Atomically precise gold nanoclusters (APGNCs) have received considerable concern in electrocatalytic carbon dioxide reduction reaction (CO2RR). The investigation of the CO2RR of APGNCs with a surface single-atom difference remains challenging. Herein, the successive addition of a surface sulfur atom (μ4-S) on Au60 was concurrently realized via a modified ligand exchange. The additional μ4-S makes the outer three kernel gold atoms in situ transform into staple gold atoms without altering other parts, endowing them with optimal model catalysts. Notably, Au60S6 exhibited high activity and CO selectivity over 95% within the entire test potentials, which decreased with the introduction of a μ4-S. DFT simulations indicate that the d-band center of the gold active site upshifts toward the Fermi level with the addition of a μ4-S, which strengthens the adsorption of intermediates, raises the energy barriers for CO desorption. This work provides an unprecedented paradigm for understanding structure–property relationships at the level of a surface single atom.
{"title":"Poisoning Electrocatalytic CO2 Conversion to CO by Adding a μ4-S Atom on Au60 Nanocluster","authors":"Yining Chen, Shuguang Wang, Yan Sun, Xiaoyang Hu, Xiaofeng Lei, Fuling Liu, Afang Dai*, Tiansheng Wei, Zibao Gan* and Xiuwen Zheng*, ","doi":"10.1021/acsmaterialslett.5c0032210.1021/acsmaterialslett.5c00322","DOIUrl":"https://doi.org/10.1021/acsmaterialslett.5c00322https://doi.org/10.1021/acsmaterialslett.5c00322","url":null,"abstract":"<p >Atomically precise gold nanoclusters (APGNCs) have received considerable concern in electrocatalytic carbon dioxide reduction reaction (CO<sub>2</sub>RR). The investigation of the CO<sub>2</sub>RR of APGNCs with a surface single-atom difference remains challenging. Herein, the successive addition of a surface sulfur atom (μ<sub>4</sub>-S) on Au<sub>60</sub> was concurrently realized via a modified ligand exchange. The additional μ<sub>4</sub>-S makes the outer three kernel gold atoms in situ transform into staple gold atoms without altering other parts, endowing them with optimal model catalysts. Notably, Au<sub>60</sub>S<sub>6</sub> exhibited high activity and CO selectivity over 95% within the entire test potentials, which decreased with the introduction of a μ<sub>4</sub>-S. DFT simulations indicate that the d-band center of the gold active site upshifts toward the Fermi level with the addition of a μ<sub>4</sub>-S, which strengthens the adsorption of intermediates, raises the energy barriers for CO desorption. This work provides an unprecedented paradigm for understanding structure–property relationships at the level of a surface single atom.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"7 6","pages":"2366–2373 2366–2373"},"PeriodicalIF":9.6,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144189144","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The production of highly efficient, stable, robust, and low-cost electrodes for the hydrogen evolution reaction (HER) is crucially important in renewable energy technologies. This article presents the production of a porous composite ceramic with a formula of 80 wt % WC–20 wt % Mo2C, with a structure of an oriented asymmetric finger-like hole. Its high catalytic activity was experimentally confirmed, attributed to the in situ MoWC2/Mo2C heterostructure during sintering. What’s more, the produced electrode exhibits both high aerophobicity and high hydrophilicity. The overpotentials of the electrode of 1500 mA·cm–2 in 0.5 M H2SO4 and 1.0 M KOH were 352 and 276 mV, respectively, better than those of the Pt-wire electrode. The chronopotentiometry curves of 10–1500 mA·cm–2 confirmed its long-term stability. Density functional theory (DFT) calculations suggested that the MoWC2/Mo2C heterostructure could regulate the electronic structure, with appropriate hydrogen adsorption energy in acidic media and minimal water dissociation potential in alkaline media.
