Pub Date : 2024-10-21eCollection Date: 2024-11-22DOI: 10.1021/acsaenm.4c00534
Rúben R Ferreira, Dario Mosca, Tiago Moreira, Vivek Chandrakant Wakchaure, Gianvito Romano, Antoine Stopin, Carlos Pinheiro, Alexander M T Luci, Luís M A Perdigão, Giovanni Costantini, Heinz Amenitsch, Cesar A T Laia, A Jorge Parola, Laura Maggini, Davide Bonifazi
Organic electrochromic polymers hold great potential for integration into low-power flexible electrochromic displays (F-ECDs) due to their wide range of colors and simple processing. However, challenges such as inefficient charge transfer and degradation upon device integration hinder their practical applications. Herein, we report an innovative, general approach that utilizes template-induced supramolecular nanostructuring to engineer established electrochromic polymers, enhancing their performance and durability. We modified a well-known, albeit underperforming in F-ECDs, poly-thiophene polymer (ECP Orange; PT) by incorporating a pyrene appendage, resulting in a copolymer (PTPy) capable of undergoing large-scale assembly in the presence of multi-walled carbon nanotubes (MWCNTs), driven by the establishment of π-π interactions between the pyrene and the MWCNTs (PTPy/MWCNTs). F-ECDs based on these hybrids, produced by spray coating, exhibit improved color switching speeds (t90OX = 3.6 s, t90RED = 0.3 s) compared to those of the PT polymer (t90OX = 53.2 s, t90RED = 2.5 s). Additionally, PTPy/MWCNTs F-ECDs demonstrate longer cyclability (half-life based on ΔE, ΔE50% = 17.6k cycles) compared to PT (ΔE50% = 278 cycles), also when blended with MWCNTs (ΔE50% = 282 cycles). This work highlights the pivotal role of engineered supramolecular nanostructuring in boosting the performance of organic electrochromic materials, making them suitable for F-ECD scalable commercial applications.
{"title":"Long-Range Supramolecular Assembly of a Pyrene-Derivatized Polythiophene/MWCNT Hybrid for Resilient Flexible Electrochromic Displays.","authors":"Rúben R Ferreira, Dario Mosca, Tiago Moreira, Vivek Chandrakant Wakchaure, Gianvito Romano, Antoine Stopin, Carlos Pinheiro, Alexander M T Luci, Luís M A Perdigão, Giovanni Costantini, Heinz Amenitsch, Cesar A T Laia, A Jorge Parola, Laura Maggini, Davide Bonifazi","doi":"10.1021/acsaenm.4c00534","DOIUrl":"10.1021/acsaenm.4c00534","url":null,"abstract":"<p><p>Organic electrochromic polymers hold great potential for integration into low-power flexible electrochromic displays (F-ECDs) due to their wide range of colors and simple processing. However, challenges such as inefficient charge transfer and degradation upon device integration hinder their practical applications. Herein, we report an innovative, general approach that utilizes template-induced supramolecular nanostructuring to engineer established electrochromic polymers, enhancing their performance and durability. We modified a well-known, albeit underperforming in F-ECDs, poly-thiophene polymer (ECP Orange; PT) by incorporating a pyrene appendage, resulting in a copolymer (<b>PTPy</b>) capable of undergoing large-scale assembly in the presence of multi-walled carbon nanotubes (MWCNTs), driven by the establishment of π-π interactions between the pyrene and the MWCNTs (<b>PTPy/MWCNTs</b>). F-ECDs based on these hybrids, produced by spray coating, exhibit improved color switching speeds (<i>t</i> <sub>90</sub> <sup>OX</sup> = 3.6 s, <i>t</i> <sub>90</sub> <sup>RED</sup> = 0.3 s) compared to those of the <b>PT</b> polymer (<i>t</i> <sub>90</sub> <sup>OX</sup> = 53.2 s, <i>t</i> <sub>90</sub> <sup>RED</sup> = 2.5 s). Additionally, <b>PTPy/MWCNTs</b> F-ECDs demonstrate longer cyclability (half-life based on Δ<i>E</i>, Δ<i>E</i> <sub>50%</sub> = 17.6k cycles) compared to <b>PT</b> (Δ<i>E</i> <sub>50%</sub> = 278 cycles), also when blended with MWCNTs (Δ<i>E</i> <sub>50%</sub> = 282 cycles). This work highlights the pivotal role of engineered supramolecular nanostructuring in boosting the performance of organic electrochromic materials, making them suitable for F-ECD scalable commercial applications.</p>","PeriodicalId":55639,"journal":{"name":"ACS Applied Engineering Materials","volume":"2 11","pages":"2640-2650"},"PeriodicalIF":0.0,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11590053/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142741532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-21DOI: 10.1021/acsaenm.4c0053410.1021/acsaenm.4c00534
Rúben R. Ferreira, Dario Mosca, Tiago Moreira, Vivek Chandrakant Wakchaure, Gianvito Romano, Antoine Stopin, Carlos Pinheiro, Alexander M. T. Luci, Luís M. A. Perdigão, Giovanni Costantini, Heinz Amenitsch, Cesar A. T. Laia, A. Jorge Parola, Laura Maggini* and Davide Bonifazi*,
Organic electrochromic polymers hold great potential for integration into low-power flexible electrochromic displays (F-ECDs) due to their wide range of colors and simple processing. However, challenges such as inefficient charge transfer and degradation upon device integration hinder their practical applications. Herein, we report an innovative, general approach that utilizes template-induced supramolecular nanostructuring to engineer established electrochromic polymers, enhancing their performance and durability. We modified a well-known, albeit underperforming in F-ECDs, poly-thiophene polymer (ECP Orange; PT) by incorporating a pyrene appendage, resulting in a copolymer (PTPy) capable of undergoing large-scale assembly in the presence of multi-walled carbon nanotubes (MWCNTs), driven by the establishment of π–π interactions between the pyrene and the MWCNTs (PTPy/MWCNTs). F-ECDs based on these hybrids, produced by spray coating, exhibit improved color switching speeds (t90OX = 3.6 s, t90RED = 0.3 s) compared to those of the PT polymer (t90OX = 53.2 s, t90RED = 2.5 s). Additionally, PTPy/MWCNTs F-ECDs demonstrate longer cyclability (half-life based on ΔE, ΔE50% = 17.6k cycles) compared to PT (ΔE50% = 278 cycles), also when blended with MWCNTs (ΔE50% = 282 cycles). This work highlights the pivotal role of engineered supramolecular nanostructuring in boosting the performance of organic electrochromic materials, making them suitable for F-ECD scalable commercial applications.
