Xuan Deng, Chao Dou, Yan Wang, Haoyue Lu, Ruoyao Sun, Yueying Li, Jing Liu
Two-dimensional transition-metal dichalcogenide (TMD) homojunctions are promising for optoelectronic applications but are fundamentally limited by inefficient carrier separation, even under reverse bias. Here, we introduce surface acoustic wave (SAW) technology as an efficient means to enhance photocarrier dissociation via strain-mediated electron-phonon interactions. To experimentally validate this approach, we constructed a hybrid acoustooptic platform by integrating a LiNbO3 substrate with interdigitated transducers onto a SiO2/Si chip. A reconfigurable WSe2 homojunction─fabricated on an hexagonal boron nitride (h-BN) intermediate layer and dynamically tunable via UV-assisted doping to form junctions with tailored built-in potentials─served as the functional device. Under SAW excitation propagating from LiNbO3 into the device stack, the homojunction exhibits a 30% photocurrent enhancement at 550 nm illumination, outperforming conventional reverse-bias operation at nearly an order-of-magnitude lower voltage, while maintaining a rectification ratio of >103 and negligible dark-current variation. Mechanistic studies reveal that the SAW induces a type-I band modulation in the nonpiezoelectric heterostructure, creating energy barriers that suppress recombination and substantially improve electron-hole separation. This work demonstrates SAW as an effective strategy for enhancing the optoelectronic performance in homojunctions and provides a scalable platform for acoustooptic applications in nonpiezoelectric low-dimensional systems.
{"title":"Acoustic-Driven Enhancement of Photocarrier Separation in a Reconfigurable WSe<sub>2</sub> Homojunction.","authors":"Xuan Deng, Chao Dou, Yan Wang, Haoyue Lu, Ruoyao Sun, Yueying Li, Jing Liu","doi":"10.1021/acsami.5c24273","DOIUrl":"https://doi.org/10.1021/acsami.5c24273","url":null,"abstract":"<p><p>Two-dimensional transition-metal dichalcogenide (TMD) homojunctions are promising for optoelectronic applications but are fundamentally limited by inefficient carrier separation, even under reverse bias. Here, we introduce surface acoustic wave (SAW) technology as an efficient means to enhance photocarrier dissociation via strain-mediated electron-phonon interactions. To experimentally validate this approach, we constructed a hybrid acoustooptic platform by integrating a LiNbO<sub>3</sub> substrate with interdigitated transducers onto a SiO<sub>2</sub>/Si chip. A reconfigurable WSe<sub>2</sub> homojunction─fabricated on an hexagonal boron nitride (h-BN) intermediate layer and dynamically tunable via UV-assisted doping to form junctions with tailored built-in potentials─served as the functional device. Under SAW excitation propagating from LiNbO<sub>3</sub> into the device stack, the homojunction exhibits a 30% photocurrent enhancement at 550 nm illumination, outperforming conventional reverse-bias operation at nearly an order-of-magnitude lower voltage, while maintaining a rectification ratio of >10<sup>3</sup> and negligible dark-current variation. Mechanistic studies reveal that the SAW induces a type-I band modulation in the nonpiezoelectric heterostructure, creating energy barriers that suppress recombination and substantially improve electron-hole separation. This work demonstrates SAW as an effective strategy for enhancing the optoelectronic performance in homojunctions and provides a scalable platform for acoustooptic applications in nonpiezoelectric low-dimensional systems.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122946","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 rapid advancement of 5G communication technology necessitates enhanced performance in electromagnetic interference (EMI) shielding and thermal management materials. We fabricated multifunctional nacre-like MXene@CuNPs(MSC)composite films via intermittent filtration and in situ reduction. The resulting composite film exhibited a high in-plane thermal conductivity of 47.6 W m-1 K-1 and demonstrated superior thermal management capability in heat dissipation tests. Containing 3.1 wt % Cu and with a thickness of 0.04 mm, the film achieved an average EMI shielding effectiveness (SE) of 64 dB within the X-band (8.2-12.4 GHz). Calculations based on the effective medium theory (EMT) elucidated the critical role of Cu nanoparticles (CuNPs) in establishing an efficient thermal conduction network. Owing to the CuNPs acting as thermal bridges, the interfacial thermal resistance within the composite film decreased by 35.6%. Furthermore, the MSC composite films exhibited rapid-response photothermal behavior. Upon irradiation with a light power density of 200 mW cm-2, the surface temperature of the MSC3.1 film rapidly reached 101 °C. The outstanding performance of this composite film underscores the broad application potential of Cu-modified MXene in electronic devices and related fields.