生产高效、稳定、坚固、低成本的析氢反应电极在可再生能源技术中至关重要。本文介绍了一种多孔复合陶瓷的制备方法,其配方为80 wt % WC-20 wt % Mo2C,具有定向不对称指状孔结构。实验证实了其高催化活性,这归因于烧结过程中原位MoWC2/Mo2C异质结构。制备的电极具有较高的疏氧性和亲水性。在0.5 M H2SO4和1.0 M KOH中,1500 mA·cm-2电极的过电位分别为352和276 mV,优于pt线电极。10 ~ 1500 mA·cm-2的时电位曲线证实了其长期稳定性。密度泛函理论(DFT)计算表明,MoWC2/Mo2C异质结构可以调节电子结构,在酸性介质中具有合适的氢吸附能,在碱性介质中具有最小的水解离电位。
{"title":"Superaerophobic WC-Mo2C Ceramic Electrode with MoWC2/Mo2C Heterostructure for Hydrogen Evolution Reaction at High Current Density","authors":"Anding Huang, Haisen Huang, Sishi Huang, Chuntian Tan, Yang Yang, Jiahao Li, Luyuan Hao, Feihong Wang*, Xin Xu* and Simeon Agathopoulos, ","doi":"10.1021/acsmaterialslett.5c0055210.1021/acsmaterialslett.5c00552","DOIUrl":"https://doi.org/10.1021/acsmaterialslett.5c00552https://doi.org/10.1021/acsmaterialslett.5c00552","url":null,"abstract":"<p >The production of highly efficient, stable, robust, and low-cost electrodes for the hydrogen evolution reaction (HER) is crucially important in renewable energy technologies. This article presents the production of a porous composite ceramic with a formula of 80 wt % WC–20 wt % Mo<sub>2</sub>C, with a structure of an oriented asymmetric finger-like hole. Its high catalytic activity was experimentally confirmed, attributed to the <i>in situ</i> MoWC<sub>2</sub>/Mo<sub>2</sub>C heterostructure during sintering. What’s more, the produced electrode exhibits both high aerophobicity and high hydrophilicity. The overpotentials of the electrode of 1500 mA·cm<sup>–2</sup> in 0.5 M H<sub>2</sub>SO<sub>4</sub> and 1.0 M KOH were 352 and 276 mV, respectively, better than those of the Pt-wire electrode. The chronopotentiometry curves of 10–1500 mA·cm<sup>–2</sup> confirmed its long-term stability. Density functional theory (DFT) calculations suggested that the MoWC<sub>2</sub>/Mo<sub>2</sub>C heterostructure could regulate the electronic structure, with appropriate hydrogen adsorption energy in acidic media and minimal water dissociation potential in alkaline media.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"7 6","pages":"2374–2381 2374–2381"},"PeriodicalIF":9.6,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144189143","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-22DOI: 10.1021/acsmaterialslett.5c0051010.1021/acsmaterialslett.5c00510
Junwei Li, Yang Tao, Zhihong Zhang, Yubo Luo, Xin Li* and Junyou Yang*,
Thermal interface materials (TIMs) are crucial for achieving efficient thermal management of electronic devices. Traditional TIMs require extreme compliance for low thermal contact resistance (Rc), resulting in the challenge of achieving both a high modulus and a low Rc. Here, we report a resilient (>96%) thermally conductive elastomer with a high elastic modulus (12.3 MPa) and a low Rc (12.3 K mm2 W–1) based on a dynamic/nondynamic hybrid cross-linking network strategy. The nondynamic cross-linking network serves as the backbone of the elastomer, providing elasticity and robustness, while the dynamic cross-linking network with dynamic features offers partial solid-state plasticity to reduce the Rc between the elastomer and the rigid substrate. Use of the thermally conductive elastomer as the TIM in chip cooling demonstrated superior heat dissipation capability, resulting in an 11 °C reduction in the chip temperature compared with that obtained with the commercial TIM. This work provides an effective strategy for balancing the Rc and modulus, broadening the application range of TIMs.
