Xinyu Zheng, Yanbin Qiu, Jing Luo, Sisheng Yang, Yan Yu, Zheyuan Liu, Ran Zhang, Chengkai Yang
Modulating interfacial electrochemistry represents a prevalent approach for mitigating lithium dendrite growth and enhancing battery performance. Nevertheless, while most additives exhibit inhibitory characteristics, the accelerating effects on interfacial electrochemistry have garnered limited attention. In this work, perfluoromorpholine (PFM) with facilitated kinetics is utilized to preferentially adsorb on the lithium metal interface. The PFM molecules disrupt the solvation structure of Li+ and enhance the migration of Li+. Combined with the benzotrifluoride, a synergistic acceleration-inhibition system is formed. The ab initio molecular dynamics (AIMD) and density functional theory (DFT) calculation of the loose outer solvation clusters and the key adsorption-deposition step supports the fast diffusion and stable interface electrochemistry with an accelerated filling mode with C─F and C─H groups. The approach induces the uniform lithium deposition. Excellent cycling performance is achieved in Li||Li symmetric cells, and even after 200 cycles in Li||NCM811 full cells, 80% of the capacity is retained. This work elucidates the accelerated electrochemical processes at the interface and expands the design strategies of acceleration fluorinated additives for lithium metal batteries.
调节界面电化学是缓解锂枝晶生长和提高电池性能的常用方法。然而,虽然大多数添加剂都具有抑制特性,但其对界面电化学的加速作用却很少受到关注。在这项研究中,全氟吗啉(PFM)具有促进动力学特性,可优先吸附在锂金属界面上。PFM 分子会破坏 Li+ 的溶解结构,并增强 Li+ 的迁移。与三氟甲苯相结合,形成了一个协同加速-抑制系统。对松散的外层溶胶团簇和关键的吸附-沉积步骤进行的 ab initio 分子动力学(AIMD)和密度泛函理论(DFT)计算,支持了以 C─F 和 C─H 基团为加速填充模式的快速扩散和稳定的界面电化学。这种方法可实现均匀的锂沉积。在锂||锂对称电池中实现了优异的循环性能,即使在锂||NCM811全电池中循环 200 次后,仍能保持 80% 的容量。这项研究阐明了界面的加速电化学过程,并拓展了锂金属电池加速含氟添加剂的设计策略。
{"title":"Perfluorinated Amines: Accelerating Lithium Electrodeposition by Tailoring Interfacial Structure and Modulated Solvation for High-Performance Batteries.","authors":"Xinyu Zheng, Yanbin Qiu, Jing Luo, Sisheng Yang, Yan Yu, Zheyuan Liu, Ran Zhang, Chengkai Yang","doi":"10.1002/smll.202404614","DOIUrl":"https://doi.org/10.1002/smll.202404614","url":null,"abstract":"<p><p>Modulating interfacial electrochemistry represents a prevalent approach for mitigating lithium dendrite growth and enhancing battery performance. Nevertheless, while most additives exhibit inhibitory characteristics, the accelerating effects on interfacial electrochemistry have garnered limited attention. In this work, perfluoromorpholine (PFM) with facilitated kinetics is utilized to preferentially adsorb on the lithium metal interface. The PFM molecules disrupt the solvation structure of Li<sup>+</sup> and enhance the migration of Li<sup>+</sup>. Combined with the benzotrifluoride, a synergistic acceleration-inhibition system is formed. The ab initio molecular dynamics (AIMD) and density functional theory (DFT) calculation of the loose outer solvation clusters and the key adsorption-deposition step supports the fast diffusion and stable interface electrochemistry with an accelerated filling mode with C─F and C─H groups. The approach induces the uniform lithium deposition. Excellent cycling performance is achieved in Li||Li symmetric cells, and even after 200 cycles in Li||NCM811 full cells, 80% of the capacity is retained. This work elucidates the accelerated electrochemical processes at the interface and expands the design strategies of acceleration fluorinated additives for lithium metal batteries.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532993","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiazheng Hu, Jing Li, Guochao Lu, Dingshuo Zhang, Qiuting Cai, Xinyang Wang, Zhishan Fang, Haoran Zhang, Zaishang Long, Jun Pan, Xingliang Dai, Zhizhen Ye, Haiping He
Quasi-2D perovskites exhibit impressive optoelectronic properties and hold significant promise for future light-emitting devices. However, the efficiency of perovskite light-emitting diodes (PeLEDs) is seriously limited by defect-induced nonradiative recombination and imbalanced charge injection. Here, the defect states are passivated and charge injection balance is effectively improved by introducing the additive cyclohexanemethylammonium (CHMA) to bromide-based Dion-Jacobson (D-J) structure quasi-2D perovskite emission layer. CHMA participates in the crystallization of perovskite, leading to high quality film composed of compact and well-contacted grains with enhanced hole transportation and less defects. As a result, the corresponding PeLEDs exhibit stable pure blue emission at 466 nm with a maximum external quantum efficiency (EQE) of 9.22%. According to current knowledge, this represents the highest EQE reported for pure-blue PeLEDs based on quasi-2D bromide perovskite thin films. These findings underscore the potential of quasi-2D perovskites for advanced light-emitting devices and pave the way for further advancements in PeLEDs.
