17137","DOIUrl":"https://doi.org/10.1021/acsami.5c17137","url":null,"abstract":"Molybdenum disulfide (MoS<sub>2</sub>) monolayers are promising candidates for next-generation nanoelectronics, yet ultraviolet (UV) irradiation during device fabrication induces surface defects that compromise device reliability. This study systematically investigates the wavelength-dependent effects of 365 nm (UV-365) and 193 nm (UV-193) irradiation on the strain and doping characteristics of chemical vapor deposition (CVD)-grown monolayer MoS<sub>2</sub>. Raman spectroscopy analysis reveals that UV-365 irradiation (1000–3000 mJ) consistently induces ∼0.1% tensile strain with minimal variation in doping levels (Δ<i>n</i> ∼ −1 × 10<sup>12</sup> cm<sup>–2</sup>). In contrast, UV-193 irradiation at identical energies generates compressive strain (∼0.2–0.3%) and pronounced p-type doping, with carrier density reaching Δ<i>n</i> ∼ −3.5 × 10<sup>12</sup> cm<sup>–2</sup> at 3000 mJ. X-ray photoelectron spectroscopy (XPS) elucidates distinct mechanisms: UV-365 promotes oxygen adsorption via photothermal effects, inducing tensile strain and weak p-type doping, and UV-193 (photon energy > Mo–S bond energy) cleaves Mo–S bonds, enabling oxygen passivation of sulfur vacancies to form MoO<sub>3</sub>. This process causes lattice compression (compressive strain) and enhances p-type doping through defect-mediated charge transfer. These findings underscore that UV-193 irradiation significantly alters critical electrical parameters (strain and doping), whereas UV-365 irradiation primarily modulates the strain. Mitigating such wavelength-specific surface modifications is essential for enhancing the reliability of wafer-scale MoS<sub>2</sub> field-effect transistors.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"34 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732089","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}
Jiale Zhao, Xuyang Jian, Ning Sun, Razium Ali Soomro, Huan Li, Bin Xu
Pitch stands out as a promising carbon precursor owing to its abundance, cost-effectiveness, and high carbon content. However, raw pitch-derived carbon generally shows typical characteristics of soft carbon, with a highly graphitized framework and narrow interlayer spacing that hamper Na-ion storage. Here, a novel cation/anion cointerference approach is introduced to steer both the microcrystalline order and closed-pore architecture of pitch-derived carbon with the assistance of zinc acetate, driving a controlled transformation from soft to hard carbon. Compared to pristine pitch pyrolytic carbon (PC), the optimal modified sample, with abundant closed pores and an increased pseudographitic phase, exhibits a significantly improved Na-storage capacity from 87.7 mAh g–1 to 262.6 mAh g–1, along with a remarkable initial Coulombic efficiency of 86.5%. When paired with a commercial O3–NaNi1/3Fe1/3Mn1/3O2 cathode, the assembled Na-ion full cell achieves a reversible capacity of 339.8 mAh g–1, and the energy density can reach 263.1 Wh kg–1 based on the mass of the cathode and anode, demonstrating the promising prospect of the fabricated pitch-derived carbons. This work offers a novel perspective on the synergistic mechanism of microcrystalline structure and closed pores for Na-ion storage, and opens new avenues for designing efficient carbon anodes for practical sodium-ion batteries.