热界面材料是实现电子器件高效热管理的关键。传统的TIMs对低热接触电阻(Rc)要求极高的顺应性,这给实现高模量和低Rc带来了挑战。在这里,我们报告了一种弹性(>96%)导热弹性体,具有高弹性模量(12.3 MPa)和低Rc (12.3 K mm2 W-1),基于动态/非动态混合交联网络策略。非动态交联网络作为弹性体的骨架,提供弹性和鲁棒性,而具有动态特性的动态交联网络提供部分固态塑性,减少弹性体与刚性基体之间的Rc。在芯片冷却中使用导热弹性体作为TIM,显示出优越的散热能力,与商用TIM相比,芯片温度降低了11°C。该工作为平衡Rc和模量提供了一种有效的策略,拓宽了TIMs的应用范围。
{"title":"Resilient Thermal Interface Materials with Low Thermal Contact Resistance and High Modulus via Hybrid Cross-Linking Strategy","authors":"Junwei Li, Yang Tao, Zhihong Zhang, Yubo Luo, Xin Li* and Junyou Yang*, ","doi":"10.1021/acsmaterialslett.5c0051010.1021/acsmaterialslett.5c00510","DOIUrl":"https://doi.org/10.1021/acsmaterialslett.5c00510https://doi.org/10.1021/acsmaterialslett.5c00510","url":null,"abstract":"<p >Thermal interface materials (TIMs) are crucial for achieving efficient thermal management of electronic devices. Traditional TIMs require extreme compliance for low thermal contact resistance (<i>R</i><sub><i>c</i></sub>), resulting in the challenge of achieving both a high modulus and a low <i>R</i><sub><i>c</i></sub>. Here, we report a resilient (>96%) thermally conductive elastomer with a high elastic modulus (12.3 MPa) and a low <i>R</i><sub><i>c</i></sub> (12.3 K mm<sup>2</sup> W<sup>–1</sup>) based on a dynamic/nondynamic hybrid cross-linking network strategy. The nondynamic cross-linking network serves as the backbone of the elastomer, providing elasticity and robustness, while the dynamic cross-linking network with dynamic features offers partial solid-state plasticity to reduce the <i>R</i><sub><i>c</i></sub> between the elastomer and the rigid substrate. Use of the thermally conductive elastomer as the TIM in chip cooling demonstrated superior heat dissipation capability, resulting in an 11 °C reduction in the chip temperature compared with that obtained with the commercial TIM. This work provides an effective strategy for balancing the <i>R</i><sub>c</sub> and modulus, broadening the application range of TIMs.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"7 6","pages":"2133–2141 2133–2141"},"PeriodicalIF":9.6,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144189097","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-21DOI: 10.1021/acsmaterialslett.5c0046410.1021/acsmaterialslett.5c00464
Wei Zhu, Yuchen Tang, Shun Hu, Wenjing Xu, Dong Yu, Jun Cao, Tingjuan Gao* and Aiguo Shen*,
In the evolving landscape of information encryption technologies, the integration of optical materials into three-dimensional (3D) codes has emerged as a promising solution. However, current approaches were limited by coding capacity, detective permeability, and a complicated preparation process. Addressing this gap, we present an approach involving the development of 3D embedded, invisible Raman codes with chemical vibrations employing 3D-printable triple-bonded nanoparticles. These colorless triple-bonded nanoparticles, characterized by the distinct and stable spectral features of spontaneous Raman scattering, ensure high transparency, durability, and coding capacity. By embedding multiple, visually undetectable Raman-based QR codes within the internal structure of 3D printed objects, rather than using visible measures on 2D surfaces, our multilayered encryption system significantly enhances the information security by invalidating single-layer decoding attempts and requiring the combination of multiple layers to decrypt the embedded information. This innovative approach offers superior security and robustness in information security.
