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Template Evolution Induced Relay Self-Assembly for Mesoporous Carbonaceous Materials via Hydrothermal Carbonization 通过水热碳化实现介孔碳质材料的模板演化诱导中继自组装
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1021/acsnano.4c03744
Xie Zhang, Xucheng Lv, Zikai Qian, Chunhong Chen, Shanjun Mao, Jun Lu, Yong Wang
Constructing carbonaceous materials with versatile surface structures still remains a great challenge due to limited self-assembly methods, especially at high temperatures. This study presents an innovative template evolution induced relay self-assembly (TEIRSA) for the fabrication of large polyoxometalate (POM)-mixed carbonaceous nanosheets featuring surface mesoporous structures through hydrothermal carbonization (HTC). The method employs POM and acetone as additives, cleverly modulating the Ostwald ripening-like process of P123-based micelles, effectively addressing the instability challenges inherent in traditional soft-template methods, especially within the demanding carbohydrate HTC process. Additionally, this method allows for the independent regulation of surface architectures through the selection of organic additives. The resulting nanosheets exhibit diverse surface morphologies, including surface spherical mesopores, 1D open channels, and smooth surfaces. Their unexpectedly versatile properties have swiftly garnered recognition, showing potential in the application of lithium–sulfur batteries.
由于自组装方法有限,尤其是在高温条件下,构建具有多功能表面结构的碳质材料仍然是一项巨大的挑战。本研究提出了一种创新的模板进化诱导接力自组装(TEIRSA)方法,用于通过水热碳化(HTC)制造具有表面介孔结构的大型聚氧化铝(POM)混合碳质纳米片。该方法采用 POM 和丙酮作为添加剂,巧妙地调节了基于 P123 胶束的类似奥斯特瓦尔德熟化的过程,有效地解决了传统软模板方法固有的不稳定性难题,尤其是在要求苛刻的碳水化合物 HTC 过程中。此外,这种方法还可以通过选择有机添加剂对表面结构进行独立调节。由此产生的纳米片呈现出多种表面形态,包括表面球形介孔、一维开放通道和光滑表面。它们出人意料的多功能特性迅速获得了认可,并显示出在锂硫电池应用中的潜力。
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引用次数: 0
Layer-Dependent Electromechanical Response in Twisted Graphene Moiré Superlattices. 扭曲石墨烯 Moiré 超晶格中取决于层的机电响应。
IF 15.8 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1021/acsnano.4c01794
Hanhao Zhang, Yuanhao Wei, Yuhao Li, Shengsheng Lin, Jiarui Wang, Takashi Taniguchi, Kenji Watanabe, Jiangyu Li, Yi Shi, Xinran Wang, Yan Shi, Zaiyao Fei

The coupling of mechanical deformation and electrical stimuli at the nanoscale has been the subject of intense investigation in the realm of materials science. Recently, twisted van der Waals (vdW) materials have emerged as a platform for exploring exotic quantum states. These states are intimately tied to the formation of moiré superlattices, which can be visualized by directly exploiting the electromechanical response. However, the origin of the response, even in twisted bilayer graphene (tBLG), remains unsettled. Here, employing lateral piezoresponse force microscopy (LPFM), we investigate the electromechanical responses of marginally twisted graphene moiré superlattices with different layer thicknesses. We observe distinct LPFM amplitudes and spatial profiles in tBLG and twisted monolayer-bilayer graphene (tMBG), exhibiting effective in-plane piezoelectric coefficients of 0.05 and 0.35 pm/V, respectively. Force tuning experiments further underscored a marked divergence in their responses. The contrasting behaviors suggest different electromechanical couplings in tBLG and tMBG. In tBLG, the response near the domain walls is attributed to the flexoelectric effect, while in tMBG, the behaviors can be comprehended within the context of the piezoelectric effect. Our results not only provide insights into electromechanical and corporative effects in twisted vdW materials with different stacking symmetries but may also offer a way to engineer them at the nanoscale.