沥青因其丰富，成本效益和高碳含量而成为一种有前途的碳前驱体。然而，原始沥青衍生碳通常表现出典型的软碳特征，具有高度石墨化的框架和狭窄的层间距，阻碍了na离子的储存。本研究引入了一种新的阳离子/阴离子共干扰方法，在醋酸锌的辅助下控制沥青衍生碳的微晶秩序和闭孔结构，从而驱动从软碳到硬碳的可控转变。与原始沥青热解碳（PC）相比，优化后的样品具有丰富的封闭孔隙和增加的假石墨相，其na存储容量从87.7 mAh g-1显著提高到262.6 mAh g-1，初始库仑效率达到86.5%。当与O3-NaNi1/3Fe1/3Mn1/3O2阴极配合使用时，组装的钠离子充满电池的可逆容量为339.8 mAh g-1，基于阴极和阳极的质量，能量密度可达到263.1 Wh kg-1，显示了制备的沥青衍生碳的良好前景。本研究为研究微晶结构和闭孔对钠离子存储的协同作用机制提供了新的视角，为设计实用钠离子电池的高效碳阳极开辟了新的途径。
{"title":"Cation/Anion Cointerference Strategy: Boosting the Na-Storage Performance of a Pitch-Derived Carbon Anode","authors":"Jiale Zhao, Xuyang Jian, Ning Sun, Razium Ali Soomro, Huan Li, Bin Xu","doi":"10.1021/acsami.5c18006","DOIUrl":"https://doi.org/10.1021/acsami.5c18006","url":null,"abstract":"Pitch stands out as a promising carbon precursor owing to its abundance, cost-effectiveness, and high carbon content. However, raw pitch-derived carbon generally shows typical characteristics of soft carbon, with a highly graphitized framework and narrow interlayer spacing that hamper Na-ion storage. Here, a novel cation/anion cointerference approach is introduced to steer both the microcrystalline order and closed-pore architecture of pitch-derived carbon with the assistance of zinc acetate, driving a controlled transformation from soft to hard carbon. Compared to pristine pitch pyrolytic carbon (PC), the optimal modified sample, with abundant closed pores and an increased pseudographitic phase, exhibits a significantly improved Na-storage capacity from 87.7 mAh g<sup>–1</sup> to 262.6 mAh g<sup>–1</sup>, along with a remarkable initial Coulombic efficiency of 86.5%. When paired with a commercial O3–NaNi<sub>1/3</sub>Fe<sub>1/3</sub>Mn<sub>1/3</sub>O<sub>2</sub> cathode, the assembled Na-ion full cell achieves a reversible capacity of 339.8 mAh g<sup>–1</sup>, and the energy density can reach 263.1 Wh kg<sup>–1</sup> based on the mass of the cathode and anode, demonstrating the promising prospect of the fabricated pitch-derived carbons. This work offers a novel perspective on the synergistic mechanism of microcrystalline structure and closed pores for Na-ion storage, and opens new avenues for designing efficient carbon anodes for practical sodium-ion batteries.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"147 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729217","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}
Qin-Ru Pu, Xi-Man He, Xiao-Dong Qi, Nan Zhang, Ting Huang, Yong Wang, Jing-Hui Yang
Passive daytime radiative cooling (PDRC) fabrics require no additional energy input and exhibit promising potential for outdoor cooling. Besides, multifunctional integration is urgently required for practical applications. Herein, a composite fabric based on poly(vinylidene fluoride) (PVDF) and UiO-66 was successfully prepared via combining electrospinning and in situ growth techniques. This composite fabric exhibits integrated functional properties, including passive cooling, respiratory monitoring, and smoke filtration. To achieve passive cooling dominated by radiative cooling, the prepared fibrous fabric is required to possess positive optical properties: a solar reflectance of 93.78% in the 0.3–2.5 μm infrared spectral range and an emissivity of 92.72% in the 8–13 μm mid-infrared band. The outdoor test is conducted in which the relative air humidity is 75% RH, the temperature ranges from 23 to 34 °C, the wind speed is 2.4–3.3 m/s, and the solar radiation measures 846 W m–2; the temperature of the composite fabrics exhibits 18.7 °C lower than ambient temperature. Upon fabrication into a cooling face mask, the fabrics achieve a 5.5 °C temperature reduction compared to a conventional nonwoven mask. In addition, in a hot and humid environment, the hydrophilic properties of UiO-66 enhance the fabric’s sweat absorption capacity and promote efficient evaporative cooling. Finally, the fabrics functionalized with UiO-66 particles successfully integrate the dual functions of smoke filtration and respiratory monitoring, meeting the diverse functional and practical needs of wearable fabrics.