{"title":"Monoammonium Modified Dion-Jacobson Quasi-2D Perovskite for High Efficiency Pure-Blue Light Emitting Diodes.","authors":"Jiazheng Hu, Jing Li, Guochao Lu, Dingshuo Zhang, Qiuting Cai, Xinyang Wang, Zhishan Fang, Haoran Zhang, Zaishang Long, Jun Pan, Xingliang Dai, Zhizhen Ye, Haiping He","doi":"10.1002/smll.202402786","DOIUrl":"https://doi.org/10.1002/smll.202402786","url":null,"abstract":"<p><p>Quasi-2D perovskites exhibit impressive optoelectronic properties and hold significant promise for future light-emitting devices. However, the efficiency of perovskite light-emitting diodes (PeLEDs) is seriously limited by defect-induced nonradiative recombination and imbalanced charge injection. Here, the defect states are passivated and charge injection balance is effectively improved by introducing the additive cyclohexanemethylammonium (CHMA) to bromide-based Dion-Jacobson (D-J) structure quasi-2D perovskite emission layer. CHMA participates in the crystallization of perovskite, leading to high quality film composed of compact and well-contacted grains with enhanced hole transportation and less defects. As a result, the corresponding PeLEDs exhibit stable pure blue emission at 466 nm with a maximum external quantum efficiency (EQE) of 9.22%. According to current knowledge, this represents the highest EQE reported for pure-blue PeLEDs based on quasi-2D bromide perovskite thin films. These findings underscore the potential of quasi-2D perovskites for advanced light-emitting devices and pave the way for further advancements in PeLEDs.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532992","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lecheng Liang, Kaiyang Xu, Jinhui Liang, Shao Ye, Binwen Zeng, Quanbing Liu, Huiyu Song, Li Du, Zhiming Cui
It is a grand challenge to deep understanding of and precise control over functional sites for the rational design of highly efficient catalysts for methanol electrooxidation. Here, an L12-Pt2RhFe intermetallic catalyst with integrated functional components is demonstrated, which exhibits exceptional CO tolerance. The Pt2RhFe/C achieves a superior mass activity of 6.43 A mgPt-1, which is 2.23-fold and 3.53-fold higher than those of PtRu/C and Pt/C. Impressively, the Pt2RhFe/C exhibits a significant enhancement in durability owing to its high CO-tolerance and stability. Density functional theory calculations reveal that high performance of Pt2RhFe intermetallic catalyst arises from the synergistic effect: the strong OH binding energy (OHBE) at Fe sites induce stably adsorbed OH species and thus facilitate the dehydrogenation step of methanol via rapid hydrogen transfer, while moderate OHBE at Rh sites promote the formation of the transition state (Pt-CO···OH-Rh) with a low activation barrier for CO removal. This work provides new insights into the role of OH binding strength in the removal of CO species, which is beneficial for the rational design of highly efficient catalysts.