{"title":"In-Situ CuNPs Reduction on MXene for High-Thermal-Conductivity Composite Films with Exceptional EMI Shielding and Photothermal Conversion.","authors":"Xianjin Yang, Enxiang Jiao, Xuehai Zhang, Ke Zhang, Anbang Sun, Yanwei Zhao, Huimin Wang, Zheng Cao, Peng Lv, Haijun Zhang, Hongwang Shen, Fulai Zhao","doi":"10.1021/acsami.5c25592","DOIUrl":"https://doi.org/10.1021/acsami.5c25592","url":null,"abstract":"<p><p>The rapid advancement of 5G communication technology necessitates enhanced performance in electromagnetic interference (EMI) shielding and thermal management materials. We fabricated multifunctional nacre-like MXene@CuNPs(MSC)composite films via intermittent filtration and in situ reduction. The resulting composite film exhibited a high in-plane thermal conductivity of 47.6 W m<sup>-1</sup> K<sup>-1</sup> and demonstrated superior thermal management capability in heat dissipation tests. Containing 3.1 wt % Cu and with a thickness of 0.04 mm, the film achieved an average EMI shielding effectiveness (SE) of 64 dB within the X-band (8.2-12.4 GHz). Calculations based on the effective medium theory (EMT) elucidated the critical role of Cu nanoparticles (CuNPs) in establishing an efficient thermal conduction network. Owing to the CuNPs acting as thermal bridges, the interfacial thermal resistance within the composite film decreased by 35.6%. Furthermore, the MSC composite films exhibited rapid-response photothermal behavior. Upon irradiation with a light power density of 200 mW cm<sup>-2</sup>, the surface temperature of the MSC<sub>3.1</sub> film rapidly reached 101 °C. The outstanding performance of this composite film underscores the broad application potential of Cu-modified MXene in electronic devices and related fields.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122961","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}
Praveen Jeyachandran, Lionel Yan Jin Lee, Si Jian Hui, Balamurugan Vellayappan, Jerry Ying Hsi Fuh, James Thomas Patrick Decourcy Hallinan, A. Senthil Kumar, Naresh Kumar
A prime focus in orthopedic research is to promote osseointegration, while improving the functionality of implantable biomaterials. Surface topographic features have been shown to influence cell–biomaterial interactions, thereby facilitating cell adhesion, proliferation, and growth. However, a key challenge lies in inducing such topographical cues through existing biofabrication technologies. This study presents a newer strategy to leverage existing 3D printing (3DP) technology, promoting topographical cues manifested as microscopic spherulitic crystals integrated with nanoscopic lamellas on printed surfaces. Poly ether–ether–ketone (PEEK) composites reinforced with hydroxyapatite (HAp) and magnesium orthosilicate (Mg2SiO4) are printed using droplet-based 3D printing (3DP) technology, wherein the printing parameters are tailored to induce a network of spherulitic topographical cues in conjunction with biochemical cues arising from exposed bioactive fillers. Human osteosarcoma (Saos-2) cells are used to investigate the synergistic influence of the topographical and biochemical cues on the cell–material biological interactions. The composites exhibit hydrophilic surfaces with enhanced surface energy, promoting cellular adhesion and the formation of numerous filopodia, indicating an active engagement with spherulitic topographies. Composite surfaces featuring spherulitic topographical and biochemical cues foster a conducive environment, augmenting the cytocompatibility and osteogenic capabilities. Furthermore, process optimization not only improves the mechanical performance of the composites but also enhances their damping capabilities, a critical attribute for implant applications. This approach demonstrates that engineered spherulitic-topographical cues, in conjunction with biochemical cues, can mimic lamellar bone morphology, yielding improved biological and dynamic mechanical responses and highlighting their potential for personalized orthopedic implant applications.