被动式日间辐射冷却（PDRC）织物不需要额外的能量输入，在室外冷却方面表现出很好的潜力。此外，在实际应用中迫切需要多功能集成。本文通过静电纺丝和原位生长技术的结合，成功制备了聚偏氟乙烯（PVDF）和UiO-66复合织物。这种复合织物具有综合的功能特性，包括被动冷却、呼吸监测和烟雾过滤。为了实现以辐射冷却为主的被动冷却，所制备的纤维织物需要具有良好的光学性能：在0.3 ~ 2.5 μm红外光谱范围内的太阳反射率为93.78%，在8 ~ 13 μm中红外光谱范围内的发射率为92.72%。室外试验条件为：空气相对湿度75% RH，温度23 ~ 34℃，风速2.4 ~ 3.3 m/s，太阳辐射846 W m - 2；复合织物的温度比环境温度低18.7℃。在制作冷却口罩时，与传统的非织造口罩相比，织物的温度降低了5.5°C。此外，在湿热环境下，UiO-66的亲水性增强了织物的吸汗能力，促进了高效的蒸发冷却。最后，UiO-66颗粒功能化织物成功融合了烟雾过滤和呼吸监测双重功能，满足了可穿戴织物多样化的功能和实用需求。
{"title":"Multifunctional Face Mask with Daytime Passive Cooling Based on PVDF/Metal–Organic Framework Hybrid Fabric","authors":"Qin-Ru Pu, Xi-Man He, Xiao-Dong Qi, Nan Zhang, Ting Huang, Yong Wang, Jing-Hui Yang","doi":"10.1021/acsami.5c17573","DOIUrl":"https://doi.org/10.1021/acsami.5c17573","url":null,"abstract":"Passive daytime radiative cooling (PDRC) fabrics require no additional energy input and exhibit promising potential for outdoor cooling. Besides, multifunctional integration is urgently required for practical applications. Herein, a composite fabric based on poly(vinylidene fluoride) (PVDF) and UiO-66 was successfully prepared via combining electrospinning and in situ growth techniques. This composite fabric exhibits integrated functional properties, including passive cooling, respiratory monitoring, and smoke filtration. To achieve passive cooling dominated by radiative cooling, the prepared fibrous fabric is required to possess positive optical properties: a solar reflectance of 93.78% in the 0.3–2.5 μm infrared spectral range and an emissivity of 92.72% in the 8–13 μm mid-infrared band. The outdoor test is conducted in which the relative air humidity is 75% RH, the temperature ranges from 23 to 34 °C, the wind speed is 2.4–3.3 m/s, and the solar radiation measures 846 W m<sup>–2</sup>; the temperature of the composite fabrics exhibits 18.7 °C lower than ambient temperature. Upon fabrication into a cooling face mask, the fabrics achieve a 5.5 °C temperature reduction compared to a conventional nonwoven mask. In addition, in a hot and humid environment, the hydrophilic properties of UiO-66 enhance the fabric’s sweat absorption capacity and promote efficient evaporative cooling. Finally, the fabrics functionalized with UiO-66 particles successfully integrate the dual functions of smoke filtration and respiratory monitoring, meeting the diverse functional and practical needs of wearable fabrics.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"116 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729216","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}
Perovskite solar cells have undergone rapid improvement over the past decade, with their efficiency rivaling that of silicon-based solar cells. Nevertheless, the solvate-based phase transition leads to hardly controlled nucleation and thus inhomogeneous film formation. Herein, we propose a “host–guest–additive” ternary solvent strategy, aiming to regulate the processing window for photovoltaic perovskites. Our analysis shows that the optimized nucleation window is the most conducive factor for fabricating high-quality perovskite films. Furthermore, by the insertion of an additive, the degree of solvent–solute interaction can be tailored. The time window for nucleation of perovskite therefore is optimized, rendering improved surface flatness, uniformity, and grain sizes. Based on these findings, we fabricated solar cells, achieving a power conversion efficiency of 24.47%, a substantial improvement over the baseline performance of 22.31%. To further verify the availability of our strategy, we also made perovskite minimodules with an active area of 12.8 cm2, which also showed improved efficiency from 18.99% to 20.86%. The 3D microscope reveals improved uniformity of the resulting perovskite film across monitored large areas, indicating the application of our ternary strategy for scaling up photovoltaic perovskites. We believe the findings unearthed here provide critical insights for systematically exploring synergistic multicomponent solvent effects in film formation of perovskites.