纳米尺度的机械变形和电刺激耦合一直是材料科学领域深入研究的课题。最近,扭曲范德华(vdW)材料成为探索奇异量子态的平台。这些状态与摩尔纹超晶格的形成密切相关,可以通过直接利用机电响应将其可视化。然而,即使在扭曲双层石墨烯(tBLG)中,这种响应的起源仍未确定。在此,我们采用横向压电响应力显微镜(LPFM)研究了不同层厚的微扭曲石墨烯摩尔超晶格的机电响应。我们在 tBLG 和扭曲单层-双层石墨烯 (tMBG) 中观察到了不同的 LPFM 振幅和空间轮廓,其平面内有效压电系数分别为 0.05 和 0.35 pm/V。力调谐实验进一步凸显了它们在响应上的明显差异。对比行为表明 tBLG 和 tMBG 具有不同的机电耦合。在 tBLG 中,畴壁附近的响应归因于挠电效应,而在 tMBG 中,这些行为可以在压电效应的背景下理解。我们的研究结果不仅让人们深入了解了具有不同堆积对称性的扭曲 vdW 材料的机电效应和体电效应,还为在纳米尺度上设计这些材料提供了一种方法。
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引用次数: 0
Nonswellable Hydrogel Patch with Tissue-Mimetic Mechanical Characteristics Remodeling In Vivo Microenvironment for Effective Adhesion Prevention. 具有组织模拟机械特性的非孔性水凝胶贴片可重塑体内微环境,有效防止粘附。
IF 15.8 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1021/acsnano.4c02321
Xuezhe Liu, Xingan Qiu, Linxia Nie, Bikun Zhou, Pengzhen Bu, Yang Li, Xinwen Xue, Bo Tang, Qian Feng, Kaiyong Cai

Postoperative adhesion is a common complication after abdominal surgery, but current clinical products have unsatisfactory therapeutic effects. Here, we present a hydrogel patch formed in a single step through dialysis. The exchange of DMSO into water facilitates hydrophobic aggregate in situ formation and the formation of hydrogen bonds within the hydrogel. Thanks to the optimized component ratio and precise structural design. The hydrogel patch has soft-tissue-like mechanical characteristics, including high strength, high toughness, low modulus similar to the abdominal wall, good fatigue resistance, and fast self-recovery properties. The nonswellable hydrogel patch retains over 80% of its original mechanical properties after 7 days of immersion in physiological saline, with a maximum swelling ratio of 5.6%. Moreover, the hydrophobic biomultifunctionality of benzyl isothiocyanate can self-assemble onto the hydrogel patch during the sol-gel transition process, enabling it to remodel the inflammatory microenvironment through synergistic antibacterial, antioxidant, and anti-inflammatory effects. The hydrogel patch prevents postsurgical adhesion in a rat sidewall defect-cecum abrasion model and outperforms the leading commercial Interceed. It holds promising potential for clinical translation, considering that FDA-approved raw materials (PVA and gelatin) form the backbone of this effective hydrogel patch.