{"title":"Leveraging 3D Printing-Induced Spherulitic Topographical and Biochemical Cues on Polyether Ether Ketone/Hydroxyapatite/Magnesium Orthosilicate Composites for Orthopedic Applications","authors":"Praveen Jeyachandran, Lionel Yan Jin Lee, Si Jian Hui, Balamurugan Vellayappan, Jerry Ying Hsi Fuh, James Thomas Patrick Decourcy Hallinan, A. Senthil Kumar, Naresh Kumar","doi":"10.1021/acsami.5c22456","DOIUrl":"https://doi.org/10.1021/acsami.5c22456","url":null,"abstract":"A prime focus in orthopedic research is to promote osseointegration, while improving the functionality of implantable biomaterials. Surface topographic features have been shown to influence cell–biomaterial interactions, thereby facilitating cell adhesion, proliferation, and growth. However, a key challenge lies in inducing such topographical cues through existing biofabrication technologies. This study presents a newer strategy to leverage existing 3D printing (3DP) technology, promoting topographical cues manifested as microscopic spherulitic crystals integrated with nanoscopic lamellas on printed surfaces. Poly ether–ether–ketone (PEEK) composites reinforced with hydroxyapatite (HAp) and magnesium orthosilicate (Mg<sub>2</sub>SiO<sub>4</sub>) are printed using droplet-based 3D printing (3DP) technology, wherein the printing parameters are tailored to induce a network of spherulitic topographical cues in conjunction with biochemical cues arising from exposed bioactive fillers. Human osteosarcoma (Saos-2) cells are used to investigate the synergistic influence of the topographical and biochemical cues on the cell–material biological interactions. The composites exhibit hydrophilic surfaces with enhanced surface energy, promoting cellular adhesion and the formation of numerous filopodia, indicating an active engagement with spherulitic topographies. Composite surfaces featuring spherulitic topographical and biochemical cues foster a conducive environment, augmenting the cytocompatibility and osteogenic capabilities. Furthermore, process optimization not only improves the mechanical performance of the composites but also enhances their damping capabilities, a critical attribute for implant applications. This approach demonstrates that engineered spherulitic-topographical cues, in conjunction with biochemical cues, can mimic lamellar bone morphology, yielding improved biological and dynamic mechanical responses and highlighting their potential for personalized orthopedic implant applications.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"301 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116074","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}
Ruthenium (Ru) has emerged as a promising next-generation metal for ultrahigh-density interconnects, offering superior electrical performance and electromigration resistance at submicrometre dimensions, and thus is a strong candidate to replace Cu in future very-large-scale integration (VLSI) technologies. However, enabling Ru/dielectric hybrid bonding at low temperatures remains exceedingly challenging. The intrinsically high melting point of Ru(∼2334 °C) and its extremely low diffusion coefficient (∼1 × 10-70 m2·s-1) typically necessitate high-temperature, high-pressure thermal compression bonding. In parallel, hydrophilic bonding with dielectric materials such as SiO2 must be achieved while suppressing Ru surface oxidation. In this study, we introduce a synergistic surface-activation strategy─Ar/H2 plasma treatment followed by immersion in NH4OH─that enables robust Ru-Ru bonding at 250 °C without oxidation. Moreover, the activated surfaces yield a 20% reduction in Ru surface resistance. This approach generates abundant -OH and -NH2 functional groups on the Ru surface, promoting interfacial reactions and the formation of a void-free interface. Intriguingly, the bond strengths exceeded 12 MPa after 1000 thermal cycles between -45 °C and +125 °C. This synergistic activation route provides a viable pathway for low-temperature Ru/dielectric hybrid bonding with high reliability. The demonstrated bonding performance underscores Ru potential as a Cu replacement in BEOL interconnects and establishes a foundation for metal/dielectric hybrid bonding in forthcoming high-density integration technologies.