如何深入了解并精确控制功能位点,以合理设计用于甲醇电氧化的高效催化剂,是一项巨大的挑战。这里展示的 L12-Pt2RhFe 金属间催化剂集成了多种功能成分,具有优异的 CO 耐受性。Pt2RhFe/C 的质量活性高达 6.43 A mgPt-1,是 PtRu/C 和 Pt/C 的 2.23 倍和 3.53 倍。令人印象深刻的是,由于 Pt2RhFe/C 具有较高的一氧化碳耐受性和稳定性,其耐久性得到了显著提高。密度泛函理论计算显示,Pt2RhFe 金属间催化剂的高性能源于协同效应:Fe 位点的强 OH 结合能(OHBE)诱导稳定吸附 OH 物种,从而通过快速氢转移促进甲醇的脱氢步骤;而 Rh 位点的适度 OHBE 则促进形成具有较低 CO 脱除活化势垒的过渡态(Pt-CO--OH-Rh)。这项工作为了解 OH 结合强度在去除 CO 物种中的作用提供了新的视角,有利于合理设计高效催化剂。
{"title":"Rationally Designed L1<sub>2</sub>-Pt<sub>2</sub>RhFe Intermetallic Catalyst with High CO-Tolerance for Alkaline Methanol Electrooxidation.","authors":"Lecheng Liang, Kaiyang Xu, Jinhui Liang, Shao Ye, Binwen Zeng, Quanbing Liu, Huiyu Song, Li Du, Zhiming Cui","doi":"10.1002/smll.202403557","DOIUrl":"https://doi.org/10.1002/smll.202403557","url":null,"abstract":"<p><p>It is a grand challenge to deep understanding of and precise control over functional sites for the rational design of highly efficient catalysts for methanol electrooxidation. Here, an L1<sub>2</sub>-Pt<sub>2</sub>RhFe intermetallic catalyst with integrated functional components is demonstrated, which exhibits exceptional CO tolerance. The Pt<sub>2</sub>RhFe/C achieves a superior mass activity of 6.43 A mg<sub>Pt</sub> <sup>-1</sup>, which is 2.23-fold and 3.53-fold higher than those of PtRu/C and Pt/C. Impressively, the Pt<sub>2</sub>RhFe/C exhibits a significant enhancement in durability owing to its high CO-tolerance and stability. Density functional theory calculations reveal that high performance of Pt<sub>2</sub>RhFe intermetallic catalyst arises from the synergistic effect: the strong OH binding energy (OHBE) at Fe sites induce stably adsorbed OH species and thus facilitate the dehydrogenation step of methanol via rapid hydrogen transfer, while moderate OHBE at Rh sites promote the formation of the transition state (Pt-CO···OH-Rh) with a low activation barrier for CO removal. This work provides new insights into the role of OH binding strength in the removal of CO species, which is beneficial for the rational design of highly efficient catalysts.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532994","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jie Wang, Ping Li, Renshuai Zhang, Miao Zhang, Chao Wang, Kaihua Zhao, Jing Wang, Ning Wang, Dongming Xing
Flexibility of nanomaterials is challenging but worthy to tune for biomedical applications. Biocompatible silica nanomaterials are under extensive exploration but are rarely observed to exhibit flexibility despite the polymeric nature. Herein, a facile one-step route is reported to ultrathin flexible silica nanosheets (NSs), whose low thickness and high diameter-to-thickness ratio enables folding. Thickness and diameter can be readily tuned to enable controlled flexibility. Mechanism study reveals that beyond the commonly used surfactant, the "uncommon" one bearing two hydrophobic tails play a guiding role in producing sheeted/layered/shelled structures, while addition of ethanol appropriately relieved the strong interfacial tension of the assembled surfactants, which will otherwise produce large curled sheeted structures. With these ultrathin NSs, it is further shown that the cellular preference for particle shape and rigidity is highly dependent on surface chemistry of nanoparticles: under high particle-cell affinity, NSs, and especially the flexible ones will be preferred by mammalian cells for internalization or attachment, while this preference is basically invalid when the affinity is low. Therefore, properties of the ultrathin silica NSs can be effectively expanded and empowered by surface chemistry to realize improved bio-sensing or drug delivery.