术后粘连是腹部手术后常见的并发症,但目前的临床产品治疗效果并不理想。在此,我们介绍一种通过透析一步成型的水凝胶补片。将二甲基亚砜(DMSO)置换成水有利于疏水聚合体的原位形成以及水凝胶内部氢键的形成。由于采用了优化的成分比例和精确的结构设计,水凝胶贴片具有柔软的触感和极佳的抗氧化性。水凝胶补片具有类似软组织的机械特性,包括高强度、高韧性、类似腹壁的低模量、良好的抗疲劳性和快速自我恢复特性。非膨胀水凝胶贴片在生理盐水中浸泡 7 天后,仍能保持 80% 以上的原有机械特性,最大膨胀率为 5.6%。此外,在溶胶-凝胶转化过程中,异硫氰酸苄酯的疏水性生物多功能性可自组装到水凝胶贴片上,使其能够通过协同抗菌、抗氧化和抗炎作用重塑炎症微环境。在大鼠侧壁缺损-骨盆擦伤模型中,水凝胶贴片可防止手术后粘连,性能优于主要的商用 Interceed。考虑到美国食品及药物管理局批准的原材料(PVA 和明胶)构成了这种高效水凝胶贴片的骨架,它具有临床转化的巨大潜力。
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引用次数: 0
Slow Hot-Exciton Cooling and Enhanced Interparticle Excitonic Coupling in HgTe Quantum Dots 碲镉汞量子点中的慢热激子冷却和增强的粒子间激子耦合
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1021/acsnano.4c05061
Kezhou Fan, Kseniia A. Sergeeva, Aleksandr A. Sergeev, Lu Zhang, Christopher C. S. Chan, Zhuo Li, Xiaoyan Zhong, Stephen V. Kershaw, Junwei Liu, Andrey L. Rogach, Kam Sing Wong
Rapid hot-carrier/exciton cooling constitutes a major loss channel for photovoltaic efficiency. How to decelerate the hot-carrier/exciton relaxation remains a crux for achieving high-performance photovoltaic devices. Here, we demonstrate slow hot-exciton cooling that can be extended to hundreds of picoseconds in colloidal HgTe quantum dots (QDs). The energy loss rate is 1 order of magnitude smaller than bulk inorganic semiconductors, mediated by phonon bottleneck and interband biexciton Auger recombination (BAR) effects, which are both augmented at reduced QD sizes. The two effects are competitive with the emergence of multiple exciton generation. Intriguingly, BAR dominates even under low excitation fluences with a decrease in interparticle distance. Both experimental evidence and numerical evidence reveal that such efficient BAR derives from the tunneling-mediated interparticle excitonic coupling induced by wave function overlap between neighboring HgTe QDs in films. Thus, our study unveils the potential for realizing efficient hot-carrier/exciton solar cells based on HgTe QDs. Fundamentally, we reveal that the delocalized nature of quantum-confined wave function intensifies BAR. The interparticle excitonic coupling may cast light on the development of next-generation photoelectronic materials, which can retain the size-tunable confinement of colloidal semiconductor QDs while simultaneously maintaining high mobilities and conductivities typical for bulk semiconductor materials.
快速的热载流子/外加子冷却是光伏效率的主要损失渠道。如何减缓热载流子/外加子弛豫仍然是实现高性能光伏设备的关键。在这里,我们展示了在胶体碲化镉量子点(QDs)中可以延长到数百皮秒的慢热激子冷却。在声子瓶颈和带间双激子奥杰尔重组(BAR)效应的介导下,能量损失率比块状无机半导体小 1 个数量级。这两种效应与多激子生成的出现相互竞争。有趣的是,即使在低激发通量下,随着粒子间距的减小,BAR 也会占主导地位。实验证据和数值证据都表明,如此高效的 BAR 源自薄膜中相邻 HgTe QD 之间波函数重叠所诱导的隧道介导的粒子间激子耦合。因此,我们的研究揭示了基于 HgTe QDs 实现高效热载流子/激子太阳能电池的潜力。从根本上说,我们揭示了量子约束波函数的非局域性强化了 BAR。粒子间的激子耦合可能会为下一代光电子材料的开发带来启示,这种材料既能保持胶体半导体 QDs 尺寸可调的约束性,又能维持块体半导体材料典型的高迁移率和高电导率。
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引用次数: 0
Visualization of Multiple-Resonance-Induced Frontier Molecular Orbitals in a Single Multiple-Resonance Thermally Activated Delayed Fluorescence Molecule. 单个多重共振热激活延迟荧光分子中多重共振诱导的前沿分子轨道的可视化。
IF 15.8 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1021/acsnano.4c04813
Jaehyun Bae, Miyabi Imai-Imada, Hyung Suk Kim, Minhui Lee, Hiroshi Imada, Youichi Tsuchiya, Takuji Hatakeyama, Chihaya Adachi, Yousoo Kim