{"title":"Long-Range Supramolecular Assembly of a Pyrene-Derivatized Polythiophene/MWCNT Hybrid for Resilient Flexible Electrochromic Displays","authors":"Rúben R. Ferreira, Dario Mosca, Tiago Moreira, Vivek Chandrakant Wakchaure, Gianvito Romano, Antoine Stopin, Carlos Pinheiro, Alexander M. T. Luci, Luís M. A. Perdigão, Giovanni Costantini, Heinz Amenitsch, Cesar A. T. Laia, A. Jorge Parola, Laura Maggini* and Davide Bonifazi*, ","doi":"10.1021/acsaenm.4c0053410.1021/acsaenm.4c00534","DOIUrl":"https://doi.org/10.1021/acsaenm.4c00534https://doi.org/10.1021/acsaenm.4c00534","url":null,"abstract":"<p >Organic electrochromic polymers hold great potential for integration into low-power flexible electrochromic displays (F-ECDs) due to their wide range of colors and simple processing. However, challenges such as inefficient charge transfer and degradation upon device integration hinder their practical applications. Herein, we report an innovative, general approach that utilizes template-induced supramolecular nanostructuring to engineer established electrochromic polymers, enhancing their performance and durability. We modified a well-known, albeit underperforming in F-ECDs, poly-thiophene polymer (ECP Orange; PT) by incorporating a pyrene appendage, resulting in a copolymer (<b>PTPy</b>) capable of undergoing large-scale assembly in the presence of multi-walled carbon nanotubes (MWCNTs), driven by the establishment of π–π interactions between the pyrene and the MWCNTs (<b>PTPy/MWCNTs</b>). F-ECDs based on these hybrids, produced by spray coating, exhibit improved color switching speeds (<i>t</i><sub>90</sub><sup>OX</sup> = 3.6 s, <i>t</i><sub>90</sub><sup>RED</sup> = 0.3 s) compared to those of the <b>PT</b> polymer (<i>t</i><sub>90</sub><sup>OX</sup> = 53.2 s, <i>t</i><sub>90</sub><sup>RED</sup> = 2.5 s). Additionally, <b>PTPy/MWCNTs</b> F-ECDs demonstrate longer cyclability (half-life based on Δ<i>E</i>, Δ<i>E</i><sub>50%</sub> = 17.6k cycles) compared to <b>PT</b> (Δ<i>E</i><sub>50%</sub> = 278 cycles), also when blended with MWCNTs (Δ<i>E</i><sub>50%</sub> = 282 cycles). This work highlights the pivotal role of engineered supramolecular nanostructuring in boosting the performance of organic electrochromic materials, making them suitable for F-ECD scalable commercial applications.</p>","PeriodicalId":55639,"journal":{"name":"ACS Applied Engineering Materials","volume":"2 11","pages":"2640–2650 2640–2650"},"PeriodicalIF":0.0,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsaenm.4c00534","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-18DOI: 10.1021/acsaenm.4c0056610.1021/acsaenm.4c00566
Jessika Pazol, Xiao Tong, Gregory S. Doerk, Dina Bracho, Samir A. Bello, Luarys Díaz-Fuentes and Eduardo Nicolau*,
Zwitterionic polymers have proven to be a promising nonfouling material that can be applied in the design of selective layers of thin film composite (TFC) membranes. Extending the permeability and usage of TFC membranes have attracted increasing interest in membrane-based desalination processes since water-flux reduction associated with biofouling nowadays persists as a common challenge. By virtue of its strong hydration, this polymer category is very useful to counteract biofouling in marine and biomedical systems, but the benefits from their application in membrane technology are still emerging. The efficacy of the nonfouling property as a function of the polymer’s molecular weight remains unknown. In pursuit of that vision, this study fosters new scientific insights via probing different molecular weights of poly(carboxybetain methacrylate) (PCBMA) coated on the surface as a selective layer for the prepared TFC membranes. The coated zwitterionic membranes (zM) exhibited excellent performance in preventing water flux decay in a bench-scale forward osmosis system. The prepared zM membranes revealed enhanced hydrophilic properties and retained their operational water flux when compared to the control. Our results suggest that using an intermediate-size molecular weight (PCBMA Mn 50,000) will result in the best operational performance. The intermediate size resulted in the lowest flux decline rate (Rt) of 0.01 ± 0.001 (zM-50) when compared to the unmodified control membrane 0.56 ± 0.071 (M0) after using a model BSA foulant solution. Furthermore, all coated membranes exhibited similar trends in the observed reverse salt flux profiles, as well. The constructed zM membranes will serve as a model to develop further selective layers in the construction of TFC membranes.
