The development of supercapacitors is pivotal for sustainable energy storage solutions, necessitating the advancement of innovative electrode materials to supplant fossil-fuel-based energy sources. Zinc oxide (ZnO) is widely studied for use in supercapacitor electrodes because of its beneficial physicochemical properties, including excellent chemical and thermal stability, semiconducting characteristics, low cost, and environmentally friendly nature. In this study, ZnO nanorods were synthesized using a simple hydrothermal method and then combined with various Ni-based layered double hydroxides (LDHs) [NiM′-LDHs (M′ = Mn, Co, and Fe)] to improve the electrochemical performance of the ZnO nanorods. These LDHs are well-known for their outstanding electrochemical and electronic properties, high specific capacitance, and efficient dispersion of cations within host nanolayers. The synthesized composites ZnO@NiMn-LDH, ZnO@NiCo-LDH, and ZnO@NiFe-LDH exhibit enhanced specific capacitances of 569.3, 284.6, and 133.0 F/g, respectively, at a current rate of 1 A/g, outperforming bare ZnO (98.4 F/g). Notably, ZnO@NiMn-LDH demonstrates superior electrochemical performance along with a capacitance retention of 76%, compared to ZnO@NiCo-LDH (58%), ZnO@NiFe-LDH (49%), and bare ZnO (23%) over 5000 cycles. Furthermore, an asymmetric supercapacitor (ASC) was developed by using ZnO@NiMn-LDH as the positive electrode and activated carbon (AC) as the negative electrode to assess its practical applicability. The fabricated ASC (ZnO@NiMn-LDH//AC) demonstrated a specific capacitance of 45.22 F/g at a current rate of 1 A/g, an energy density of 16.08 W h/kg at a power density of 798.8 W/kg, and a capacitance retention of 75% over 5000 cycles. These findings underscore the potential of the composite formation of ZnO with Ni-based LDHs in advancing the efficiency and durability of supercapacitors.
{"title":"Synergistic Effects of ZnO@NiM′-Layered Double Hydroxide (M′ = Mn, Co, and Fe) Composites on Supercapacitor Performance: A Comparative Evaluation","authors":"Gaurav Pandey, Surendra Serawat, Kamlendra Awasthi","doi":"10.1021/acsnanoscienceau.4c00029","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00029","url":null,"abstract":"The development of supercapacitors is pivotal for sustainable energy storage solutions, necessitating the advancement of innovative electrode materials to supplant fossil-fuel-based energy sources. Zinc oxide (ZnO) is widely studied for use in supercapacitor electrodes because of its beneficial physicochemical properties, including excellent chemical and thermal stability, semiconducting characteristics, low cost, and environmentally friendly nature. In this study, ZnO nanorods were synthesized using a simple hydrothermal method and then combined with various Ni-based layered double hydroxides (LDHs) [NiM′-LDHs (M′ = Mn, Co, and Fe)] to improve the electrochemical performance of the ZnO nanorods. These LDHs are well-known for their outstanding electrochemical and electronic properties, high specific capacitance, and efficient dispersion of cations within host nanolayers. The synthesized composites ZnO@NiMn-LDH, ZnO@NiCo-LDH, and ZnO@NiFe-LDH exhibit enhanced specific capacitances of 569.3, 284.6, and 133.0 F/g, respectively, at a current rate of 1 A/g, outperforming bare ZnO (98.4 F/g). Notably, ZnO@NiMn-LDH demonstrates superior electrochemical performance along with a capacitance retention of 76%, compared to ZnO@NiCo-LDH (58%), ZnO@NiFe-LDH (49%), and bare ZnO (23%) over 5000 cycles. Furthermore, an asymmetric supercapacitor (ASC) was developed by using ZnO@NiMn-LDH as the positive electrode and activated carbon (AC) as the negative electrode to assess its practical applicability. The fabricated ASC (ZnO@NiMn-LDH//AC) demonstrated a specific capacitance of 45.22 F/g at a current rate of 1 A/g, an energy density of 16.08 W h/kg at a power density of 798.8 W/kg, and a capacitance retention of 75% over 5000 cycles. These findings underscore the potential of the composite formation of ZnO with Ni-based LDHs in advancing the efficiency and durability of supercapacitors.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":"41 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142266161","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 : 2024-09-12DOI: 10.1021/acsnanoscienceau.4c00037
Mengting Zhao, Hanfeng Liang
Acidic oxygen evolution reaction (OER) has long been the bottleneck of proton exchange membrane water electrolysis. Ru- and Ir-based oxides are currently state-of-the-art electrocatalysts for acidic OER, but their high cost limits their widespread application. Co3O4 is a promising alternative, yet the performance requires further improvement. Crystal facet engineering can effectively regulate the kinetics of surface electrochemistry and thus enhance the OER performance. However, the facet-dependent OER activity and corrosion behavior of Co3O4 have not been thoroughly studied. In this study, we systematically investigated the OER performance and crystal facet dependency of Co3O4. The results demonstrate that Co3O4 with mixed {111} and {110} facets exhibits better OER activity and stability than Co3O4 with {111} or {100} facets. The surface Co3+ species are responsible for the high OER activity, but its transformation to CoO2 is also the root cause of the dissolution, leading to an activity–stability trade-off effect. The possible approach to addressing this issue would be to increase the Co3+ contents by nanostructure engineering. To further improve the performance, Ru is introduced to the best-performing Co3O4. The resulting Co3O4/RuO2 heterostructure exhibits an overpotential of 257 mV at 10 mA cm–2 and can stably catalyze the OER for 100 h.