The spatial distribution and electronic properties of the frontier molecular orbitals (FMOs) in a thermally activated delayed fluorescence (TADF) molecule contribute significantly to the TADF properties, and thus, a detailed understanding and sophisticated control of the FMOs are fundamental to the design of TADF molecules. However, for multiple-resonance (MR)-TADF molecules that achieve spatial separation of FMOs by the MR effect, the distinctive distribution of these molecular orbitals poses significant challenges for conventional computational analysis and ensemble averaging methods to elucidate the FMOs' separation and the precise mechanism of luminescence. Therefore, the visualization and analysis of electronic states with the specific energy level of a single MR-TADF molecule will provide a deeper understanding of the TADF mechanism. Here, scanning tunneling microscopy/spectroscopy (STM/STS) was used to investigate the electronic states of the DABNA-1 molecule at the atomic scale. FMOs' visualization and local density of states analysis of the DABNA-1 molecule clearly show that MR-TADF molecules also have well-separated FMOs according to the internal heteroatom arrangement, providing insights that complement existing theoretical prediction methods.

热激活延迟荧光(TADF)分子中前沿分子轨道(FMO)的空间分布和电子特性对 TADF 特性有重要影响,因此,对 FMO 的详细了解和精密控制是 TADF 分子设计的基础。然而,对于通过磁共振效应实现 FMO 空间分离的多重共振(MR)-TADF 分子来说,这些分子轨道的独特分布对传统的计算分析和集合平均法阐明 FMO 的分离和精确的发光机制构成了巨大挑战。因此,对单个 MR-TADF 分子特定能级的电子状态进行可视化分析将有助于加深对 TADF 机制的理解。在此,我们使用扫描隧道显微镜/光谱学(STM/STS)在原子尺度上研究了 DABNA-1 分子的电子态。DABNA-1分子的FMOs可视化和局域态密度分析清楚地表明,MR-TADF分子根据内部杂原子的排列也具有良好分离的FMOs,这为补充现有的理论预测方法提供了启示。
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引用次数: 0
Near-Infrared Light-Activatable DNA Tentacles for Efficient Inhibition of Tumor Metastasis by Bio-Orthogonal Cell Assembly 近红外线可激活 DNA 触手,通过生物横向细胞组装高效抑制肿瘤转移
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1021/acsnano.4c05216
Lingzhi Cao, Xinjian Yang, Yimei Li, Yang Yang, Qiulin Liu, Massimo Bottini, Yi Jin, Bei Wang, Jinchao Zhang, Xing-jie Liang
Tumor metastasis remains a major challenge in cancer management. Among various treatment strategies, immune cell-based cancer therapy holds a great potential for inhibiting metastasis. However, its wide application in cancer therapy is restricted by complex preparations, as well as inadequate homing and controllability. Herein, we present a groundbreaking approach for bioorthogonally manipulating tumor-NK (natural killer) cell assembly to inhibit tumor metastasis. Multiple dibenzocyclootyne (DBCO) groups decorated long single-stranded DNA were tail-modified on core–shell upconversion nanoparticles (CSUCNPs) and condensed by photosensitive chemical linker (PC-Linker) DNA to shield most of the DBCO groups. On the one hand, the light-triggered DNA scaffolds formed a cross-linked network by click chemistry, effectively impeding tumor cell migration. On the other hand, the efficient cellular assembly facilitated the effective communication between tumor cells and NK-92 cells, leading to enhanced immune response against tumors and further suppression of tumor metastasis. These features make our strategy highly applicable to a wide range of metastatic cancers.