{"title":"Insights into Probing the Effect of Molecular Weight of Poly(carboxybetaine methacrylate) on the Performance of Forward Osmosis Desalination","authors":"Jessika Pazol, Xiao Tong, Gregory S. Doerk, Dina Bracho, Samir A. Bello, Luarys Díaz-Fuentes and Eduardo Nicolau*, ","doi":"10.1021/acsaenm.4c0056610.1021/acsaenm.4c00566","DOIUrl":"https://doi.org/10.1021/acsaenm.4c00566https://doi.org/10.1021/acsaenm.4c00566","url":null,"abstract":"<p >Zwitterionic polymers have proven to be a promising nonfouling material that can be applied in the design of selective layers of thin film composite (TFC) membranes. Extending the permeability and usage of TFC membranes have attracted increasing interest in membrane-based desalination processes since water-flux reduction associated with biofouling nowadays persists as a common challenge. By virtue of its strong hydration, this polymer category is very useful to counteract biofouling in marine and biomedical systems, but the benefits from their application in membrane technology are still emerging. The efficacy of the nonfouling property as a function of the polymer’s molecular weight remains unknown. In pursuit of that vision, this study fosters new scientific insights via probing different molecular weights of poly(carboxybetain methacrylate) (PCBMA) coated on the surface as a selective layer for the prepared TFC membranes. The coated zwitterionic membranes (zM) exhibited excellent performance in preventing water flux decay in a bench-scale forward osmosis system. The prepared zM membranes revealed enhanced hydrophilic properties and retained their operational water flux when compared to the control. Our results suggest that using an intermediate-size molecular weight (PCBMA <i>M</i><sub>n</sub> 50,000) will result in the best operational performance. The intermediate size resulted in the lowest flux decline rate (<i>R</i><sub>t</sub>) of 0.01 ± 0.001 (zM-50) when compared to the unmodified control membrane 0.56 ± 0.071 (M0) after using a model BSA foulant solution. Furthermore, all coated membranes exhibited similar trends in the observed reverse salt flux profiles, as well. The constructed zM membranes will serve as a model to develop further selective layers in the construction of TFC membranes.</p>","PeriodicalId":55639,"journal":{"name":"ACS Applied Engineering Materials","volume":"2 11","pages":"2675–2688 2675–2688"},"PeriodicalIF":0.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685157","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-14DOI: 10.1021/acsaenm.4c0055310.1021/acsaenm.4c00553
Man He, Chen Wang, Hua Yang, Dong-Ying Wu, Jey-Jau Lee, Fangwei Wang*, Maxim Avdeev* and Wang Hay Kan*,
Since the development of Ti2.08Zr null matrix alloy by Sidhu et al. in 1956, only a handful of new null matrix alloys have been reported over the past 70 years. Most of them are not suitable to be utilized in applications due to the poor chemical/physical stabilities and the presence of strong short-range ordering in the structures. For the first time, a new family of V-based null matrix alloys V1–xMx (M = Al, Nb, Ta, Ni, Fe, Sn, and Mo; x < 0.1 in molar ratio) were synthesized by an arc melting method. The structural and physical properties were systematically evaluated. All of the alloys crystallize into a cubic body center structure with a space group of Im3̅m. Based on the neutron diffraction (ND), X-ray diffraction, and X-ray pair distribution function, the dopants (except Mo) and V atoms were atomically homogeneous and distributed into the 2a sites of Im3̅m. Small angle neutron scattering was used to probe the bulk neutron transparent properties and the possibilities of dopant clustering at the mesoscopic level. These conditions yield a specific feature in which the ND patterns of the alloys have no diffraction peaks. Hard X-ray absorption spectroscopy revealed that the valence states of V remained 0 in all investigated alloys. Nonetheless, a small degree of charge redistribution were observed. The Coulombic energies of configurations of supercells with different degrees of dopants clustering were also computed for comparison. Tensile tests were also conducted to evaluate the mechanical stress and strain properties. The high-temperature oxidation properties were examined by thermogravimetric analysis differential scanning calorimetry. Among the investigated samples, Nb-doped and Ni-doped V-based alloys show superior chemical and mechanical properties, which could be promising to be utilized to develop advanced in situ devices and high-temperature/pressure neutron scattering sample holders for ND and total scattering measurements.