{"title":"Three-Dimensional Printable Triple-Bonded Polymer Nanoparticles for Invisible Information Encryption and Robust Anti-Counterfeiting","authors":"Wei Zhu, Yuchen Tang, Shun Hu, Wenjing Xu, Dong Yu, Jun Cao, Tingjuan Gao* and Aiguo Shen*, ","doi":"10.1021/acsmaterialslett.5c0046410.1021/acsmaterialslett.5c00464","DOIUrl":"https://doi.org/10.1021/acsmaterialslett.5c00464https://doi.org/10.1021/acsmaterialslett.5c00464","url":null,"abstract":"<p >In the evolving landscape of information encryption technologies, the integration of optical materials into three-dimensional (3D) codes has emerged as a promising solution. However, current approaches were limited by coding capacity, detective permeability, and a complicated preparation process. Addressing this gap, we present an approach involving the development of 3D embedded, invisible Raman codes with chemical vibrations employing 3D-printable triple-bonded nanoparticles. These colorless triple-bonded nanoparticles, characterized by the distinct and stable spectral features of spontaneous Raman scattering, ensure high transparency, durability, and coding capacity. By embedding multiple, visually undetectable Raman-based QR codes within the internal structure of 3D printed objects, rather than using visible measures on 2D surfaces, our multilayered encryption system significantly enhances the information security by invalidating single-layer decoding attempts and requiring the combination of multiple layers to decrypt the embedded information. This innovative approach offers superior security and robustness in information security.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"7 6","pages":"2343–2351 2343–2351"},"PeriodicalIF":9.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144189086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cerium metal–organic frameworks (Ce-MOFs) have attracted extensive attention due to their potential in photocatalytic applications. However, Ce-MOFs constructed with organic carboxylic acids as ligands typically exhibit wide band gaps, which limit their utilization in the visible-light region. This work proposes a strategy to design visible-light-active Ce-MOFs by employing quinoline sulfonic acid as a ligand. The synthesized compound (1-Ce) features a high surface area, open Ce metal sites, and large-sized 1D channels. Benefiting from ligand-to-metal charge transfer, 1-Ce demonstrates good visible light absorption. Additionally, the chelating coordination of nitrogen and oxygen atoms endows 1-Ce with excellent chemical stability. Owing to its abundant metal sites, high porosity, and visible light responsiveness, 1-Ce exhibits outstanding photocatalytic activity for CO2 reduction under visible light, achieving a CO production rate of 138 μmol·g–1·h–1─surpassing previously reported Ce-MOF photocatalysts.
{"title":"Cerium Metal–Organic Framework Incorporating Quinoline Sulfonic Acid for Photocatalytic Carbon Dioxide Reduction","authors":"Yingying Li, Tong Hao, Yu-Peng Han, Hui-Zi Li, Yayu Yan, Qiao-Hong Li, Shumei Chen*, Fei Wang* and Jian Zhang*, ","doi":"10.1021/acsmaterialslett.5c0034210.1021/acsmaterialslett.5c00342","DOIUrl":"https://doi.org/10.1021/acsmaterialslett.5c00342https://doi.org/10.1021/acsmaterialslett.5c00342","url":null,"abstract":"<p >Cerium metal–organic frameworks (Ce-MOFs) have attracted extensive attention due to their potential in photocatalytic applications. However, Ce-MOFs constructed with organic carboxylic acids as ligands typically exhibit wide band gaps, which limit their utilization in the visible-light region. This work proposes a strategy to design visible-light-active Ce-MOFs by employing quinoline sulfonic acid as a ligand. The synthesized compound (<b>1-Ce</b>) features a high surface area, open Ce metal sites, and large-sized 1D channels. Benefiting from ligand-to-metal charge transfer, <b>1-Ce</b> demonstrates good visible light absorption. Additionally, the chelating coordination of nitrogen and oxygen atoms endows <b>1-Ce</b> with excellent chemical stability. Owing to its abundant metal sites, high porosity, and visible light responsiveness, <b>1-Ce</b> exhibits outstanding photocatalytic activity for CO<sub>2</sub> reduction under visible light, achieving a CO production rate of 138 μmol·g<sup>–1</sup>·h<sup>–1</sup>─surpassing previously reported Ce-MOF photocatalysts.