长期以来，酸性氧进化反应（OER）一直是质子交换膜水电解的瓶颈。基于 Ru 和 Ir 的氧化物是目前最先进的酸性 OER 电催化剂，但其高昂的成本限制了其广泛应用。Co3O4 是一种很有前途的替代品，但其性能还需要进一步提高。晶面工程可以有效调节表面电化学动力学，从而提高 OER 性能。然而，人们对 Co3O4 晶面依赖性 OER 活性和腐蚀行为的研究还不够深入。在本研究中，我们系统地研究了 Co3O4 的 OER 性能和晶面依赖性。结果表明，具有{111}和{110}混合晶面的 Co3O4 比具有{111}或{100}晶面的 Co3O4 表现出更好的 OER 活性和稳定性。表面 Co3+ 物种是产生高 OER 活性的原因，但其向 CoO2 的转化也是导致溶解的根本原因，从而产生了活性-稳定性权衡效应。解决这一问题的可行方法是通过纳米结构工程增加 Co3+ 的含量。为了进一步提高性能，在性能最好的 Co3O4 中引入了 Ru。由此产生的 Co3O4/RuO2 异质结构在 10 mA cm-2 时的过电位为 257 mV，可稳定催化 OER 100 小时。
{"title":"Crystal Facet Regulation and Ru Incorporation of Co3O4 for Acidic Oxygen Evolution Reaction Electrocatalysis","authors":"Mengting Zhao, Hanfeng Liang","doi":"10.1021/acsnanoscienceau.4c00037","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00037","url":null,"abstract":"Acidic oxygen evolution reaction (OER) has long been the bottleneck of proton exchange membrane water electrolysis. Ru- and Ir-based oxides are currently state-of-the-art electrocatalysts for acidic OER, but their high cost limits their widespread application. Co<sub>3</sub>O<sub>4</sub> is a promising alternative, yet the performance requires further improvement. Crystal facet engineering can effectively regulate the kinetics of surface electrochemistry and thus enhance the OER performance. However, the facet-dependent OER activity and corrosion behavior of Co<sub>3</sub>O<sub>4</sub> have not been thoroughly studied. In this study, we systematically investigated the OER performance and crystal facet dependency of Co<sub>3</sub>O<sub>4</sub>. The results demonstrate that Co<sub>3</sub>O<sub>4</sub> with mixed {111} and {110} facets exhibits better OER activity and stability than Co<sub>3</sub>O<sub>4</sub> with {111} or {100} facets. The surface Co<sup>3+</sup> species are responsible for the high OER activity, but its transformation to CoO<sub>2</sub> is also the root cause of the dissolution, leading to an activity–stability trade-off effect. The possible approach to addressing this issue would be to increase the Co<sup>3+</sup> contents by nanostructure engineering. To further improve the performance, Ru is introduced to the best-performing Co<sub>3</sub>O<sub>4</sub>. The resulting Co<sub>3</sub>O<sub>4</sub>/RuO<sub>2</sub> heterostructure exhibits an overpotential of 257 mV at 10 mA cm<sup>–2</sup> and can stably catalyze the OER for 100 h.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":"189 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142266119","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 : 2024-09-06DOI: 10.1021/acsnanoscienceau.4c00025
Zechariah Mengrani, Weiying Hong, Matteo Palma
Herein, we present a strategy for the controlled assembly of single-walled carbon nanotube (SWCNT) linear junctions mediated by DNA as a functional linker. We demonstrate this by employing SWCNTs of two different chiralities via the specific design of DNA sequences and chiral selection. Streptavidin and AuNP labeling of the SWCNT sidewalls demonstrate the presence of two different chirality within each individual CNT–DNA–CNT junction. These one-dimensional nanohybrids were further organized from solution to devices. The approach we developed is of general applicability for the assembly of functional nanohybrids based on carbon nanotubes toward functional applications.