{"title":"Ultrathin Flexible Silica Nanosheets with Surface Chemistry-Modulated Affinity to Mammalian Cells.","authors":"Jie Wang, Ping Li, Renshuai Zhang, Miao Zhang, Chao Wang, Kaihua Zhao, Jing Wang, Ning Wang, Dongming Xing","doi":"10.1002/smll.202401772","DOIUrl":"https://doi.org/10.1002/smll.202401772","url":null,"abstract":"<p><p>Flexibility of nanomaterials is challenging but worthy to tune for biomedical applications. Biocompatible silica nanomaterials are under extensive exploration but are rarely observed to exhibit flexibility despite the polymeric nature. Herein, a facile one-step route is reported to ultrathin flexible silica nanosheets (NSs), whose low thickness and high diameter-to-thickness ratio enables folding. Thickness and diameter can be readily tuned to enable controlled flexibility. Mechanism study reveals that beyond the commonly used surfactant, the \"uncommon\" one bearing two hydrophobic tails play a guiding role in producing sheeted/layered/shelled structures, while addition of ethanol appropriately relieved the strong interfacial tension of the assembled surfactants, which will otherwise produce large curled sheeted structures. With these ultrathin NSs, it is further shown that the cellular preference for particle shape and rigidity is highly dependent on surface chemistry of nanoparticles: under high particle-cell affinity, NSs, and especially the flexible ones will be preferred by mammalian cells for internalization or attachment, while this preference is basically invalid when the affinity is low. Therefore, properties of the ultrathin silica NSs can be effectively expanded and empowered by surface chemistry to realize improved bio-sensing or drug delivery.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141533000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Constructing versatile metal nanoclusters (NCs) assemblies through noncovalent weak interactions between inter-ligands is a long-standing challenge in interfacial chemistry, while compelling interfacial hydrogen-bond-driven metal NCs assemblies remain unexplored so far. Here, the study reports an amination-ligand o-phenylenediamine-coordinated copper NCs (CuNCs), demonstrating the impact of interfacial hydrogen-bonds (IHBs) motifs on the luminescent behaviors of metal NCs as the alteration of protic solvent. Experimental results supported by theoretical calculation unveil that the flexibility of interfacial ligand and the distance of cuprophilic CuI···CuI interaction between intra-/inter-NCs can be tailored by manipulating the cooperation between the diverse IHBs motifs reconstruction, therewith the IHBs-modulated fundamental structure-property relationships are established. Importantly, by utilizing the IHBs-mediated optical polychromatism of aminated CuNCs, portable visualization of humidity sensing test-strips with fast response is successfully manufactured. This work not only provides further insights into exploring the interfacial chemistry of NCs based on inter-ligands hydrogen-bond interactions, but also offers a new opportunity to expand the practical application for optical sensing of metal NCs.
{"title":"Interfacial Hydrogen-Bond Interactions Driven Assembly toward Polychromatic Copper Nanoclusters.","authors":"Zhong-Xia Wang, Hang Gao, Yi-Lei Jia, Xiao-Qiong Li, Ting Wang, Shou-Nian Ding, Hong-Yuan Chen, Jing-Juan Xu","doi":"10.1002/smll.202403842","DOIUrl":"https://doi.org/10.1002/smll.202403842","url":null,"abstract":"<p><p>Constructing versatile metal nanoclusters (NCs) assemblies through noncovalent weak interactions between inter-ligands is a long-standing challenge in interfacial chemistry, while compelling interfacial hydrogen-bond-driven metal NCs assemblies remain unexplored so far. Here, the study reports an amination-ligand o-phenylenediamine-coordinated copper NCs (CuNCs), demonstrating the impact of interfacial hydrogen-bonds (IHBs) motifs on the luminescent behaviors of metal NCs as the alteration of protic solvent. Experimental results supported by theoretical calculation unveil that the flexibility of interfacial ligand and the distance of cuprophilic Cu<sup>I</sup>···Cu<sup>I</sup> interaction between intra-/inter-NCs can be tailored by manipulating the cooperation between the diverse IHBs motifs reconstruction, therewith the IHBs-modulated fundamental structure-property relationships are established. Importantly, by utilizing the IHBs-mediated optical polychromatism of aminated CuNCs, portable visualization of humidity sensing test-strips with fast response is successfully manufactured. This work not only provides further insights into exploring the interfacial chemistry of NCs based on inter-ligands hydrogen-bond interactions, but also offers a new opportunity to expand the practical application for optical sensing of metal NCs.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141533068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pore size sieving, Donnan exclusion, and their combined effects seriously affect ion separation of membrane processes. However, traditional polymer-based membranes face some challenges in precisely controlling both charge distribution and pore size on the membrane surface, which hinders the ion separation performance, such as heavy metal ion removal. Herein, the heterocharged covalent organic framework (COF) membrane is reported by assembling two kinds of ionic COF nanosheets with opposite charges and different pore sizes. By manipulating the stacking quantity and sequence of two kinds of nanosheets, the impact of membrane surface charge and pore size on the separation performance of monovalent and multivalent ions is investigated. For the separation of anions, the effect of pore size sieving is dominant, while for the separation of cations, the effect of Donnan exclusion is dominant. The heterocharged TpEBr/TpPa-SO3H membrane with a positively charged upper layer and a negatively charged bottom layer exhibits excellent rejection of multivalent anions and cations (Ni2+, Cd2+, Cr2+, CrO42-, SeO32-, etc). The strategy provides not only high-performance COF membranes for ion separation but also an inspiration for the engineering of heterocharged membranes.