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"7 6","pages":"2337–2342 2337–2342"},"PeriodicalIF":9.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144189083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ultrablack coatings traditionally rely on complex micro/nanoengineering, limiting scalability and durability. Herein, we present a hyper-dispersion-based approach for the creation of micro- and nanostructured ultrablack coatings (solar absorptance of over 99%) via controlled aggregation of carboxylated carbon nanotubes (C–CNTs) in high-concentration colloidal systems. Molecular dynamics simulations revealed that the self-assembled hierarchical structures arise from the C–CNT aggregation. The use of high-temperature-resistant epoxy resin enhances adhesion, environmental resistance, and mechanical durability. The coatings maintained high solar absorptance and structural integrity under extreme thermal cycling and water flushing. In addition, we demonstrated that the coatings have excellent photothermal conversion efficiency, significantly raising the temperature of coated silk textiles under low solar irradiation and increasing the voltage output of thermoelectric devices by four times compared with uncoated ones. This scalable, efficient fabrication method requires no extra materials or complicated steps, demonstrating broad potential for solar energy and thermal management.
{"title":"Hyper-Dispersion-Driven Fabrication of Ultrablack Coatings","authors":"Xun-En Wu, Yong Zhang, Yida Wang, Xiaoping Liang, Mei Zou, Yaoyao Zhou, Siming Zhao, Haomin Wang, Mengjia Zhu, Haojie Lu, Jiongke Jin, Donghang Li, Rufan Zhang and Yingying Zhang*, ","doi":"10.1021/acsmaterialslett.5c0043510.1021/acsmaterialslett.5c00435","DOIUrl":"https://doi.org/10.1021/acsmaterialslett.5c00435https://doi.org/10.1021/acsmaterialslett.5c00435","url":null,"abstract":"<p >Ultrablack coatings traditionally rely on complex micro/nanoengineering, limiting scalability and durability. Herein, we present a hyper-dispersion-based approach for the creation of micro- and nanostructured ultrablack coatings (solar absorptance of over 99%) via controlled aggregation of carboxylated carbon nanotubes (C–CNTs) in high-concentration colloidal systems. Molecular dynamics simulations revealed that the self-assembled hierarchical structures arise from the C–CNT aggregation. The use of high-temperature-resistant epoxy resin enhances adhesion, environmental resistance, and mechanical durability. The coatings maintained high solar absorptance and structural integrity under extreme thermal cycling and water flushing. In addition, we demonstrated that the coatings have excellent photothermal conversion efficiency, significantly raising the temperature of coated silk textiles under low solar irradiation and increasing the voltage output of thermoelectric devices by four times compared with uncoated ones. This scalable, efficient fabrication method requires no extra materials or complicated steps, demonstrating broad potential for solar energy and thermal management.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"7 6","pages":"2352–2359 2352–2359"},"PeriodicalIF":9.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144189084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-21DOI: 10.1021/acsmaterialslett.5c0049610.1021/acsmaterialslett.5c00496
Kenichi Goushi*, Masahiro Nagano and Chihaya Adachi*,
In this study, we focus on benzobisoxazole (BOX) derivatives with the aim of achieving large stimulated emission cross sections, which are expected to contribute to lower laser thresholds and high stability. While both optically and electrically pumped organic semiconductor lasers have the potential to provide miniaturized lasers with wavelength tunability from ultraviolet to infrared, the development of organic semiconductors with low laser thresholds remains crucial for realizing stable devices. We report a low amplified spontaneous emission (ASE) threshold of BOX derivatives, which are doped into 4,4′-bis(carbazol-9-yl)biphenyl (CBP) host layers, with values as low as approximately 1 μJ/cm2. Further, we demonstrate high photostability under continuous photoexcitation, suggesting that BOX derivatives are promising candidates as emitting materials for organic semiconductor lasers (OSLs).