在此，我们提出了一种以 DNA 为功能连接体，控制单壁碳纳米管 (SWCNT) 线性连接组装的策略。我们通过 DNA 序列的特定设计和手性选择，采用了两种不同手性的 SWCNT，证明了这一点。SWCNT 侧壁的链霉亲和素和 AuNP 标记表明，每个 CNT-DNA-CNT 连接中都存在两种不同的手性。这些一维纳米混合物被进一步从溶液组织成器件。我们开发的方法普遍适用于基于碳纳米管的功能性纳米杂化组装，以实现功能性应用。
{"title":"DNA-Mediated Carbon Nanotubes Heterojunction Assembly","authors":"Zechariah Mengrani, Weiying Hong, Matteo Palma","doi":"10.1021/acsnanoscienceau.4c00025","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00025","url":null,"abstract":"Herein, we present a strategy for the controlled assembly of single-walled carbon nanotube (SWCNT) linear junctions mediated by DNA as a functional linker. We demonstrate this by employing SWCNTs of two different chiralities via the specific design of DNA sequences and chiral selection. Streptavidin and AuNP labeling of the SWCNT sidewalls demonstrate the presence of two different chirality within each individual CNT–DNA–CNT junction. These one-dimensional nanohybrids were further organized from solution to devices. The approach we developed is of general applicability for the assembly of functional nanohybrids based on carbon nanotubes toward functional applications.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":"24 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192266","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 : 2024-09-03DOI: 10.1021/acsnanoscienceau.4c00032
Carolina Guida, Anthony Chappaz, Agnieszka Poulain, Jean-Marc Grenèche, Alexandre Gloter, Nicolas Menguy, Nathaniel Findling, Laurent Charlet
A promising superparamagnetic nanomagnetite dipped with Gd was synthesized for possible medical applications. Its size and morphology are independent of Gd content ranging from 1 to 5%. Gadolinium (III) replaced Fe(III) in the lattice. The sizes of Gd-doped nanoparticles ranged from 5 to 50 nm and exhibited a pure magnetite mineralogical phase.
{"title":"Exploring the Substitution of Fe(III) by Gd(III) in Nanomagnetite","authors":"Carolina Guida, Anthony Chappaz, Agnieszka Poulain, Jean-Marc Grenèche, Alexandre Gloter, Nicolas Menguy, Nathaniel Findling, Laurent Charlet","doi":"10.1021/acsnanoscienceau.4c00032","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00032","url":null,"abstract":"A promising superparamagnetic nanomagnetite dipped with Gd was synthesized for possible medical applications. Its size and morphology are independent of Gd content ranging from 1 to 5%. Gadolinium (III) replaced Fe(III) in the lattice. The sizes of Gd-doped nanoparticles ranged from 5 to 50 nm and exhibited a pure magnetite mineralogical phase.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":"5 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142224799","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 : 2024-08-30DOI: 10.1021/acsnanoscienceau.4c00035
Mengqi Sun, Ankai Wang, Min Zhang, Shengli Zou, Hui Wang
Photoexcited nonthermal electrons and holes in metallic nanoparticles, known as hot carriers, can be judiciously harnessed to drive interesting photocatalytic molecule-transforming processes on nanoparticle surfaces. Interband hot carriers are generated upon direct photoexcitation of electronic transitions between different electronic bands, whereas intraband hot carriers are derived from nonradiative decay of plasmonic electron oscillations. Due to their fundamentally distinct photogeneration mechanisms, these two types of hot carriers differ strikingly from each other in terms of energy distribution profiles, lifetimes, diffusion lengths, and relaxation dynamics, thereby exhibiting remarkably different photocatalytic behaviors. The spectral overlap between plasmon resonances and interband transitions has been identified as a key factor that modulates the interband damping of plasmon resonances, which regulates the relative populations, energy distributions, and photocatalytic efficacies of intraband and interband hot carriers in light-illuminated metallic nanoparticles. As exemplified by the Au–Cu alloy nanoparticles investigated in this work, both the resonant frequencies of plasmons and the energy threshold for the d-to-sp interband transitions can be systematically tuned in bimetallic alloy nanoparticles by varying the compositional stoichiometries and particle sizes. Choosing photocatalytic degradation of Rhodamine B as a model reaction, we elaborate on how the variation of the particle sizes and compositional stoichiometries profoundly influences the photocatalytic efficacies of interband and intraband hot carriers in Au–Cu alloy nanoparticles under different photoexcitation conditions.