自 1956 年 Sidhu 等人开发出 Ti2.08Zr 空基合金以来,过去 70 年中仅有少数几种新型空基合金被报道。由于化学/物理稳定性较差以及结构中存在较强的短程有序性,它们大多不适合在应用中使用。我们首次采用电弧熔化法合成了一系列新型 V 基空基合金 V1-xMx(M = Al、Nb、Ta、Ni、Fe、Sn 和 Mo;x < 摩尔比为 0.1)。对其结构和物理性质进行了系统评估。所有合金都结晶成立方体中心结构,空间群为 Im3̅m。根据中子衍射(ND)、X 射线衍射和 X 射线对分布函数,掺杂物(除 Mo 外)和 V 原子在原子上是均匀的,并分布在 Im3̅m 的 2a 位点上。小角中子散射被用来探测体中子透明特性以及掺杂剂在介观层面上聚类的可能性。这些条件产生了一个特殊的特征,即合金的 ND 图形没有衍射峰。硬 X 射线吸收光谱显示,在所有研究合金中,V 的价态都保持为 0。尽管如此,还是观察到了少量的电荷再分布。为了进行比较,还计算了不同掺杂程度的超级电池构型的库仑能量。此外,还进行了拉伸试验,以评估机械应力和应变特性。通过热重分析差示扫描量热法检测了高温氧化特性。在所研究的样品中,掺铌和掺镍的 V 基合金显示出优异的化学和机械性能,有望用于开发先进的原位设备和高温/高压中子散射样品架,以进行 ND 和全散射测量。
{"title":"A Family of V-Based Null Matrix Alloys with Atomic and Mesoscopic Homogeneity","authors":"Man He, Chen Wang, Hua Yang, Dong-Ying Wu, Jey-Jau Lee, Fangwei Wang*, Maxim Avdeev* and Wang Hay Kan*, ","doi":"10.1021/acsaenm.4c0055310.1021/acsaenm.4c00553","DOIUrl":"https://doi.org/10.1021/acsaenm.4c00553https://doi.org/10.1021/acsaenm.4c00553","url":null,"abstract":"<p >Since the development of Ti<sub>2.08</sub>Zr null matrix alloy by Sidhu et al. in 1956, only a handful of new null matrix alloys have been reported over the past 70 years. Most of them are not suitable to be utilized in applications due to the poor chemical/physical stabilities and the presence of strong short-range ordering in the structures. For the first time, a new family of V-based null matrix alloys V<sub>1–<i>x</i></sub>M<sub><i>x</i></sub> (M = Al, Nb, Ta, Ni, Fe, Sn, and Mo; <i>x</i> < 0.1 in molar ratio) were synthesized by an arc melting method. The structural and physical properties were systematically evaluated. All of the alloys crystallize into a cubic body center structure with a space group of <i>Im</i>3̅<i>m</i>. Based on the neutron diffraction (ND), X-ray diffraction, and X-ray pair distribution function, the dopants (except Mo) and V atoms were atomically homogeneous and distributed into the 2a sites of <i>Im</i>3̅<i>m</i>. Small angle neutron scattering was used to probe the bulk neutron transparent properties and the possibilities of dopant clustering at the mesoscopic level. These conditions yield a specific feature in which the ND patterns of the alloys have no diffraction peaks. Hard X-ray absorption spectroscopy revealed that the valence states of V remained 0 in all investigated alloys. Nonetheless, a small degree of charge redistribution were observed. The Coulombic energies of configurations of supercells with different degrees of dopants clustering were also computed for comparison. Tensile tests were also conducted to evaluate the mechanical stress and strain properties. The high-temperature oxidation properties were examined by thermogravimetric analysis differential scanning calorimetry. Among the investigated samples, Nb-doped and Ni-doped V-based alloys show superior chemical and mechanical properties, which could be promising to be utilized to develop advanced in situ devices and high-temperature/pressure neutron scattering sample holders for ND and total scattering measurements.</p>","PeriodicalId":55639,"journal":{"name":"ACS Applied Engineering Materials","volume":"2 10","pages":"2468–2477 2468–2477"},"PeriodicalIF":0.0,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142517505","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hydride content in perovskite oxyhydrides represents a crucial parameter that governs properties of the materials. However, the synthesis of the oxyhidrides with precise control over the hydride content x remains a challenging task because of the time-consuming and/or destructive analytical methods typically used for the determination of x. Here, we report an image-based machine learning (ML) system for prediction of the hydride contents x in a perovskite oxyhydride BaTiO3–xHx using a picture of powder material as a quick evaluation method of hydride content x. The ML system, which employs the ExtraTrees algorithm, enabled the prediction of x with a mean absolute error of 0.013 and a low running cost. Although a similar ML system constructed by convolutional neural networks (CNN) that we used in the previous study demonstrated comparable accuracy in the prediction, the system with ExtraTrees was more computationally efficient, thus was applied as a nondestructive and quick analytical method for hydride content x. Using the ML system, detailed profiles of thermal hydrogen release of BaTiO3–xHx were quantitatively analyzed to demonstrate the feasibility of fine-tuning the hydride content within 0 ≤ x ≤ 0.4 by adjusting the processing temperature. In the case of powder samples comprising mixtures of the oxyhydride with different hydride contents, the ML-based prediction provided an almost averaged value for x. The present results demonstrate an application of image-based ML for the fine-tuning of oxyhidride materials.