{"title":"Tailor-Made Heterocharged Covalent Organic Framework Membrane for Efficient Ion Separation.","authors":"Yu Zheng, ZhiChao Li, Zixu Yang, Jianliang Shen, Chao Yang, Hui Wang, Kai Xu, Lijuan Cheng, Yihui Hu, Yuxuan Zhao, Runnan Zhang, Zhongyi Jiang","doi":"10.1002/smll.202403300","DOIUrl":"https://doi.org/10.1002/smll.202403300","url":null,"abstract":"<p><p>Pore size sieving, Donnan exclusion, and their combined effects seriously affect ion separation of membrane processes. However, traditional polymer-based membranes face some challenges in precisely controlling both charge distribution and pore size on the membrane surface, which hinders the ion separation performance, such as heavy metal ion removal. Herein, the heterocharged covalent organic framework (COF) membrane is reported by assembling two kinds of ionic COF nanosheets with opposite charges and different pore sizes. By manipulating the stacking quantity and sequence of two kinds of nanosheets, the impact of membrane surface charge and pore size on the separation performance of monovalent and multivalent ions is investigated. For the separation of anions, the effect of pore size sieving is dominant, while for the separation of cations, the effect of Donnan exclusion is dominant. The heterocharged TpEBr/TpPa-SO<sub>3</sub>H membrane with a positively charged upper layer and a negatively charged bottom layer exhibits excellent rejection of multivalent anions and cations (Ni<sup>2+</sup>, Cd<sup>2+</sup>, Cr<sup>2+</sup>, CrO<sub>4</sub> <sup>2-</sup>, SeO<sub>3</sub> <sup>2-</sup>, etc). The strategy provides not only high-performance COF membranes for ion separation but also an inspiration for the engineering of heterocharged membranes.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532997","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hydrogen peroxide (H2O2) plays a pivotal role in advancing sustainable technologies due to its eco-friendly oxidizing capability. The electrochemical two-electron (2e-) oxygen reduction reaction and water oxidation reaction present an environmentally green method for H2O2 production. Over the past three years, significant progress is made in the field of carbon-based metal-free electrochemical catalysts (C-MFECs) for low-cost and efficient production of H2O2 (H2O2EP). This article offers a focused and comprehensive review of designing C-MFECs for H2O2EP, exploring the construction of dual-doping configurations, heteroatom-defect coupling sites, and strategic dopant positioning to enhance H2O2EP efficiency; innovative structural tuning that improves interfacial reactant concentration and promote the timely release of H2O2; modulation of electrolyte and electrode interfaces to support the 2e- pathways; and the application of C-MFECs in reactors and integrated energy systems. Finally, the current challenges and future directions in this burgeoning field are discussed.