金属纳米粒子中的光激发非热电子和空穴被称为热载流子，可被明智地利用来驱动纳米粒子表面有趣的光催化分子转化过程。带间热载流子是在不同电子带之间的电子跃迁受到直接光激发时产生的，而带内热载流子则来自质子电子振荡的非辐射衰减。由于这两种热载流子的光生成机制截然不同，它们在能量分布轮廓、寿命、扩散长度和弛豫动力学方面也大相径庭，从而表现出明显不同的光催化行为。等离子体共振和带间跃迁之间的光谱重叠被认为是调节等离子体共振带间阻尼的关键因素，而带间阻尼调节着光照金属纳米粒子中带内和带间热载流子的相对数量、能量分布和光催化效率。以本研究中的金铜合金纳米粒子为例，通过改变成分的化学计量和颗粒大小，可以系统地调整双金属合金纳米粒子中的质子共振频率和带内到带间转变的能量阈值。我们以光催化降解罗丹明 B 为模型反应，详细阐述了在不同的光激发条件下，颗粒尺寸和成分配比的变化如何深刻影响金-铜合金纳米颗粒中带间和带内热载流子的光催化效率。
{"title":"Interband and Intraband Hot Carrier-Driven Photocatalysis on Plasmonic Bimetallic Nanoparticles: A Case Study of Au–Cu Alloy Nanoparticles","authors":"Mengqi Sun, Ankai Wang, Min Zhang, Shengli Zou, Hui Wang","doi":"10.1021/acsnanoscienceau.4c00035","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00035","url":null,"abstract":"Photoexcited nonthermal electrons and holes in metallic nanoparticles, known as hot carriers, can be judiciously harnessed to drive interesting photocatalytic molecule-transforming processes on nanoparticle surfaces. Interband hot carriers are generated upon direct photoexcitation of electronic transitions between different electronic bands, whereas intraband hot carriers are derived from nonradiative decay of plasmonic electron oscillations. Due to their fundamentally distinct photogeneration mechanisms, these two types of hot carriers differ strikingly from each other in terms of energy distribution profiles, lifetimes, diffusion lengths, and relaxation dynamics, thereby exhibiting remarkably different photocatalytic behaviors. The spectral overlap between plasmon resonances and interband transitions has been identified as a key factor that modulates the interband damping of plasmon resonances, which regulates the relative populations, energy distributions, and photocatalytic efficacies of intraband and interband hot carriers in light-illuminated metallic nanoparticles. As exemplified by the Au–Cu alloy nanoparticles investigated in this work, both the resonant frequencies of plasmons and the energy threshold for the <i>d</i>-to-<i>sp</i> interband transitions can be systematically tuned in bimetallic alloy nanoparticles by varying the compositional stoichiometries and particle sizes. Choosing photocatalytic degradation of Rhodamine B as a model reaction, we elaborate on how the variation of the particle sizes and compositional stoichiometries profoundly influences the photocatalytic efficacies of interband and intraband hot carriers in Au–Cu alloy nanoparticles under different photoexcitation conditions.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":"136 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192242","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}
Given that daily exposure to nanoparticles is now unavoidable, there are concerns that nanoparticles have unexpected biological effects due to their small size. Here, we examined the biodistribution of silver nanoparticles, which are the most frequently used nanoparticles owing to their antibacterial activity, with a diameter of 10 nm (nAg10) to the male genital tract, and the effects of paternal treatment with nAg10 on fetal development. Male Slc:ICR male mice were orally treated with nAg10 for 14 consecutive days. Inductively coupled plasma mass spectrometry analysis detected silver in the blood and testis of male mice, but no general toxicological effects were induced. Moreover, there were no significant changes in fetal development when these treated male mice were mated with nontreated female mice. This implies that although orally ingested nAg10 is distributed to the male genital tract, it does not affect fetal development under the present treatment conditions.