{"title":"Low-Threshold Amplified Spontaneous Emission of Benzobisoxazole Derivatives in a Doped Film","authors":"Kenichi Goushi*, Masahiro Nagano and Chihaya Adachi*, ","doi":"10.1021/acsmaterialslett.5c0049610.1021/acsmaterialslett.5c00496","DOIUrl":"https://doi.org/10.1021/acsmaterialslett.5c00496https://doi.org/10.1021/acsmaterialslett.5c00496","url":null,"abstract":"<p >In this study, we focus on benzobisoxazole (BOX) derivatives with the aim of achieving large stimulated emission cross sections, which are expected to contribute to lower laser thresholds and high stability. While both optically and electrically pumped organic semiconductor lasers have the potential to provide miniaturized lasers with wavelength tunability from ultraviolet to infrared, the development of organic semiconductors with low laser thresholds remains crucial for realizing stable devices. We report a low amplified spontaneous emission (ASE) threshold of BOX derivatives, which are doped into 4,4′-bis(carbazol-9-yl)biphenyl (CBP) host layers, with values as low as approximately 1 μJ/cm<sup>2</sup>. Further, we demonstrate high photostability under continuous photoexcitation, suggesting that BOX derivatives are promising candidates as emitting materials for organic semiconductor lasers (OSLs).</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"7 6","pages":"2360–2365 2360–2365"},"PeriodicalIF":9.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144189087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-21DOI: 10.1021/acsmaterialslett.5c0049510.1021/acsmaterialslett.5c00495
Jing Kang, Xiaohan Wang* and Junqi Sun,
Shock-absorbing fibers (SAFs) are highly regarded for their effectiveness in energy-absorbing applications. Existing SAFs are plastic fibers that can only be used once, are nonrecyclable, and lack damage tolerance. Herein, we fabricate recyclable, mechanically robust elastic SAFs with exceptional damage tolerance via wet spinning of multiblock polyurethane (PU) composed of polycaprolactone (PCL) and polytetrahydrofuran (PTMG) segments. The SAFs are denoted as PU–PCL70, achieving an ultrahigh true strength of 908.8 MPa, a high damping efficiency of 87%, and a record fracture energy of 4042 kJ m–2. Mechanistic analysis reveals that the superior performance of PU–PCL70 originated from the oriented hierarchical phase-separated nanodomains formed by hydrogen and coordination bonds and rigid PCL segments. These rigid nanodomains are capable of deformation and disintegration to effectively absorb energy. These nanodomains can autonomously re-form, enabling the fibers with reusability without treatment. The dynamic nature of these nanodomains allows for complete recyclability of PU–PCL70 through respinning.