{"title":"Low-Temperature Ru-Ru Hybrid Bonding: Ar/H<sub>2</sub> Plasma and NH<sub>4</sub>OH Synergistic Activation for Ultrahigh Density Interconnection.","authors":"Yufei Bai, Jia Yang, Xinze Li, Qiushi Kang, Ziyang Xiu, Tadatomo Suga, Chenxi Wang","doi":"10.1021/acsami.5c23710","DOIUrl":"https://doi.org/10.1021/acsami.5c23710","url":null,"abstract":"<p><p>Ruthenium (Ru) has emerged as a promising next-generation metal for ultrahigh-density interconnects, offering superior electrical performance and electromigration resistance at submicrometre dimensions, and thus is a strong candidate to replace Cu in future very-large-scale integration (VLSI) technologies. However, enabling Ru/dielectric hybrid bonding at low temperatures remains exceedingly challenging. The intrinsically high melting point of Ru(∼2334 °C) and its extremely low diffusion coefficient (∼1 × 10<sup>-70</sup> m<sup>2</sup>·s<sup>-1</sup>) typically necessitate high-temperature, high-pressure thermal compression bonding. In parallel, hydrophilic bonding with dielectric materials such as SiO<sub>2</sub> must be achieved while suppressing Ru surface oxidation. In this study, we introduce a synergistic surface-activation strategy─Ar/H<sub>2</sub> plasma treatment followed by immersion in NH<sub>4</sub>OH─that enables robust Ru-Ru bonding at 250 °C without oxidation. Moreover, the activated surfaces yield a 20% reduction in Ru surface resistance. This approach generates abundant -OH and -NH<sub>2</sub> functional groups on the Ru surface, promoting interfacial reactions and the formation of a void-free interface. Intriguingly, the bond strengths exceeded 12 MPa after 1000 thermal cycles between -45 °C and +125 °C. This synergistic activation route provides a viable pathway for low-temperature Ru/dielectric hybrid bonding with high reliability. The demonstrated bonding performance underscores Ru potential as a Cu replacement in BEOL interconnects and establishes a foundation for metal/dielectric hybrid bonding in forthcoming high-density integration technologies.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146117139","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}
Lithium metal batteries have gained renewed attention after a recent surge in high-energy battery systems. Lithium metal, known for its exceptional specific capacity and voltage, suffers from dendrite formation, which affects the cell performance and poses a severe safety threat, like internal short circuits and thermal runaway. Artificial solid electrolyte (ASEI) has emerged as an effective strategy to guide uniform lithium deposition, but only a few studies have explored the correlation between the interfacial kinetics and the nucleation behavior at the molecular level. In our work, we developed an inorganic-organic hybrid bilayer protective coating on the lithium anode, enabling over 1000 h of Li/Li symmetric cell cycling at 0.5 mA/cm2 (0.5 mAh/cm2) with low overpotentials. The impact of this bilayer on the nucleation behavior has been addressed using chronoamperometric studies and a modified SEI model based on S-H classical nucleation. Ab initio molecular dynamics (AIMD) simulations revealed the role of bilayer components in homogenizing the lithium flux by decreasing the coordination number of lithium ions and promoting lateral growth. These led to a relatively uniform lithium deposition morphology with better capacity retention of more than 80% after 80 cycles for protected lithium (p-Li)/NMC-622 half-cells cycled at 1.7 C with a high loading of 23 mg/cm2. Our findings establish the importance of interface engineering in controlling the nucleation kinetics of lithium deposition for the development of high-voltage lithium metal batteries.
{"title":"A Hybrid Bilayer Design to Control Lithium Nucleation and Dendrite Growth in Lithium Metal Batteries.","authors":"Ashwin P V, Supriya Sau, Novotna Seal, Amreen Bano, Sagar Mitra","doi":"10.1021/acsami.5c23307","DOIUrl":"https://doi.org/10.1021/acsami.5c23307","url":null,"abstract":"<p><p>Lithium metal batteries have gained renewed attention after a recent surge in high-energy battery systems. Lithium metal, known for its exceptional specific capacity and voltage, suffers from dendrite formation, which affects the cell performance and poses a severe safety threat, like internal short circuits and thermal runaway. Artificial solid electrolyte (ASEI) has emerged as an effective strategy to guide uniform lithium deposition, but only a few studies have explored the correlation between the interfacial kinetics and the nucleation behavior at the molecular level. In our work, we developed an inorganic-organic hybrid bilayer protective coating on the lithium anode, enabling over 1000 h of Li/Li symmetric cell cycling at 0.5 mA/cm<sup>2</sup> (0.5 mAh/cm<sup>2</sup>) with low overpotentials. The impact of this bilayer on the nucleation behavior has been addressed using chronoamperometric studies and a modified SEI model based on S-H classical nucleation. Ab initio molecular dynamics (AIMD) simulations revealed the role of bilayer components in homogenizing the lithium flux by decreasing the coordination number of lithium ions and promoting lateral growth. These led to a relatively uniform lithium deposition morphology with better capacity retention of more than 80% after 80 cycles for protected lithium (p-Li)/NMC-622 half-cells cycled at 1.7 C with a high loading of 23 mg/cm<sup>2</sup>. Our findings establish the importance of interface engineering in controlling the nucleation kinetics of lithium deposition for the development of high-voltage lithium metal batteries.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122906","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}
Fateme Yekefalah, Albert Minj, Ankit Nalin Mehta, Thomas Nuytten, Pawan Kumar, Claudia Fleischmann, Ingrid De Wolf
In this work, an in-depth correlated study of the impact of grain boundaries on the excitonic and electronic properties of monolayer WS2 is reported. Signatures of defect- and strain-induced gap states are detected and studied in the vicinity of the grain boundaries using tip-enhanced photoluminescence, Kelvin probe force microscopy, and conductive atomic force microscopy. These gap states demonstrate a trap-like behavior for the free excitons, resulting in the radiative recombination of the localized excitonic states at room temperature. The trapping behavior is also detected for the free carriers, indicated by the abundance of fixed charges at the grain boundaries. The carrier trapping is corroborated through (tip-enhanced) photoluminescence spectroscopy at the grain boundaries, particularly after photoinjection of carriers. Comparison of the photoluminescence response acquired under ambient and high vacuum indicates the high reactivity of these defect sites and physisorption of ambient species. The ambient molecules seemingly passivate the defect sites and locally modulate the layer properties.