肿瘤转移仍然是癌症治疗的一大挑战。在各种治疗策略中,基于免疫细胞的癌症疗法在抑制转移方面具有巨大潜力。然而,其在癌症治疗中的广泛应用受制于复杂的制备方法以及不充分的归巢性和可控性。在此,我们提出了一种开创性的生物正交操纵肿瘤-NK(自然杀伤)细胞集结以抑制肿瘤转移的方法。在核壳上转换纳米粒子(CSUCNPs)上尾部修饰了装饰长单链DNA的多个二苯并环羰基(DBCO)基团,并通过光敏化学连接体(PC-Linker)DNA凝结以屏蔽大部分DBCO基团。一方面,光诱导 DNA 支架通过点击化学反应形成交联网络,有效阻止肿瘤细胞迁移。另一方面,高效的细胞组装促进了肿瘤细胞与 NK-92 细胞之间的有效交流,从而增强了对肿瘤的免疫反应,进一步抑制了肿瘤转移。这些特点使我们的策略非常适用于各种转移性癌症。
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引用次数: 0
MicroRNA and Gut Microbiota Alter Intergenerational Effects of Paternal Exposure to Polyethylene Nanoplastics 微RNA和肠道微生物群改变父辈接触聚乙烯纳米塑料的代际效应
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1021/acsnano.4c06298
Jiaqi Sun, Miaomiao Teng, Wentao Zhu, Xiaoli Zhao, Lihui Zhao, Yunxia Li, Zixuan Zhang, Yunjie Liu, Sheng Bi, Fengchang Wu
Nanoplastics (NPs), as emerging contaminants, have been shown to cause testicular disorders in mammals. However, whether paternal inheritance effects on offspring health are involved in NP-induced reproductive toxicity remains unclear. In this study, we developed a mouse model where male mice were administered 200 nm polyethylene nanoparticles (PE-NPs) at a concentration of 2 mg/L through daily gavage for 35 days to evaluate the intergenerational effects of PE-NPs in an exclusive male-lineage transmission paradigm. We observed that paternal exposure to PE-NPs significantly affected growth phenotypes and sex hormone levels and induced histological damage in the testicular tissue of both F0 and F1 generations. In addition, consistent changes in sperm count, motility, abnormalities, and gene expression related to endoplasmic reticulum stress, sex hormone synthesis, and spermatogenesis were observed across paternal generations. The upregulation of microRNA (miR)-1983 and the downregulation of miR-122-5p, miR-5100, and miR-6240 were observed in both F0 and F1 mice, which may have been influenced by reproductive signaling pathways, as indicated by the RNA sequencing of testis tissues and quantitative real-time polymerase chain reaction findings. Furthermore, alterations in the gut microbiota and subsequent Spearman correlation analysis revealed that an increased abundance of Desulfovibrio (C21_c20) and Ruminococcus (gnavus) and a decreased abundance of Allobaculum were positively associated with spermatogenic dysfunction. These findings were validated in a fecal microbiota transplantation trial. Our results demonstrate that changes in miRNAs and the gut microbiota caused by paternal exposure to PE-NPs mediated intergenerational effects, providing deeper insights into mechanisms underlying the impact of paternal inheritance.