{"title":"Orally Administered Silver Nanoparticles Are Absorbed and Migrate to Testes in Mice","authors":"Yuma Saeki, Kazuma Higashisaka, Rina Izutani, Jiwon Seo, Kazuki Miyaji, Yuya Haga, Yasuo Tsutsumi","doi":"10.1021/acsnanoscienceau.4c00021","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00021","url":null,"abstract":"Given that daily exposure to nanoparticles is now unavoidable, there are concerns that nanoparticles have unexpected biological effects due to their small size. Here, we examined the biodistribution of silver nanoparticles, which are the most frequently used nanoparticles owing to their antibacterial activity, with a diameter of 10 nm (nAg10) to the male genital tract, and the effects of paternal treatment with nAg10 on fetal development. Male Slc:ICR male mice were orally treated with nAg10 for 14 consecutive days. Inductively coupled plasma mass spectrometry analysis detected silver in the blood and testis of male mice, but no general toxicological effects were induced. Moreover, there were no significant changes in fetal development when these treated male mice were mated with nontreated female mice. This implies that although orally ingested nAg10 is distributed to the male genital tract, it does not affect fetal development under the present treatment conditions.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":"48 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192240","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}
Electrochemical semihydrogenation (ESH) of alkynes to alkenes is an appealing technique for producing pharmaceutical precursors and polymer monomers, while also preventing catalyst poisoning by alkyne impurities. Cu is recognized as a cost-effective and highly selective catalyst for ESH, whereas its activity is somewhat limited. Here, from a mechanistic standpoint, we hypothesize that electron-deficient Cu can enhance ESH activity by promoting the rate-determining step of alkene desorption. We test this hypothesis by utilizing Cu–Ag hybrids as electrocatalysts, developed through a welding process of Ag nanoparticles with Cu nanowires. Our findings reveal that these rationally engineered Cu–Ag hybrids exhibit a notable enhancement (2–4 times greater) in alkyne conversion rates compared to isolated Ag NPs or Cu NWs, while maintaining over 99% selectivity for alkene products. Through a combination of operando and computational studies, we verify that the electron-depleted Cu sites, resulting from electron transfer between Ag nanoparticles and Cu nanowires, effectively weaken the adsorption of alkenes, thereby substantially boosting ESH activity. This work not only provides mechanistic insights into ESH but also stimulates compelling strategies involving hybridizing distinct metals to optimize ESH activity.
将炔烃电化学半氢化（ESH）为烯烃是生产药物前体和聚合物单体的一项极具吸引力的技术，同时还能防止炔烃杂质对催化剂的毒害。铜被认为是一种成本效益高、选择性强的 ESH 催化剂，但其活性受到一定限制。在此，我们从机理的角度出发，假设缺电子的 Cu 可以通过促进烯解吸附的速率决定步骤来提高 ESH 活性。我们利用铜银杂化物作为电催化剂来验证这一假设，铜银杂化物是通过银纳米颗粒与铜纳米线的焊接工艺开发出来的。我们的研究结果表明，与孤立的 Ag NPs 或 Cu NWs 相比，这些合理设计的 Cu-Ag 混合物能显著提高（2-4 倍）炔烃的转化率，同时对烯产物的选择性保持在 99% 以上。通过结合操作和计算研究，我们验证了银纳米粒子和铜纳米线之间的电子转移所产生的贫电子铜位点有效地削弱了对烯烃的吸附，从而大大提高了 ESH 活性。这项工作不仅从机理上揭示了 ESH 的机理，还激发了人们采取令人信服的策略，通过杂交不同的金属来优化 ESH 的活性。