{"title":"Detection and Modulation of Gap States at the Grain Boundaries of Monolayer WS<sub>2</sub>.","authors":"Fateme Yekefalah, Albert Minj, Ankit Nalin Mehta, Thomas Nuytten, Pawan Kumar, Claudia Fleischmann, Ingrid De Wolf","doi":"10.1021/acsami.5c24211","DOIUrl":"https://doi.org/10.1021/acsami.5c24211","url":null,"abstract":"<p><p>In this work, an in-depth correlated study of the impact of grain boundaries on the excitonic and electronic properties of monolayer WS<sub>2</sub> is reported. Signatures of defect- and strain-induced gap states are detected and studied in the vicinity of the grain boundaries using tip-enhanced photoluminescence, Kelvin probe force microscopy, and conductive atomic force microscopy. These gap states demonstrate a trap-like behavior for the free excitons, resulting in the radiative recombination of the localized excitonic states at room temperature. The trapping behavior is also detected for the free carriers, indicated by the abundance of fixed charges at the grain boundaries. The carrier trapping is corroborated through (tip-enhanced) photoluminescence spectroscopy at the grain boundaries, particularly after photoinjection of carriers. Comparison of the photoluminescence response acquired under ambient and high vacuum indicates the high reactivity of these defect sites and physisorption of ambient species. The ambient molecules seemingly passivate the defect sites and locally modulate the layer properties.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122952","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}
Shanshan Xu, Rui Li, Chendong Shuang, Zhao Wang, Yang Yu, Rong Ji, Qing Zhou, Aimin Li, Tao Hou
Anion-exchange resins (AER) are widely applied in water treatment, although their chemical-intensive regeneration remains a bottleneck for the consumption of chemicals and generation of wastes. This study presents a thermo-regenerable AER composite (TR@AER) prepared via the interpenetration of poly(acrylic acid-co-acrylamide) (p(AA-co-AM)) within the AER matrix. TR@AER exhibits thermoresponsive hydrophilicity and surface charge, evidenced by a decrease in contact angle from 88.1° (25 °C) to 76.7° (50 °C) and a drop in ζ-potential from +36.9 mV (25 °C) to +31.1 mV (50 °C). In situ variothermal FTIR and molecular dynamics simulations reveal that this dual response is triggered by the dissociation of hydrogen bonds between −COOH and −CONH2 groups in p(AA-co-AM). The dissociation simultaneously drives the hydrophobic-to-hydrophilic transition and deprotonation of −COOH groups in p(AA-co-AM), which subsequently interact with quaternary ammonium (−NR3+) moieties of AER and alter surface charge characteristics. This enables a switchable adsorption and desorption of organic contaminants. At 25 °C, TR@AER rapidly adsorbs diclofenac and ibuprofen through synergistic electrostatic and hydrophobic interactions. Heating to 50 °C disrupts these interactions, significantly enhancing desorption. The desorption efficiency correlates with p(AA-co-AM) content in TR@AER. At the optimal p(AA-co-AM) loading (26–37 wt%), diclofenac desorption reached 92.2% and ibuprofen desorption reached 96.0% at 50 °C, representing 1.7- and 1.8-fold that of 25 °C, respectively. By circumventing chemical-intensive regeneration protocols, this work highlights an innovative strategy for stimuli-responsive adsorbent design with excellent regeneration capabilities.