过氧化物氧氢化物中的氢化物含量是影响材料特性的关键参数。然而,由于测定氢化物含量 x 通常采用耗时和/或破坏性的分析方法,因此合成氢氧化合物并精确控制氢化物含量 x 仍然是一项具有挑战性的任务。在此,我们报告了一种基于图像的机器学习(ML)系统,该系统使用粉末材料的图片作为氢化物含量 x 的快速评估方法,用于预测包晶氧酸酐 BaTiO3-xHx 中的氢化物含量 x。虽然我们在之前的研究中使用的由卷积神经网络(CNN)构建的类似 ML 系统的预测精度相当,但使用 ExtraTrees 算法的系统计算效率更高,因此被用作氢化物含量 x 的无损快速分析方法。使用 ML 系统,我们定量分析了 BaTiO3-xHx 的热氢释放的详细曲线,证明了通过调整加工温度在 0 ≤ x ≤ 0.4 范围内微调氢化物含量的可行性。对于由不同氢化物含量的氢氧化合物混合物组成的粉末样品,基于 ML 的预测几乎提供了 x 的平均值。
{"title":"Hydride Content Control of Perovskite Oxyhydride BaTiO3–xHx Supported by Image-Based Machine Learning","authors":"Taichi Sano, Yuki Ide*, Tatsuya Tsumori, Hiroki Ubukata, Ichigaku Takigawa, Hiroshi Kageyama and Yasuhide Inokuma*, ","doi":"10.1021/acsaenm.4c0041710.1021/acsaenm.4c00417","DOIUrl":"https://doi.org/10.1021/acsaenm.4c00417https://doi.org/10.1021/acsaenm.4c00417","url":null,"abstract":"<p >Hydride content in perovskite oxyhydrides represents a crucial parameter that governs properties of the materials. However, the synthesis of the oxyhidrides with precise control over the hydride content <i>x</i> remains a challenging task because of the time-consuming and/or destructive analytical methods typically used for the determination of <i>x</i>. Here, we report an image-based machine learning (ML) system for prediction of the hydride contents <i>x</i> in a perovskite oxyhydride BaTiO<sub>3–<i>x</i></sub>H<sub><i>x</i></sub> using a picture of powder material as a quick evaluation method of hydride content <i>x</i>. The ML system, which employs the ExtraTrees algorithm, enabled the prediction of <i>x</i> with a mean absolute error of 0.013 and a low running cost. Although a similar ML system constructed by convolutional neural networks (CNN) that we used in the previous study demonstrated comparable accuracy in the prediction, the system with ExtraTrees was more computationally efficient, thus was applied as a nondestructive and quick analytical method for hydride content <i>x</i>. Using the ML system, detailed profiles of thermal hydrogen release of BaTiO<sub>3–<i>x</i></sub>H<sub><i>x</i></sub> were quantitatively analyzed to demonstrate the feasibility of fine-tuning the hydride content within 0 ≤ <i>x</i> ≤ 0.4 by adjusting the processing temperature. In the case of powder samples comprising mixtures of the oxyhydride with different hydride contents, the ML-based prediction provided an almost averaged value for <i>x</i>. The present results demonstrate an application of image-based ML for the fine-tuning of oxyhidride materials.</p>","PeriodicalId":55639,"journal":{"name":"ACS Applied Engineering Materials","volume":"2 10","pages":"2391–2396 2391–2396"},"PeriodicalIF":0.0,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142551077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-11DOI: 10.1021/acsaenm.4c0048310.1021/acsaenm.4c00483
Irfan Majeed Bhat, Tabassum Ara and Saifullah Lone*,
The spontaneous extraction of organic immiscible liquids using oil-repellent membranes holds substantial research significance, particularly in the domain of oil–water mixture separation. However, the development of such membranes is inherently challenging due to the traditionally complex and multistep fabrication processes. This work introduces a single-step hydrothermal approach to engineer a surface with exceptional underwater–oil-repellent properties. Through a hydrothermal reaction, nanoneedles are deposited onto porous hydrophobic nickel foam, imparting it with superhydrophilicity in air and underwater superoleophobicity. The resultant membrane demonstrates gravity-driven separation of immiscible organic liquid mixtures, achieving an impressive separation efficiency of up to 99.6% and an extraordinary flux of 33,839 L m–2 h–1. The nanoneedles exhibit negligible oil droplet adhesion and an exceptionally low underwater–oil sliding angle. The unique low oil adhesion properties of the membrane permit seamless underwater manipulation and the transport of immiscible organic microdroplets without any loss. Utilizing its antioil adhesiveness, the membrane facilitates oil transportation in a drop-to-drop configuration, showcasing its potential for sophisticated applications in oil-based microreactors. Furthermore, the membrane exhibits admirable reusability, chemical and thermal stability, and robust resistance to salinity and temperature fluctuations. The simplified fabrication process offers a promising method for producing oil-repellent membranes with profound implications for applications in diverse and demanding underwater environments. Potential applications include oil spill remediation, underwater–oil transport, precise reagent transfer, and the development of droplet-based reactors.