{"title":"Advanced Nanocarbons Toward two-Electron Oxygen Electrode Reactions for H<sub>2</sub>O<sub>2</sub> Production and Integrated Energy Conversion.","authors":"Linjie Zhao, Riqing Yan, Baoguang Mao, Rajib Paul, Wenjie Duan, Liming Dai, Chuangang Hu","doi":"10.1002/smll.202403029","DOIUrl":"https://doi.org/10.1002/smll.202403029","url":null,"abstract":"<p><p>Hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) plays a pivotal role in advancing sustainable technologies due to its eco-friendly oxidizing capability. The electrochemical two-electron (2e<sup>-</sup>) oxygen reduction reaction and water oxidation reaction present an environmentally green method for H<sub>2</sub>O<sub>2</sub> production. Over the past three years, significant progress is made in the field of carbon-based metal-free electrochemical catalysts (C-MFECs) for low-cost and efficient production of H<sub>2</sub>O<sub>2</sub> (H<sub>2</sub>O<sub>2</sub>EP). This article offers a focused and comprehensive review of designing C-MFECs for H<sub>2</sub>O<sub>2</sub>EP, exploring the construction of dual-doping configurations, heteroatom-defect coupling sites, and strategic dopant positioning to enhance H<sub>2</sub>O<sub>2</sub>EP efficiency; innovative structural tuning that improves interfacial reactant concentration and promote the timely release of H<sub>2</sub>O<sub>2</sub>; modulation of electrolyte and electrode interfaces to support the 2e<sup>-</sup> pathways; and the application of C-MFECs in reactors and integrated energy systems. Finally, the current challenges and future directions in this burgeoning field are discussed.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141533059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xijun Cheng, Siyang Nie, Yuan Huang, Qingda Liu, Liang Wu, Xun Wang
Integration of inherently incompatible elements into a single sublattice, resulting in the formation of monophasic metal oxide, holds great scientific promise; it unveils that the overlooked surface entropy in subnanometer materials can thermodynamically facilitate the formation of homogeneous single-phase structures. Here a facile approach is proposed for synthesizing multimetallic oxide subnanometer nanobelts (MMO-PMA SNBs) by harnessing the potential of phosphomolybdic acid (PMA) clusters to capture inorganic nuclei and inhibiting their subsequent growth in solvothermal reactions. Experimental and theoretical analyses show that PMA in MMO-PMA SNBs not only aids subnanometer structure formation but also induces in situ modifications to catalytic sites. The electron transfer from PMA, coupled with the loss of elemental identity of transition metals, leads to electron delocalization, jointly activating the reaction sites. The unique structure makes pentametallic oxide (PMO-PMA SNBs) achieve a current density of 10 mA cm-2 at a low potential of 1.34 V and remain stable for 24 h at 10 mA cm-2 on urea oxidation reaction (UOR). The exceptional UOR catalytic activity suggests a potential for utilizing multimetallic subnanometer nanostructures in energy conversion and environmental remediation.
将本质上不相容的元素整合到一个单一的亚晶格中,形成单相金属氧化物,具有巨大的科学前景;它揭示了亚纳米材料中被忽视的表面熵可以在热力学上促进均匀单相结构的形成。本文提出了一种简便的方法,通过利用磷钼酸(PMA)团簇捕获无机核的潜力,抑制它们在溶热反应中的后续生长,从而合成多金属氧化物亚纳米颗粒(MMO-PMA SNBs)。实验和理论分析表明,MMO-PMA SNB 中的 PMA 不仅有助于亚纳米结构的形成,还能诱导催化位点的原位修饰。PMA 的电子转移以及过渡金属元素特性的丧失导致了电子析出,从而共同激活了反应位点。这种独特的结构使得五金属氧化物(PMO-PMA SNBs)在 1.34 V 的低电位下电流密度达到 10 mA cm-2,并在 10 mA cm-2 的尿素氧化反应(UOR)中保持稳定 24 小时。卓越的尿素氧化反应催化活性表明,多金属亚纳米结构在能源转换和环境修复方面具有广阔的应用前景。
{"title":"Electron-Delocalization Across High Surface Entropy Sub-1 nm Nanobelts Toward Enhanced Electrocatalytic Urea Oxidation.","authors":"Xijun Cheng, Siyang Nie, Yuan Huang, Qingda Liu, Liang Wu, Xun Wang","doi":"10.1002/smll.202404595","DOIUrl":"https://doi.org/10.1002/smll.202404595","url":null,"abstract":"<p><p>Integration of inherently incompatible elements into a single sublattice, resulting in the formation of monophasic metal oxide, holds great scientific promise; it unveils that the overlooked surface entropy in subnanometer materials can thermodynamically facilitate the formation of homogeneous single-phase structures. Here a facile approach is proposed for synthesizing multimetallic oxide subnanometer nanobelts (MMO-PMA SNBs) by harnessing the potential of phosphomolybdic acid (PMA) clusters to capture inorganic nuclei and inhibiting their subsequent growth in solvothermal reactions. Experimental and theoretical analyses show that PMA in MMO-PMA SNBs not only aids subnanometer structure formation but also induces in situ modifications to catalytic sites. The electron transfer from PMA, coupled with the loss of elemental identity of transition metals, leads to electron delocalization, jointly activating the reaction sites. The unique structure makes pentametallic oxide (PMO-PMA SNBs) achieve a current density of 10 mA cm<sup>-2</sup> at a low potential of 1.34 V and remain stable for 24 h at 10 mA cm<sup>-2</sup> on urea oxidation reaction (UOR). The exceptional UOR catalytic activity suggests a potential for utilizing multimetallic subnanometer nanostructures in energy conversion and environmental remediation.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141533063","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaodong Zhu, Xide Zhang, Jiahao Guo, Lei He, Fuming Wang, Zhiwen Qiu, Ang Li, Jing Zhang, Fu Gao, Wei Li