{"title":"Enhancing Electrocatalytic Semihydrogenation of Alkynes via Weakening Alkene Adsorption over Electron-Depleted Cu Nanowires","authors":"Dan Luo, Zhiheng Xie, Shuangqun Chen, Tianyi Yang, Yalin Guo, Ying Liu, Zhouhao Zhu, Liyong Gan, Lingmei Liu, Jianfeng Huang","doi":"10.1021/acsnanoscienceau.4c00030","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00030","url":null,"abstract":"Electrochemical semihydrogenation (ESH) of alkynes to alkenes is an appealing technique for producing pharmaceutical precursors and polymer monomers, while also preventing catalyst poisoning by alkyne impurities. Cu is recognized as a cost-effective and highly selective catalyst for ESH, whereas its activity is somewhat limited. Here, from a mechanistic standpoint, we hypothesize that electron-deficient Cu can enhance ESH activity by promoting the rate-determining step of alkene desorption. We test this hypothesis by utilizing Cu–Ag hybrids as electrocatalysts, developed through a welding process of Ag nanoparticles with Cu nanowires. Our findings reveal that these rationally engineered Cu–Ag hybrids exhibit a notable enhancement (2–4 times greater) in alkyne conversion rates compared to isolated Ag NPs or Cu NWs, while maintaining over 99% selectivity for alkene products. Through a combination of operando and computational studies, we verify that the electron-depleted Cu sites, resulting from electron transfer between Ag nanoparticles and Cu nanowires, effectively weaken the adsorption of alkenes, thereby substantially boosting ESH activity. This work not only provides mechanistic insights into ESH but also stimulates compelling strategies involving hybridizing distinct metals to optimize ESH activity.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":"2011 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141937714","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 : 2024-07-18DOI: 10.1021/acsnanoscienceau.4c00016
Luiz H. Vieira, Marco A. Rossi, Letícia F. Rasteiro, José M. Assaf, Elisabete M. Assaf
Although chemical promotion led to essential improvements in Cu-based catalysts for CO2 hydrogenation to methanol, surpassing structural limitations such as active phase aggregation under reaction conditions remains challenging. In this report, we improved the textural properties of Cu/In2O3/CeO2 and Cu/In2O3/ZrO2 catalysts by coating the nanoparticles with a mesoporous SiO2 shell. This strategy limited particle size up to 3.5 nm, increasing metal dispersion and widening the metal–metal oxide interface region. Chemometric analysis revealed that these structures could maintain high activity and selectivity in a wide range of reaction conditions, with methanol space-time yields up to 4 times higher than those of the uncoated catalysts.
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Pub Date : 2024-07-18DOI: 10.1021/acsnanoscienceau.4c0001610.1021/acsnanoscienceau.4c00016
Luiz H. Vieira*, Marco A. Rossi, Letícia F. Rasteiro, José M. Assaf and Elisabete M. Assaf*,
Although chemical promotion led to essential improvements in Cu-based catalysts for CO2 hydrogenation to methanol, surpassing structural limitations such as active phase aggregation under reaction conditions remains challenging. In this report, we improved the textural properties of Cu/In2O3/CeO2 and Cu/In2O3/ZrO2 catalysts by coating the nanoparticles with a mesoporous SiO2 shell. This strategy limited particle size up to 3.5 nm, increasing metal dispersion and widening the metal–metal oxide interface region. Chemometric analysis revealed that these structures could maintain high activity and selectivity in a wide range of reaction conditions, with methanol space-time yields up to 4 times higher than those of the uncoated catalysts.