{"title":"Regulating the Nucleation Kinetics of Photovoltaic Perovskites via a Ternary Solvent Strategy Renders Efficient Solar Cells and Modules","authors":"Jin Wang, Jun Lv, Weihui Bi, Hanzhi Zhang, Yu Zhang, Yingying Xu, Haijun Wang, Guangtong Hai, Mengyuan Li, Po-Chuan Yang, Zongbao Zhang, Yufei Zhong","doi":"10.1021/acsami.5c19210","DOIUrl":"https://doi.org/10.1021/acsami.5c19210","url":null,"abstract":"Perovskite solar cells have undergone rapid improvement over the past decade, with their efficiency rivaling that of silicon-based solar cells. Nevertheless, the solvate-based phase transition leads to hardly controlled nucleation and thus inhomogeneous film formation. Herein, we propose a “host–guest–additive” ternary solvent strategy, aiming to regulate the processing window for photovoltaic perovskites. Our analysis shows that the optimized nucleation window is the most conducive factor for fabricating high-quality perovskite films. Furthermore, by the insertion of an additive, the degree of solvent–solute interaction can be tailored. The time window for nucleation of perovskite therefore is optimized, rendering improved surface flatness, uniformity, and grain sizes. Based on these findings, we fabricated solar cells, achieving a power conversion efficiency of 24.47%, a substantial improvement over the baseline performance of 22.31%. To further verify the availability of our strategy, we also made perovskite minimodules with an active area of 12.8 cm<sup>2</sup>, which also showed improved efficiency from 18.99% to 20.86%. The 3D microscope reveals improved uniformity of the resulting perovskite film across monitored large areas, indicating the application of our ternary strategy for scaling up photovoltaic perovskites. We believe the findings unearthed here provide critical insights for systematically exploring synergistic multicomponent solvent effects in film formation of perovskites.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"20 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732091","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}
The deep removal of sulfur dioxide (SO2) from flue gas is of significant importance for environmental protection, yet developing adsorbents with high uptake capacity and selectivity, as well as excellent cycling stability, remains a formidable challenge. Herein, two porous aromatic frameworks (PAFs) with electron-rich conjugated structures (termed PAF-TrP and PAF-SBF) were prepared for the selective capture of SO2 from flue gas. A systematic investigation involving static gas adsorption, dynamic breakthrough experiments, stability tests, and molecular-level simulations demonstrated that both PAFs exhibit an exceptional SO2 capture performance. Under conditions of 298 K and 1 bar, the uptake capacities of SO2 in PAF-TrP and PAF-SBF reach 259.1 and 344.7 cm–3·g–1, respectively. The IAST (ideal adsorbed solution theory) selectivities of PAF-TrP and PAF-SBF toward SO2 in the SO2/N2 binary gas mixture are 4159.3 ∼ 902.8 and 3769.1 ∼ 844.3, respectively, at 298 K and 1 bar. Molecular-level simulation calculations based on density functional theory (DFT) revealed the intrinsic mechanism underlying the highly selective SO2 capture by the two PAFs. Specifically, the localized charge separation on the electron-rich aromatic conjugated frameworks of both PAFs generates a gradient electric field, which induces strong dipole–dipole and dipole−π interactions with polar SO2 molecules. Additionally, the construction mode of the two PAFs via strong covalent linkages endows them with remarkable stability and favorable regenerability. This study represents a meaningful endeavor toward developing high-performance adsorbents for flue gas desulfurization.
{"title":"Efficient SO2 Capture Mediated via a Gradient Electric Field in Electron-Rich Conjugated Porous Aromatic Frameworks","authors":"Wenxiang Zhang, Yue Wu, Yinhui Li, Qingkuan Meng, Yongzheng Wang, Heping Ma","doi":"10.1021/acsami.5c21777","DOIUrl":"https://doi.org/10.1021/acsami.5c21777","url":null,"abstract":"The deep removal of sulfur dioxide (SO<sub>2</sub>) from flue gas is of significant importance for environmental protection, yet developing adsorbents with high uptake capacity and selectivity, as well as excellent cycling stability, remains a formidable challenge. Herein, two porous aromatic frameworks (PAFs) with electron-rich conjugated structures (termed PAF-TrP and PAF-SBF) were prepared for the selective capture of SO<sub>2</sub> from flue gas. A systematic investigation involving static gas adsorption, dynamic breakthrough experiments, stability tests, and molecular-level simulations demonstrated that both PAFs exhibit an exceptional SO<sub>2</sub> capture performance. Under conditions of 298 K and 1 bar, the uptake capacities of SO<sub>2</sub> in PAF-TrP and PAF-SBF reach 259.1 and 344.7 cm<sup>–3</sup>·g<sup>–1</sup>, respectively. The IAST (ideal adsorbed solution theory) selectivities of PAF-TrP and PAF-SBF toward SO<sub>2</sub> in the SO<sub>2</sub>/N<sub>2</sub> binary gas mixture are 4159.3 ∼ 902.8 and 3769.1 ∼ 844.3, respectively, at 298 K and 1 bar. Molecular-level simulation calculations based on density functional theory (DFT) revealed the intrinsic mechanism underlying the highly selective SO<sub>2</sub> capture by the two PAFs. Specifically, the localized charge separation on the electron-rich aromatic conjugated frameworks of both PAFs generates a gradient electric field, which induces strong dipole–dipole and dipole−π interactions with polar SO<sub>2</sub> molecules. Additionally, the construction mode of the two PAFs via strong covalent linkages endows them with remarkable stability and favorable regenerability. This study represents a meaningful endeavor toward developing high-performance adsorbents for flue gas desulfurization.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"93 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729219","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}