{"title":"Engineering of Hierarchical Phase-Separated Nanodomains toward Elastic and Recyclable Shock-Absorbing Fibers with Exceptional Damage Tolerance and Damping Capacity","authors":"Jing Kang, Xiaohan Wang* and Junqi Sun, ","doi":"10.1021/acsmaterialslett.5c0049510.1021/acsmaterialslett.5c00495","DOIUrl":"https://doi.org/10.1021/acsmaterialslett.5c00495https://doi.org/10.1021/acsmaterialslett.5c00495","url":null,"abstract":"<p >Shock-absorbing fibers (SAFs) are highly regarded for their effectiveness in energy-absorbing applications. Existing SAFs are plastic fibers that can only be used once, are nonrecyclable, and lack damage tolerance. Herein, we fabricate recyclable, mechanically robust elastic SAFs with exceptional damage tolerance via wet spinning of multiblock polyurethane (PU) composed of polycaprolactone (PCL) and polytetrahydrofuran (PTMG) segments. The SAFs are denoted as PU–PCL<sub>70</sub>, achieving an ultrahigh true strength of 908.8 MPa, a high damping efficiency of 87%, and a record fracture energy of 4042 kJ m<sup>–2</sup>. Mechanistic analysis reveals that the superior performance of PU–PCL<sub>70</sub> originated from the oriented hierarchical phase-separated nanodomains formed by hydrogen and coordination bonds and rigid PCL segments. These rigid nanodomains are capable of deformation and disintegration to effectively absorb energy. These nanodomains can autonomously re-form, enabling the fibers with reusability without treatment. The dynamic nature of these nanodomains allows for complete recyclability of PU–PCL<sub>70</sub> through respinning.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"7 6","pages":"2328–2336 2328–2336"},"PeriodicalIF":9.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144189156","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Calcium ion (Ca2+) overload has been extensively explored in tumor therapy; however, the inadequate concentrations of Ca2+ frequently result in suboptimal therapeutic outcomes. In this study, we developed curcumin (Cur)-loaded amorphous carbonated calcium nanoparticles (CaCur, NPs), which were coated with cancer cell membranes (CCM) to facilitate targeted delivery. Additionally, the fluorescence dye DiR was embedded into the CCM to achieve photothermal effects, thereby enabling the opening of the transient receptor potential vanilloid 1 (TRPV1) channel, which promotes amplified Ca2+ overload through increased Ca2+ influx. This work provides a photothermal amplification strategy aiming at improving antitumor efficacy by robustly enhancing the extent of Ca2+ overload through a tripartite collaboration.
{"title":"Photothermal Amplification of Calcium Ion Overload for Tumor Homing Therapy","authors":"Yu Chen, Shuo Gao, Cong-Min Huo, Xin-Cheng He, Yucheng Zuo, Jun-Nan Zhang, Wei Xue* and Jing-Yi Zhu*, ","doi":"10.1021/acsmaterialslett.5c0046110.1021/acsmaterialslett.5c00461","DOIUrl":"https://doi.org/10.1021/acsmaterialslett.5c00461https://doi.org/10.1021/acsmaterialslett.5c00461","url":null,"abstract":"<p >Calcium ion (Ca<sup>2+</sup>) overload has been extensively explored in tumor therapy; however, the inadequate concentrations of Ca<sup>2+</sup> frequently result in suboptimal therapeutic outcomes. In this study, we developed curcumin (Cur)-loaded amorphous carbonated calcium nanoparticles (CaCur, NPs), which were coated with cancer cell membranes (CCM) to facilitate targeted delivery. Additionally, the fluorescence dye DiR was embedded into the CCM to achieve photothermal effects, thereby enabling the opening of the transient receptor potential vanilloid 1 (TRPV1) channel, which promotes amplified Ca<sup>2+</sup> overload through increased Ca<sup>2+</sup> influx. This work provides a photothermal amplification strategy aiming at improving antitumor efficacy by robustly enhancing the extent of Ca<sup>2+</sup> overload through a tripartite collaboration.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"7 6","pages":"2319–2327 2319–2327"},"PeriodicalIF":9.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144189085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-20DOI: 10.1021/acsmaterialslett.5c0062710.1021/acsmaterialslett.5c00627
Rou Yuan, Xiao-Hui Wang, Shi-Bin Yin, Xuan Ai, Yun-Chao Yin*, Yu Chen* and Shu-Ni Li*,
The hydrazine oxidation reaction (HzOR)-assisted nitrate reduction reaction (NO3RR) technology provides an energy-efficient alternative to traditional ammonia (NH3) synthesis while promoting environmental sustainability. Herein, we synthesized hierarchical CuCo2O4 nanodendrites (NDs) composed of ultrathin nanosheet subunits with a spinel structure via a simple coprecipitation method followed by annealing. This spinel framework features well-defined Cu–Co pairs. In an alkaline solution, CuCo2O4 NDs achieve a high Faradaic efficiency (97.86%) and an impressive NH3 yield (34.23 mg h–1 mgcat–1) at −0.3 V for NO3RR, accompanied by excellent stability. These properties arise from the synergistic effect of Cu–Co pairs and the two-dimensional architecture. When applied in a CuCo2O4 NDs||CuCo2O4 NDs electrolyzer, the HzOR-assisted NO3RR operates at 0.997 V (10 mA cm–2), which is 573 mV lower than the conventional NO3RR system with oxygen evolution. This work presents a low-voltage NH3 synthesis strategy coupled with nitrogen pollutant mitigation.