使用憎油膜自发萃取有机不相溶液体具有重要的研究意义,尤其是在油水混合物分离领域。然而,由于传统上复杂的多步骤制造工艺,这类膜的开发本身就具有挑战性。这项工作介绍了一种单步水热法,用于设计具有特殊水下斥油性能的表面。通过水热反应,纳米针沉积到多孔疏水镍泡沫上,赋予其在空气中的超亲水性和在水下的超疏水性。由此产生的膜可在重力驱动下分离不相溶的有机液体混合物,分离效率高达 99.6%,通量高达 33 839 L m-2 h-1。纳米针头的油滴附着力可以忽略不计,水下与油的滑动角也非常低。该膜独特的低油粘附特性允许进行无缝水下操作,并能无损地传输不相溶的有机微滴。利用其抗油污粘附性,该膜可在液滴到液滴的配置中促进油污输送,展示了其在油基微反应器中复杂应用的潜力。此外,这种膜还具有令人赞叹的可重复使用性、化学和热稳定性,以及强大的抗盐度和温度波动能力。简化的制造工艺为生产斥油膜提供了一种前景广阔的方法,对各种苛刻的水下环境应用具有深远影响。潜在的应用包括溢油补救、水下石油运输、精确试剂传输以及基于液滴的反应器的开发。
{"title":"Fish-Scale-Inspired Underwater Superoleophobic Nanosurface for Efficient Oil–Water Separation and Manipulation","authors":"Irfan Majeed Bhat, Tabassum Ara and Saifullah Lone*, ","doi":"10.1021/acsaenm.4c0048310.1021/acsaenm.4c00483","DOIUrl":"https://doi.org/10.1021/acsaenm.4c00483https://doi.org/10.1021/acsaenm.4c00483","url":null,"abstract":"<p >The spontaneous extraction of organic immiscible liquids using oil-repellent membranes holds substantial research significance, particularly in the domain of oil–water mixture separation. However, the development of such membranes is inherently challenging due to the traditionally complex and multistep fabrication processes. This work introduces a single-step hydrothermal approach to engineer a surface with exceptional underwater–oil-repellent properties. Through a hydrothermal reaction, nanoneedles are deposited onto porous hydrophobic nickel foam, imparting it with superhydrophilicity in air and underwater superoleophobicity. The resultant membrane demonstrates gravity-driven separation of immiscible organic liquid mixtures, achieving an impressive separation efficiency of up to 99.6% and an extraordinary flux of 33,839 L m<sup>–2</sup> h<sup>–1</sup>. The nanoneedles exhibit negligible oil droplet adhesion and an exceptionally low underwater–oil sliding angle. The unique low oil adhesion properties of the membrane permit seamless underwater manipulation and the transport of immiscible organic microdroplets without any loss. Utilizing its antioil adhesiveness, the membrane facilitates oil transportation in a drop-to-drop configuration, showcasing its potential for sophisticated applications in oil-based microreactors. Furthermore, the membrane exhibits admirable reusability, chemical and thermal stability, and robust resistance to salinity and temperature fluctuations. The simplified fabrication process offers a promising method for producing oil-repellent membranes with profound implications for applications in diverse and demanding underwater environments. Potential applications include oil spill remediation, underwater–oil transport, precise reagent transfer, and the development of droplet-based reactors.</p>","PeriodicalId":55639,"journal":{"name":"ACS Applied Engineering Materials","volume":"2 10","pages":"2414–2424 2414–2424"},"PeriodicalIF":0.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142551069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-09DOI: 10.1021/acsaenm.4c0059310.1021/acsaenm.4c00593
Dilshad Ahmad, Jing Zhang, Jing Xu and Jun Luo*,
{"title":"Correction to “Comparative Study on the Effects of O2 Flow Rate on As-Deposited Polycrystalline IAZO Films”","authors":"Dilshad Ahmad, Jing Zhang, Jing Xu and Jun Luo*, ","doi":"10.1021/acsaenm.4c0059310.1021/acsaenm.4c00593","DOIUrl":"https://doi.org/10.1021/acsaenm.4c00593https://doi.org/10.1021/acsaenm.4c00593","url":null,"abstract":"","PeriodicalId":55639,"journal":{"name":"ACS Applied Engineering Materials","volume":"2 10","pages":"2478 2478"},"PeriodicalIF":0.0,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142550444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-09DOI: 10.1021/acsaenm.4c0035610.1021/acsaenm.4c00356
Debdyuti Mukherjee*, Ramesh Aswin and K. Ramya*,
Hydrogen is attractive as a clean fuel as it can be produced directly from water and electricity (electrochemical hydrogen evolution reaction, one of the half-cell reactions in water electrolyzers) and creates the same products (water and electricity) when utilized in a fuel cell. Electrocatalysts are often used to accelerate the kinetics of these reactions, which led to a bloom in the field of electrocatalyst research to search for an efficient, stable, and cost-effective material. Hybrid organic–inorganic 2D electrocatalysts are presented in the current studies, which were prepared by combining two different class of 2D-layered materials: poly(benzoquinone-pyrrole) polymer (BQ-Py polymer) as the organic counterpart and MoS2 as the inorganic counterpart. The hybrid composite catalysts (named BQ-Py-MoS2_NS_US and BQ-Py-MoS2_hyd) exhibit efficient HER activities with high durability in both acidic (aqueous 0.5 M H2SO4) and simulated seawater (3.5 wt % of aqueous NaCl) solutions. The studies also reveal some kinetic parameters for electrochemical HER, where it is observed that only 100 mV of extra overpotential is required for the hydrothermally formed hybrid composite to achieve 10 mA cm–2 of current density as compared to the state-of-the-art HER catalyst (40 wt % Pt–C). This opens up an avenue to develop organic–inorganic hybrid composite catalysts for various electrochemical reactions.