{"title":"CO2 Hydrogenation to Methanol over Mesoporous SiO2-Coated Cu-Based Catalysts","authors":"Luiz H. Vieira*, Marco A. Rossi, Letícia F. Rasteiro, José M. Assaf and Elisabete M. Assaf*, ","doi":"10.1021/acsnanoscienceau.4c0001610.1021/acsnanoscienceau.4c00016","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00016https://doi.org/10.1021/acsnanoscienceau.4c00016","url":null,"abstract":"<p >Although chemical promotion led to essential improvements in Cu-based catalysts for CO<sub>2</sub> hydrogenation to methanol, surpassing structural limitations such as active phase aggregation under reaction conditions remains challenging. In this report, we improved the textural properties of Cu/In<sub>2</sub>O<sub>3</sub>/CeO<sub>2</sub> and Cu/In<sub>2</sub>O<sub>3</sub>/ZrO<sub>2</sub> catalysts by coating the nanoparticles with a mesoporous SiO<sub>2</sub> shell. This strategy limited particle size up to 3.5 nm, increasing metal dispersion and widening the metal–metal oxide interface region. Chemometric analysis revealed that these structures could maintain high activity and selectivity in a wide range of reaction conditions, with methanol space-time yields up to 4 times higher than those of the uncoated catalysts.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":"4 4","pages":"235–242 235–242"},"PeriodicalIF":4.8,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.4c00016","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142011081","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 : 2024-06-25DOI: 10.1021/acsnanoscienceau.4c00012
Yongjiu Chen, Ruixia Wang, Ming Xu
The increasing use of silver nanoparticles (AgNPs) in consumer products has led to concerns about potential health risks after oral exposure as a result of the transformation and absorption in the gastrointestinal tract (GIT). However, the intricate condition of the GIT poses challenges in understanding the fate and toxicity of AgNPs as they traverse from the mouth to the rectum. For an in-depth understanding of the nanobio interactions, we employed a simulated digestion model to investigate alterations in the physicochemical properties of AgNPs in vitro. Meanwhile, we investigated the underlying toxicological mechanisms of digested AgNPs in enterocytes through metabolomics analysis. In contrast to route means that primarily apply salt solutions to mimic dietary digestion, this in vitro model is a semidynamic sequential digestion system that includes artificial oral, gastric, and intestinal fluids, which are similar to those under physiological conditions including electrolytes, enzymes, bile, pH, and time of digestion. Our results suggest that the formation of Ag–Cl and Ag–S species within the simulated digestion model can lead to an increase in the size of digested AgNPs and that the acidic condition promotes the release of Ag+ from particles. More critically, the presence of digestive enzymes and high concentrations of salt enhances the uptake of Ag by human colon enterocytes, ultimately promoting ROS generation and exacerbating cytotoxicity. Metabolomics analysis further reveals that the sequentially digested AgNPs may disorder lipid metabolism, including the biosynthesis of unsaturated fatty acids and arachidonic acid metabolism, thus increasing the possibility of ferroptosis activation in enterocytes. These findings offer significant insights into the fate and potential adverse effects of AgNPs in the GIT, providing important implications for assessing the health risks of AgNPs via oral exposure.
{"title":"Metabolomics Analysis for Unveiling the Toxicological Mechanism of Silver Nanoparticles Using an In Vitro Gastrointestinal Digestion Model","authors":"Yongjiu Chen, Ruixia Wang, Ming Xu","doi":"10.1021/acsnanoscienceau.4c00012","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00012","url":null,"abstract":"The increasing use of silver nanoparticles (AgNPs) in consumer products has led to concerns about potential health risks after oral exposure as a result of the transformation and absorption in the gastrointestinal tract (GIT). However, the intricate condition of the GIT poses challenges in understanding the fate and toxicity of AgNPs as they traverse from the mouth to the rectum. For an in-depth understanding of the nanobio interactions, we employed a simulated digestion model to investigate alterations in the physicochemical properties of AgNPs <i>in vitro</i>. Meanwhile, we investigated the underlying toxicological mechanisms of digested AgNPs in enterocytes through metabolomics analysis. In contrast to route means that primarily apply salt solutions to mimic dietary digestion, this <i>in vitro</i> model is a semidynamic sequential digestion system that includes artificial oral, gastric, and intestinal fluids, which are similar to those under physiological conditions including electrolytes, enzymes, bile, pH, and time of digestion. Our results suggest that the formation of Ag–Cl and Ag–S species within the simulated digestion model can lead to an increase in the size of digested AgNPs and that the acidic condition promotes the release of Ag<sup>+</sup> from particles. More critically, the presence of digestive enzymes and high concentrations of salt enhances the uptake of Ag by human colon enterocytes, ultimately promoting ROS generation and exacerbating cytotoxicity. Metabolomics analysis further reveals that the sequentially digested AgNPs may disorder lipid metabolism, including the biosynthesis of unsaturated fatty acids and arachidonic acid metabolism, thus increasing the possibility of ferroptosis activation in enterocytes. These findings offer significant insights into the fate and potential adverse effects of AgNPs in the GIT, providing important implications for assessing the health risks of AgNPs via oral exposure.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":"30 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510132","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}
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