肼氧化反应(HzOR)辅助硝酸还原反应(NO3RR)技术为传统氨(NH3)合成提供了一种节能的替代方案,同时促进了环境的可持续性。本文采用简单共沉淀法和退火法制备了具有尖晶石结构的超薄纳米片亚基CuCo2O4纳米枝晶(ndds)。这种尖晶石骨架具有明确定义的Cu-Co对。在碱性溶液中,CuCo2O4 NDs在−0.3 V NO3RR条件下具有较高的法拉第效率(97.86%)和NH3产率(34.23 mg h-1 mgcat-1),并具有良好的稳定性。这些性质源于Cu-Co对的协同效应和二维结构。当应用于CuCo2O4 NDs||CuCo2O4 NDs电解槽时,hzor辅助NO3RR工作在0.997 V (10 mA cm-2),比传统的出氧NO3RR系统低573 mV。这项工作提出了一种低压NH3合成策略,结合氮污染物的缓解。
{"title":"Energy-Efficient Ammonia Production via Coupled Hydrazine Hydrate Oxidation Using CuCo2O4 Nanodendrites with Ultrathin Nanosheet Subunits","authors":"Rou Yuan, Xiao-Hui Wang, Shi-Bin Yin, Xuan Ai, Yun-Chao Yin*, Yu Chen* and Shu-Ni Li*, ","doi":"10.1021/acsmaterialslett.5c0062710.1021/acsmaterialslett.5c00627","DOIUrl":"https://doi.org/10.1021/acsmaterialslett.5c00627https://doi.org/10.1021/acsmaterialslett.5c00627","url":null,"abstract":"<p >The hydrazine oxidation reaction (HzOR)-assisted nitrate reduction reaction (NO<sub>3</sub>RR) technology provides an energy-efficient alternative to traditional ammonia (NH<sub>3</sub>) synthesis while promoting environmental sustainability. Herein, we synthesized hierarchical CuCo<sub>2</sub>O<sub>4</sub> nanodendrites (NDs) composed of ultrathin nanosheet subunits with a spinel structure via a simple coprecipitation method followed by annealing. This spinel framework features well-defined Cu–Co pairs. In an alkaline solution, CuCo<sub>2</sub>O<sub>4</sub> NDs achieve a high Faradaic efficiency (97.86%) and an impressive NH<sub>3</sub> yield (34.23 mg h<sup>–1</sup> mg<sub>cat</sub><sup>–1</sup>) at −0.3 V for NO<sub>3</sub>RR, accompanied by excellent stability. These properties arise from the synergistic effect of Cu–Co pairs and the two-dimensional architecture. When applied in a CuCo<sub>2</sub>O<sub>4</sub> NDs||CuCo<sub>2</sub>O<sub>4</sub> NDs electrolyzer, the HzOR-assisted NO<sub>3</sub>RR operates at 0.997 V (10 mA cm<sup>–2</sup>), which is 573 mV lower than the conventional NO<sub>3</sub>RR system with oxygen evolution. This work presents a low-voltage NH<sub>3</sub> synthesis strategy coupled with nitrogen pollutant mitigation.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"7 6","pages":"2310–2318 2310–2318"},"PeriodicalIF":9.6,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144189080","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}