氢作为一种清洁燃料具有吸引力,因为它可以直接从水和电中产生(电化学氢进化反应,水电解槽中的半电池反应之一),并且在燃料电池中使用时产生相同的产物(水和电)。电催化剂通常被用来加速这些反应的动力学过程,因此电催化剂研究领域出现了寻找高效、稳定、经济的材料的热潮。本研究介绍了有机-无机混合二维电催化剂,其制备方法是将两种不同类型的二维层状材料结合在一起:聚(苯醌-吡咯)聚合物(BQ-Py 聚合物)作为有机催化剂,MoS2 作为无机催化剂。混合复合催化剂(命名为 BQ-Py-MoS2_NS_US 和 BQ-Py-MoS2_hyd)在酸性(0.5 M H2SO4 水溶液)和模拟海水(3.5 wt % NaCl 水溶液)溶液中均表现出高效的 HER 活性和高耐久性。研究还揭示了电化学 HER 的一些动力学参数,与最先进的 HER 催化剂(40 wt % Pt-C)相比,水热形成的混合复合材料只需要 100 mV 的额外过电位就能达到 10 mA cm-2 的电流密度。这为开发用于各种电化学反应的有机-无机杂化复合催化剂开辟了一条途径。
{"title":"Poly(benzoquinone-pyrrole)-MoS2─A Class of 2D Organic–Inorganic Hybrid Layered Catalysts for Electrochemical Hydrogen Generation","authors":"Debdyuti Mukherjee*, Ramesh Aswin and K. Ramya*, ","doi":"10.1021/acsaenm.4c0035610.1021/acsaenm.4c00356","DOIUrl":"https://doi.org/10.1021/acsaenm.4c00356https://doi.org/10.1021/acsaenm.4c00356","url":null,"abstract":"<p >Hydrogen is attractive as a clean fuel as it can be produced directly from water and electricity (electrochemical hydrogen evolution reaction, one of the half-cell reactions in water electrolyzers) and creates the same products (water and electricity) when utilized in a fuel cell. Electrocatalysts are often used to accelerate the kinetics of these reactions, which led to a bloom in the field of electrocatalyst research to search for an efficient, stable, and cost-effective material. Hybrid organic–inorganic 2D electrocatalysts are presented in the current studies, which were prepared by combining two different class of 2D-layered materials: poly(benzoquinone-pyrrole) polymer (BQ-Py polymer) as the organic counterpart and MoS<sub>2</sub> as the inorganic counterpart. The hybrid composite catalysts (named BQ-Py-MoS<sub>2</sub>_NS_US and BQ-Py-MoS<sub>2</sub>_hyd) exhibit efficient HER activities with high durability in both acidic (aqueous 0.5 M H<sub>2</sub>SO<sub>4</sub>) and simulated seawater (3.5 wt % of aqueous NaCl) solutions. The studies also reveal some kinetic parameters for electrochemical HER, where it is observed that only 100 mV of extra overpotential is required for the hydrothermally formed hybrid composite to achieve 10 mA cm<sup>–2</sup> of current density as compared to the state-of-the-art HER catalyst (40 wt % Pt–C). This opens up an avenue to develop organic–inorganic hybrid composite catalysts for various electrochemical reactions.</p>","PeriodicalId":55639,"journal":{"name":"ACS Applied Engineering Materials","volume":"2 10","pages":"2351–2360 2351–2360"},"PeriodicalIF":0.0,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142550439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-07DOI: 10.1021/acsaenm.4c0051010.1021/acsaenm.4c00510
Lianna Johnson, Bernadette L. Schneider, Husain Mithaiwala, Matthew D. Green, Julie N. Renner* and Christine E. Duval*,
Rare earth elements (REEs) are crucial for clean energy technologies but are predominantly purified by solvent extraction using strong acids. This work explores two adsorbents with selective chemistry based on lanmodulin-derived peptides. Two membrane adsorber platforms were synthesized: (1) a poly(vinylbenzyl chloride) membrane with a grafted poly(allyl methacrylate) network and (2) a poly(arylene ether sulfone) membrane with allyl pendant groups. Both membrane adsorbers were functionalized with LanM1 peptides via a thiol–ene click reaction. The morphology, surface chemistry, and adsorption of select trivalent lanthanides (La, Ce, Pr, Nd) were characterized in pH 4–5 solutions, mimicking phosphogypsum waste streams. Results from the adsorption experiments indicate that the lanmodulin peptide sequence maintains its ability to bind when it is immobilized on the surface of polymer fibers for some ions. Despite the different adsorbent designs, the measured capacity of both adsorbents is on the same order of magnitude, which may be explained by differences in the surface area of the fibers.