{"title":"Thermo-Regenerable Anion-Exchange Composites for the Removal of Diclofenac and Ibuprofen","authors":"Shanshan Xu, Rui Li, Chendong Shuang, Zhao Wang, Yang Yu, Rong Ji, Qing Zhou, Aimin Li, Tao Hou","doi":"10.1021/acsami.5c21493","DOIUrl":"https://doi.org/10.1021/acsami.5c21493","url":null,"abstract":"Anion-exchange resins (AER) are widely applied in water treatment, although their chemical-intensive regeneration remains a bottleneck for the consumption of chemicals and generation of wastes. This study presents a thermo-regenerable AER composite (TR@AER) prepared via the interpenetration of poly(acrylic acid-<i>co</i>-acrylamide) (p(AA-<i>co</i>-AM)) within the AER matrix. TR@AER exhibits thermoresponsive hydrophilicity and surface charge, evidenced by a decrease in contact angle from 88.1° (25 °C) to 76.7° (50 °C) and a drop in ζ-potential from +36.9 mV (25 °C) to +31.1 mV (50 °C). <i>In situ</i> variothermal FTIR and molecular dynamics simulations reveal that this dual response is triggered by the dissociation of hydrogen bonds between −COOH and −CONH<sub>2</sub> groups in p(AA-<i>co</i>-AM). The dissociation simultaneously drives the hydrophobic-to-hydrophilic transition and deprotonation of −COOH groups in p(AA-<i>co</i>-AM), which subsequently interact with quaternary ammonium (−NR<sub>3</sub><sup>+</sup>) moieties of AER and alter surface charge characteristics. This enables a switchable adsorption and desorption of organic contaminants. At 25 °C, TR@AER rapidly adsorbs diclofenac and ibuprofen through synergistic electrostatic and hydrophobic interactions. Heating to 50 °C disrupts these interactions, significantly enhancing desorption. The desorption efficiency correlates with p(AA-<i>co</i>-AM) content in TR@AER. At the optimal p(AA-<i>co</i>-AM) loading (26–37 wt%), diclofenac desorption reached 92.2% and ibuprofen desorption reached 96.0% at 50 °C, representing 1.7- and 1.8-fold that of 25 °C, respectively. By circumventing chemical-intensive regeneration protocols, this work highlights an innovative strategy for stimuli-responsive adsorbent design with excellent regeneration capabilities.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"234 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111021","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}
Xiao-Yuan Lin, Dhananjay S. Nipate, Shih-Kang Chen, Mai Harada, U-Ser Jeng, Michal Kohout, Hong-Cheu Lin, Yasutaka Kitagawa, Tomoyuki Akutagawa, Wen-Ya Lee, Hsiu-Hui Chen
The meniscus-guided coating (MGC) method was used to prepare well-aligned films of hybrid systems composed of the conjugated polymer poly{3,6-dithiophen-2-yl-2,5-di(2-decyltetra-decyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-thienylenevinylene-2,5-yl} (PDVT-10) and a photoresponsive small molecule dopant, dithienylperfluorocyclopentene (DTCP), at various concentrations in their open-ring form (DTCP-o) or closed-ring (DTCP-c) form. The structures of the coated films were characterized with polarized optical microscopy (POM), grazing-incidence X-ray diffraction (GIXRD), and atomic force microscopy (AFM). The DTCP can undergo reversible isomerization between a more twisted open-ring form and a more conjugated closed-ring form under UV and visible light, respectively. Both DTCP isomers were found to function as morphology-modulating additives that facilitate cooperative crystallization, an effect attributed to enhanced solution-phase molecular association, which impacts the packing of the polymer film. Organic field-effect transistors (OFETs) were fabricated from these films. The DTCP-c doping progressively enhanced charge transport, reaching the highest mobility of 2.44 cm2 V−1 s−1 at 10 wt %. Notably, 3 wt % DTCP-o, typically considered insulating molecule, increased PDVT-10 mobility from 2.12 to 3.23 cm2 V−1 s−1. This improvement is suggested to arise from the combined effects of precise molecular alignment by the MGC method and a favorable HOMO–HOMO energy level alignment predicted by DFT, enabling cooperative charge transfer despite the nominally insulating nature of the open-ring form. The photoswitchable DTCP provides a unique opportunity to optically modulate frontier molecular orbital energy levels, thereby opening up an avenue for designing electronic devices such as photocontrollable OFETs.