Despite the advantages of high tissue penetration depth, selectivity, and non-invasiveness of photothermal therapy for cancer treatment, developing NIR-II photothermal agents with desirable photothermal performance and advanced theranostics ability remains a key challenge. Herein, a universal surface modification strategy is proposed to effectively improve the photothermal performance of vanadium carbide MXene nanosheets (L-V2C) with the removal of surface impurity ions and generation of mesopores. Subsequently, MnOx coating capable of T1-weighted magnetic resonance imaging can be in situ formed through surface redox reaction on L-V2C, and then, stable nanoplatforms (LVM-PEG) under physiological conditions can be obtained after further PEGylation. In the tumor microenvironment irradiated by NIR-II laser, multivalent Mn ions released from LVM-PEG, as a reversible electronic station, can consume the overexpression of glutathione and catalyze a Fenton-like reaction to produce ·OH, resulting in synchronous cellular oxidative damage. Efficient synergistic therapy promotes immunogenic cell death, improving tumor-related immune microenvironment and immunomodulation, and thus, LVM-PEG can demonstrate high accuracy and excellent anticancer efficiency guided by multimodal imaging. As a result, this study provides a new approach for the customization of 2D surface strategies and the study of synergistic therapy mechanisms, highlighting the application of MXene-based materials in the biomedical field.
{"title":"Surface Engineering Enhances Vanadium Carbide MXene-Based Nanoplatform Triggered by NIR-II for Cancer Theranostics.","authors":"Xiaodong Zhu, Xide Zhang, Jiahao Guo, Lei He, Fuming Wang, Zhiwen Qiu, Ang Li, Jing Zhang, Fu Gao, Wei Li","doi":"10.1002/smll.202401655","DOIUrl":"https://doi.org/10.1002/smll.202401655","url":null,"abstract":"<p><p>Despite the advantages of high tissue penetration depth, selectivity, and non-invasiveness of photothermal therapy for cancer treatment, developing NIR-II photothermal agents with desirable photothermal performance and advanced theranostics ability remains a key challenge. Herein, a universal surface modification strategy is proposed to effectively improve the photothermal performance of vanadium carbide MXene nanosheets (L-V<sub>2</sub>C) with the removal of surface impurity ions and generation of mesopores. Subsequently, MnO<sub>x</sub> coating capable of T1-weighted magnetic resonance imaging can be in situ formed through surface redox reaction on L-V<sub>2</sub>C, and then, stable nanoplatforms (LVM-PEG) under physiological conditions can be obtained after further PEGylation. In the tumor microenvironment irradiated by NIR-II laser, multivalent Mn ions released from LVM-PEG, as a reversible electronic station, can consume the overexpression of glutathione and catalyze a Fenton-like reaction to produce ·OH, resulting in synchronous cellular oxidative damage. Efficient synergistic therapy promotes immunogenic cell death, improving tumor-related immune microenvironment and immunomodulation, and thus, LVM-PEG can demonstrate high accuracy and excellent anticancer efficiency guided by multimodal imaging. As a result, this study provides a new approach for the customization of 2D surface strategies and the study of synergistic therapy mechanisms, highlighting the application of MXene-based materials in the biomedical field.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532996","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Drug-resistant bacterial infections and their lipopolysaccharide-related inflammatory complications continue to pose significant challenges in traditional treatments. Inspired by the rapid initiation of resident macrophages to form aggregates for efficient antibacterial action, this study proposes a multifunctional and enhanced antibacterial strategy through the construction of novel biomimetic cell membrane polypeptide nanonets (R-DPB-TA-Ce). The design involves the fusion of end-terminal lipidated polypeptides containing side-chain cationic boronic acid groups (DNPLBA) with cell membrane intercalation engineering (R-DPB), followed by coordination with the tannic acid-cerium complex (TA-Ce) to assemble into a biomimetic nanonet through boronic acid-polyphenol-metal ion interactions. In addition to the ability of RAW 264.7 macrophages cell membrane components' (R) ability to neutralize lipopolysaccharide (LPS), R-DPB-TA-Ce demonstrated enhanced capture of bacteria and its LPS, leveraging nanoconfinement-enhanced multiple interactions based on the boronic acid-polyphenol nanonets skeleton combined with polysaccharide. Utilizing these advantages, indocyanine green (ICG) is further employed as a model drug for delivery, showcasing the exceptional treatment effect of R-DPB-TA-Ce as a new biomimetic assembled drug delivery system in antibacterial, anti-inflammatory, and wound healing promotion. Thus, this strategy of mimicking macrophage aggregates is anticipated to be further applicable to various types of cell membrane engineering for enhanced antibacterial treatment.