{"title":"Electrospun Membranes Modified with Lanmodulin-Derived Peptides for Lanthanide Adsorption","authors":"Lianna Johnson, Bernadette L. Schneider, Husain Mithaiwala, Matthew D. Green, Julie N. Renner* and Christine E. Duval*, ","doi":"10.1021/acsaenm.4c0051010.1021/acsaenm.4c00510","DOIUrl":"https://doi.org/10.1021/acsaenm.4c00510https://doi.org/10.1021/acsaenm.4c00510","url":null,"abstract":"<p >Rare earth elements (REEs) are crucial for clean energy technologies but are predominantly purified by solvent extraction using strong acids. This work explores two adsorbents with selective chemistry based on lanmodulin-derived peptides. Two membrane adsorber platforms were synthesized: (1) a poly(vinylbenzyl chloride) membrane with a grafted poly(allyl methacrylate) network and (2) a poly(arylene ether sulfone) membrane with allyl pendant groups. Both membrane adsorbers were functionalized with LanM1 peptides via a thiol–ene click reaction. The morphology, surface chemistry, and adsorption of select trivalent lanthanides (La, Ce, Pr, Nd) were characterized in pH 4–5 solutions, mimicking phosphogypsum waste streams. Results from the adsorption experiments indicate that the lanmodulin peptide sequence maintains its ability to bind when it is immobilized on the surface of polymer fibers for some ions. Despite the different adsorbent designs, the measured capacity of both adsorbents is on the same order of magnitude, which may be explained by differences in the surface area of the fibers.</p>","PeriodicalId":55639,"journal":{"name":"ACS Applied Engineering Materials","volume":"2 10","pages":"2442–2453 2442–2453"},"PeriodicalIF":0.0,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142551815","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-03DOI: 10.1021/acsaenm.4c0041110.1021/acsaenm.4c00411
Gary Germanton, Kara Lindsey Martin, Md Alamgir Hossain, Nicholas Dunn Posey, James F. Ponder Jr., Camilo Ramirez, Pitchaimari Gnanasekar, Lutz Wiegart, Pavan Polisetty, Daniel T. Hallinan Jr., Matthew B. Dickerson* and Subramanian Ramakrishnan*,
Preceramic polymers (PCPs) offer advantages in producing ceramics due to their processability and ability to tailor the final chemistry of the produced material. However, challenges such as volumetric shrinkage and mass loss during pyrolysis often result in polymer-derived ceramics containing pores and cracks. PCP-grafted ceramic nanoparticles (PCPGNPs) have been proposed and studied as a route to mitigate the shrinkage issues associated with neat PCPs. Prior studies on PCPGNPs have principally focused on the synthesis and characterization of neat materials. Dispersing PCPGNPs in commercial preceramic polymer is another attractive, but underexplored, route to control the rheological and char yield properties of PCP systems. In this work, a systematic rheological study of commercial PCP (SMP-877) and PCPGNP (silica with poly(1,1-dimethylpropylsilane) corona) mixtures was executed to develop design rules for the processing of such systems. A rheological study demonstrated the effect of increasing particle concentration on network formation with percolation occurring between 50 and 60 wt %. Samples above the percolation threshold exhibited higher viscosities and rapid shear thinning thus demonstrating their direct-write printability. X-ray photon correlation spectroscopy (XPCS) corroborated the rheology and showed two diffusive modes when the material was above percolation. Mixtures of PCPGNPs and SMP-877 had synergistically higher char yields upon thermal treatment and pyrolysis. XPCS and rheological measurements during thermal treatment identified thermal jamming of the polymer grafts as a key factor in improving the char yield. With the insights gained here, we expect these mixed systems to provide attractive feedstocks for polymer-derived ceramics, with proof-of-principal application as feedstocks for direct ink write (DIW) additive manufacturing.
{"title":"Insights into Preceramic Polymer-Based Additive Manufacturing Inks via Rheological and Scattering Studies of Preceramic Polymer-Grafted Nanoparticles Suspended in Polycarbosilane","authors":"Gary Germanton, Kara Lindsey Martin, Md Alamgir Hossain, Nicholas Dunn Posey, James F. Ponder Jr., Camilo Ramirez, Pitchaimari Gnanasekar, Lutz Wiegart, Pavan Polisetty, Daniel T. Hallinan Jr., Matthew B. Dickerson* and Subramanian Ramakrishnan*, ","doi":"10.1021/acsaenm.4c0041110.1021/acsaenm.4c00411","DOIUrl":"https://doi.org/10.1021/acsaenm.4c00411https://doi.org/10.1021/acsaenm.4c00411","url":null,"abstract":"<p >Preceramic polymers (PCPs) offer advantages in producing ceramics due to their processability and ability to tailor the final chemistry of the produced material. However, challenges such as volumetric shrinkage and mass loss during pyrolysis often result in polymer-derived ceramics containing pores and cracks. PCP-grafted ceramic nanoparticles (PCPGNPs) have been proposed and studied as a route to mitigate the shrinkage issues associated with neat PCPs. Prior studies on PCPGNPs have principally focused on the synthesis and characterization of neat materials. Dispersing PCPGNPs in commercial preceramic polymer is another attractive, but underexplored, route to control the rheological and char yield properties of PCP systems. In this work, a systematic rheological study of commercial PCP (SMP-877) and PCPGNP (silica with poly(1,1-dimethylpropylsilane) corona) mixtures was executed to develop design rules for the processing of such systems. A rheological study demonstrated the effect of increasing particle concentration on network formation with percolation occurring between 50 and 60 wt %. Samples above the percolation threshold exhibited higher viscosities and rapid shear thinning thus demonstrating their direct-write printability. X-ray photon correlation spectroscopy (XPCS) corroborated the rheology and showed two diffusive modes when the material was above percolation. Mixtures of PCPGNPs and SMP-877 had synergistically higher char yields upon thermal treatment and pyrolysis. XPCS and rheological measurements during thermal treatment identified thermal jamming of the polymer grafts as a key factor in improving the char yield. With the insights gained here, we expect these mixed systems to provide attractive feedstocks for polymer-derived ceramics, with proof-of-principal application as feedstocks for direct ink write (DIW) additive manufacturing.</p>","PeriodicalId":55639,"journal":{"name":"ACS Applied Engineering Materials","volume":"2 10","pages":"2379–2390 2379–2390"},"PeriodicalIF":0.0,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142517089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}