{"title":"Morphology Control in PDVT-10/DTCP Hybrid Films via Meniscus-Guided Cooperative Crystallization for High-Performance OFETs","authors":"Xiao-Yuan Lin, Dhananjay S. Nipate, Shih-Kang Chen, Mai Harada, U-Ser Jeng, Michal Kohout, Hong-Cheu Lin, Yasutaka Kitagawa, Tomoyuki Akutagawa, Wen-Ya Lee, Hsiu-Hui Chen","doi":"10.1021/acsami.5c23619","DOIUrl":"https://doi.org/10.1021/acsami.5c23619","url":null,"abstract":"The meniscus-guided coating (MGC) method was used to prepare well-aligned films of hybrid systems composed of the conjugated polymer poly{3,6-dithiophen-2-yl-2,5-di(2-decyltetra-decyl)-pyrrolo[3,4-<i>c</i>]pyrrole-1,4-dione-<i>alt</i>-thienylenevinylene-2,5-yl} (<b>PDVT-10)</b> and a photoresponsive small molecule dopant, dithienylperfluorocyclopentene (<b>DTCP</b>), at various concentrations in their open-ring form (<b>DTCP-o</b>) or closed-ring (<b>DTCP-c</b>) form. The structures of the coated films were characterized with polarized optical microscopy (POM), grazing-incidence X-ray diffraction (GIXRD), and atomic force microscopy (AFM). The <b>DTCP</b> can undergo reversible isomerization between a more twisted open-ring form and a more conjugated closed-ring form under UV and visible light, respectively. Both <b>DTCP</b> isomers were found to function as morphology-modulating additives that facilitate cooperative crystallization, an effect attributed to enhanced solution-phase molecular association, which impacts the packing of the polymer film. Organic field-effect transistors (OFETs) were fabricated from these films. The <b>DTCP-c</b> doping progressively enhanced charge transport, reaching the highest mobility of 2.44 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup> at 10 wt %. Notably, 3 wt % <b>DTCP-o</b>, typically considered insulating molecule, increased <b>PDVT-10</b> mobility from 2.12 to 3.23 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup>. This improvement is suggested to arise from the combined effects of precise molecular alignment by the MGC method and a favorable HOMO–HOMO energy level alignment predicted by DFT, enabling cooperative charge transfer despite the nominally insulating nature of the open-ring form. The photoswitchable <b>DTCP</b> provides a unique opportunity to optically modulate frontier molecular orbital energy levels, thereby opening up an avenue for designing electronic devices such as photocontrollable OFETs.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"34 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111049","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}
Julia Schwieg,Namodhi Wijerathne,Kyle Morgan,Margaret Alexandre,Wei David Wei
Organic semiconductors offer a uniquely versatile and cost-effective platform for solar-driven hydrogen generation from water by leveraging scalable and earth-abundant material design. Their high degree of tunability in molecular, optical, and electronic structures has enabled drastic improvements in solar absorptivity, energy level alignment with redox potentials of hydrogen evolution, longer photogenerated charge carrier lifetimes, and improved overall kinetics. This review focuses on the photocatalytic hydrogen generation from water, highlighting the key challenges that continue to limit performance and practical implementation. In particular, we examine recent strategies to address insufficient light absorption, inefficient charge carrier separation, and poor long-term stability across a broad range of organic semiconductor platforms, including conjugated polymers, covalent organic frameworks, and supramolecular assemblies. Finally, we provide an outlook on underexplored opportunities in both reaction kinetics and material design, providing approaches to overcome these persistent limitations and advance organic-semiconductor-based photocatalytic systems.
{"title":"Advances in Organic Semiconductors for Solar-Driven Hydrogen Generation from Water","authors":"Julia Schwieg,Namodhi Wijerathne,Kyle Morgan,Margaret Alexandre,Wei David Wei","doi":"10.1021/acsami.5c19875","DOIUrl":"https://doi.org/10.1021/acsami.5c19875","url":null,"abstract":"Organic semiconductors offer a uniquely versatile and cost-effective platform for solar-driven hydrogen generation from water by leveraging scalable and earth-abundant material design. Their high degree of tunability in molecular, optical, and electronic structures has enabled drastic improvements in solar absorptivity, energy level alignment with redox potentials of hydrogen evolution, longer photogenerated charge carrier lifetimes, and improved overall kinetics. This review focuses on the photocatalytic hydrogen generation from water, highlighting the key challenges that continue to limit performance and practical implementation. In particular, we examine recent strategies to address insufficient light absorption, inefficient charge carrier separation, and poor long-term stability across a broad range of organic semiconductor platforms, including conjugated polymers, covalent organic frameworks, and supramolecular assemblies. Finally, we provide an outlook on underexplored opportunities in both reaction kinetics and material design, providing approaches to overcome these persistent limitations and advance organic-semiconductor-based photocatalytic systems.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"88 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111233","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}
Jinsuo Ma, Qian Ma, Qi Wang, Yu Li, Wenxin Ji, Yulong Ma, Yonggang Sun, Yuanyuan Li
To address the critical limitations of natural bentonite, including restricted specific surface area and low cation exchange capacity (CEC) caused by interlayer impurities, this study proposes an in situ structural reconstruction strategy via simultaneous alkaline activation and aluminum doping. This approach directly transforms bentonite frameworks into a hierarchically porous SOD-type sodalite with an ultralow Si/Al ratio. The engineered material integrates three synergistic advantages: abundant surface hydroxyl groups, maximized CEC (saturation capacity, 242.56 mg/g), and a dual-scale pore architecture (micropores/mesopores). Combined experimental and computational analyses reveal the underlying mechanisms: The ultralow Si/Al ratio generates Al–O–Si bridging sites, strengthening electrostatic interactions with Pb2+ (adsorption energy: −1.356 eV) and reducing the migration energy barrier. Local charge redistribution at Al-rich domains optimizes Pb2+ occupation, achieving a stable Pb–O bond length of 2.35 Å. Hierarchical porosity facilitates rapid mass transfer, enabling 93% adsorption capacity retention after eight regeneration cycles. This work establishes a quantitative structure–performance relationship among Si/Al ratio, charge distribution, and adsorption efficiency through bentonite interlayer reconstruction. It provides fundamental insights for designing high-performance, low-cost heavy metal adsorbents, demonstrating a 2.7-fold increase in Pb2+ uptake compared to conventional bentonite, developing high-performance, low-cost heavy metal adsorbents.