Anky Fitrian Wibowo,Muhamad Junda Azizi,Nurwarrohman Andre Sasongko,Jung Ha Kim,Yulia Shara Br Sembiring,Siti Aisyah Nurmaulia Entifar,Jonghee Lee,Min-Seok Kim,Soyeon Kim,Dong Chan Lim,Myeongkee Park,Yong Hyun Kim
Stretchable devices have attracted significant attention due to their mechanical versatility and potential applications in wearable electronics, soft robotics, and biomedical devices. However, their practical implementation is often hindered by challenges in surface engineering, particularly at the interface between stretchable elastomers and conducting polymers like poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). This study introduces a novel strategy to enhance the performance of stretchable devices by engineering the elastomer substrate surface with 2,6-diaminopimelic acid (DAP), an amino-functionalization approach that improves integration with lab-synthesized PEDOT:PSS. DAP, a key diamino dicarboxylic acid component of Gram-negative bacterial cell wall peptidoglycan, is employed to facilitate amino and hydroxyl group activation on the elastomer surface. This process consequently improves the adhesion, mechanical stability, surface energy, and electrical conductivity at the interface between the elastomer and PEDOT:PSS. The electrical properties of the modified films were assessed under various mechanical deformations, demonstrating enhanced conductivity and stability. Chemical analyses using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) revealed that DAP functions as an interfacial bridge, forming chemical bonds or complexes between the elastomer surface and the functional groups in PEDOT:PSS. Increased adhesivity was confirmed by a lower contact angle and an improved adhesion energy of 134.4 mN/m. In conclusion, DAP-based surface modification is a promising approach for improving the key properties of stretchable devices. These findings support the development of robust electronics, including wearable heaters and alternating current electroluminescent (ACEL) devices, for broader applications in stretchable technologies.
{"title":"Amino-Functionalized Surface Engineering of Elastomers for Robust PEDOT:PSS-Based Stretchable Electronics.","authors":"Anky Fitrian Wibowo,Muhamad Junda Azizi,Nurwarrohman Andre Sasongko,Jung Ha Kim,Yulia Shara Br Sembiring,Siti Aisyah Nurmaulia Entifar,Jonghee Lee,Min-Seok Kim,Soyeon Kim,Dong Chan Lim,Myeongkee Park,Yong Hyun Kim","doi":"10.1021/acsami.5c19272","DOIUrl":"https://doi.org/10.1021/acsami.5c19272","url":null,"abstract":"Stretchable devices have attracted significant attention due to their mechanical versatility and potential applications in wearable electronics, soft robotics, and biomedical devices. However, their practical implementation is often hindered by challenges in surface engineering, particularly at the interface between stretchable elastomers and conducting polymers like poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). This study introduces a novel strategy to enhance the performance of stretchable devices by engineering the elastomer substrate surface with 2,6-diaminopimelic acid (DAP), an amino-functionalization approach that improves integration with lab-synthesized PEDOT:PSS. DAP, a key diamino dicarboxylic acid component of Gram-negative bacterial cell wall peptidoglycan, is employed to facilitate amino and hydroxyl group activation on the elastomer surface. This process consequently improves the adhesion, mechanical stability, surface energy, and electrical conductivity at the interface between the elastomer and PEDOT:PSS. The electrical properties of the modified films were assessed under various mechanical deformations, demonstrating enhanced conductivity and stability. Chemical analyses using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) revealed that DAP functions as an interfacial bridge, forming chemical bonds or complexes between the elastomer surface and the functional groups in PEDOT:PSS. Increased adhesivity was confirmed by a lower contact angle and an improved adhesion energy of 134.4 mN/m. In conclusion, DAP-based surface modification is a promising approach for improving the key properties of stretchable devices. These findings support the development of robust electronics, including wearable heaters and alternating current electroluminescent (ACEL) devices, for broader applications in stretchable technologies.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"148 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728624","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：