耐药性细菌感染及其与脂多糖相关的炎症并发症仍然是传统治疗方法面临的重大挑战。受驻留巨噬细胞迅速形成聚集体以达到高效抗菌作用的启发,本研究通过构建新型仿生物细胞膜多肽纳米网(R-DPB-TA-Ce),提出了一种多功能增强型抗菌策略。该设计包括将含有侧链阳离子硼酸基团(DNPLBA)的末端脂化多肽与细胞膜插层工程(R-DPB)融合,然后与单宁酸铈复合物(TA-Ce)配位,通过硼酸-多酚-金属离子的相互作用组装成仿生纳米网。除了 RAW 264.7 巨噬细胞细胞膜成分(R)中和脂多糖(LPS)的能力外,R-DPB-TA-Ce 还利用基于硼酸-多酚纳米网骨架与多糖结合的纳米膦强化多重相互作用,增强了对细菌及其 LPS 的捕获能力。利用这些优势,吲哚菁绿(ICG)被进一步用作给药模型,展示了 R-DPB-TA-Ce 作为一种新型仿生组装给药系统在抗菌、消炎和促进伤口愈合方面的卓越治疗效果。因此,这种模拟巨噬细胞聚集体的策略有望进一步应用于各类细胞膜工程,以增强抗菌治疗效果。
{"title":"Cell Membrane Engineered Polypeptide Nanonets Mimicking Macrophage Aggregates for Enhanced Antibacterial Treatment.","authors":"Jiang Xiao, Zhongquan Song, Tengfei Liu, Zengchao Guo, Xiaohui Liu, Hui Jiang, Xuemei Wang","doi":"10.1002/smll.202401845","DOIUrl":"https://doi.org/10.1002/smll.202401845","url":null,"abstract":"<p><p>Drug-resistant bacterial infections and their lipopolysaccharide-related inflammatory complications continue to pose significant challenges in traditional treatments. Inspired by the rapid initiation of resident macrophages to form aggregates for efficient antibacterial action, this study proposes a multifunctional and enhanced antibacterial strategy through the construction of novel biomimetic cell membrane polypeptide nanonets (R-DPB-TA-Ce). The design involves the fusion of end-terminal lipidated polypeptides containing side-chain cationic boronic acid groups (DNPLBA) with cell membrane intercalation engineering (R-DPB), followed by coordination with the tannic acid-cerium complex (TA-Ce) to assemble into a biomimetic nanonet through boronic acid-polyphenol-metal ion interactions. In addition to the ability of RAW 264.7 macrophages cell membrane components' (R) ability to neutralize lipopolysaccharide (LPS), R-DPB-TA-Ce demonstrated enhanced capture of bacteria and its LPS, leveraging nanoconfinement-enhanced multiple interactions based on the boronic acid-polyphenol nanonets skeleton combined with polysaccharide. Utilizing these advantages, indocyanine green (ICG) is further employed as a model drug for delivery, showcasing the exceptional treatment effect of R-DPB-TA-Ce as a new biomimetic assembled drug delivery system in antibacterial, anti-inflammatory, and wound healing promotion. Thus, this strategy of mimicking macrophage aggregates is anticipated to be further applicable to various types of cell membrane engineering for enhanced antibacterial treatment.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141533060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}