为了解决天然膨润土的关键缺陷,包括层间杂质导致的比表面积限制和阳离子交换容量(CEC)低,本研究提出了一种通过同时碱性活化和铝掺杂的原位结构重建策略。这种方法直接将膨润土框架转化为具有超低Si/Al比的分层多孔sods型苏打石。该工程材料集成了三个协同优势:丰富的表面羟基,最大的CEC(饱和容量,242.56 mg/g)和双尺度孔隙结构(微孔/中孔)。结合实验和计算分析揭示了潜在的机制:超低Si/Al比产生了Al - o - Si桥接位点,增强了与Pb2+的静电相互作用(吸附能:- 1.356 eV),降低了迁移能垒。富al畴的局部电荷重分配优化了Pb2+的占据,使Pb-O键长稳定在2.35 Å。分层孔隙有利于快速传质,在8次再生循环后保持93%的吸附容量。本研究通过膨润土层间重构,建立了硅铝比、电荷分布和吸附效率之间的定量结构-性能关系。它为设计高性能、低成本的重金属吸附剂提供了基础见解,证明了与传统膨润土相比,Pb2+的吸收率提高了2.7倍,开发了高性能、低成本的重金属吸附剂。
{"title":"Synergistic Enhancement of Pb2+ Adsorption by Hierarchical Pore Structure and Ultralow Si/Al Ratio in Bentonite-Derived Sodalite","authors":"Jinsuo Ma, Qian Ma, Qi Wang, Yu Li, Wenxin Ji, Yulong Ma, Yonggang Sun, Yuanyuan Li","doi":"10.1021/acsami.5c20799","DOIUrl":"https://doi.org/10.1021/acsami.5c20799","url":null,"abstract":"To address the critical limitations of natural bentonite, including restricted specific surface area and low cation exchange capacity (CEC) caused by interlayer impurities, this study proposes an in situ structural reconstruction strategy via simultaneous alkaline activation and aluminum doping. This approach directly transforms bentonite frameworks into a hierarchically porous SOD-type sodalite with an ultralow Si/Al ratio. The engineered material integrates three synergistic advantages: abundant surface hydroxyl groups, maximized CEC (saturation capacity, 242.56 mg/g), and a dual-scale pore architecture (micropores/mesopores). Combined experimental and computational analyses reveal the underlying mechanisms: The ultralow Si/Al ratio generates Al–O–Si bridging sites, strengthening electrostatic interactions with Pb<sup>2+</sup> (adsorption energy: −1.356 eV) and reducing the migration energy barrier. Local charge redistribution at Al-rich domains optimizes Pb<sup>2+</sup> occupation, achieving a stable Pb–O bond length of 2.35 Å. Hierarchical porosity facilitates rapid mass transfer, enabling 93% adsorption capacity retention after eight regeneration cycles. This work establishes a quantitative structure–performance relationship among Si/Al ratio, charge distribution, and adsorption efficiency through bentonite interlayer reconstruction. It provides fundamental insights for designing high-performance, low-cost heavy metal adsorbents, demonstrating a 2.7-fold increase in Pb<sup>2+</sup> uptake compared to conventional bentonite, developing high-performance, low-cost heavy metal adsorbents.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"89 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146115967","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}