纳米塑料(NPs)作为一种新出现的污染物,已被证明会导致哺乳动物睾丸功能紊乱。然而,NP诱导的生殖毒性是否涉及父系遗传对后代健康的影响仍不清楚。在本研究中,我们建立了一个小鼠模型,通过每天灌胃给雄性小鼠注射浓度为 2 毫克/升的 200 纳米聚乙烯纳米粒子(PE-NPs),持续 35 天,以评估 PE-NPs 在专有雄性血统传递范例中的代际效应。我们观察到,父代暴露于 PE-NPs 会显著影响 F0 代和 F1 代的生长表型和性激素水平,并诱发睾丸组织的组织学损伤。此外,我们还观察到不同父代的精子数量、活力、畸形以及与内质网应激、性激素合成和精子发生有关的基因表达发生了一致的变化。睾丸组织的 RNA 测序和实时定量聚合酶链反应结果表明,F0 和 F1 小鼠的微 RNA (miR)-1983 上调,miR-122-5p、miR-5100 和 miR-6240 下调,这可能受到生殖信号通路的影响。此外,肠道微生物群的改变和随后的斯皮尔曼相关性分析表明,脱硫弧菌(C21_c20)和小反刍球菌(gnavus)丰度的增加以及Allobaculum丰度的降低与生精功能障碍呈正相关。这些发现在粪便微生物群移植试验中得到了验证。我们的研究结果表明,父亲暴露于PE-NPs导致的miRNA和肠道微生物群的变化会产生代际效应,从而使人们对父系遗传影响的机制有了更深入的了解。
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引用次数: 0
Engineered Cyanobacteria-Based Living Materials for Bioremediation of Heavy Metals Both In Vitro and In Vivo. 体外和体内重金属生物修复的蓝藻生物材料工程。
IF 15.8 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1021/acsnano.4c02493
Tao Sun, Huaishu Huo, Yingying Zhang, Yaru Xie, Yize Li, Kungang Pan, Fenfang Zhang, Jing Liu, Yindong Tong, Weiwen Zhang, Lei Chen

The pollution caused by heavy metals (HMs) represents a global concern due to their serious environmental threat. Photosynthetic cyanobacteria have a natural niche and the ability to remediate HMs such as cadmium. However, their practical application is hindered by a low tolerance to HMs and issues related to recycling. In response to these challenges, this study focuses on the development and evaluation of engineered cyanobacteria-based living materials for HMs bioremediation. Genes encoding phytochelatins (PCSs) and metallothioneins (MTs) were introduced into the model cyanobacterium Synechocystis sp. PCC 6803, creating PM/6803. The strain exhibited improved tolerance to multiple HMs and effectively removed a combination of Cd2+, Zn2+, and Cu2+. Using Cd2+ as a representative, PM/6803 achieved a bioremediation rate of approximately 21 μg of Cd2+/OD750 under the given test conditions. To facilitate its controllable application, PM/6803 was encapsulated using sodium alginate-based hydrogels (PM/6803@SA) to create "living materials" with different shapes. This system was feasible, biocompatible, and effective for removing Cd2+ under simulated conditions of zebrafish and mice models. Briefly, in vitro application of PM/6803@SA efficiently rescued zebrafish from polluted water containing Cd2+, while in vivo use of PM/6803@SA significantly decreased the Cd2+ content in mice bodies and restored their active behavior. The study offers feasible strategies for HMs bioremediation using the interesting biomaterials of engineered cyanobacteria both in vitro and in vivo.

重金属(HMs)污染对环境造成严重威胁,已成为全球关注的问题。光合蓝藻具有天然的生态位,能够修复镉等重金属。然而,由于蓝藻对 HMs 的耐受性较低以及与回收相关的问题,它们的实际应用受到了阻碍。为应对这些挑战,本研究重点开发和评估用于 HMs 生物修复的基于蓝藻的工程生物材料。将编码植物螯合素(PCS)和金属硫蛋白(MT)的基因引入模式蓝藻 Synechocystis sp.该菌株对多种 HM 的耐受性有所提高,并能有效去除 Cd2+、Zn2+ 和 Cu2+。以 Cd2+ 为代表,在给定的测试条件下,PM/6803 的生物修复率约为 21 μg Cd2+/OD750。为了便于可控应用,PM/6803 被海藻酸钠水凝胶(PM/6803@SA)包裹,以创造出不同形状的 "活材料"。在模拟斑马鱼和小鼠模型的条件下,该系统具有可行性、生物相容性和去除 Cd2+ 的有效性。简而言之,体外应用 PM/6803@SA 能有效地将斑马鱼从含 Cd2+ 的污染水中解救出来,而体内应用 PM/6803@SA 则能显著降低小鼠体内的 Cd2+ 含量,并恢复其活跃的行为。这项研究为利用工程蓝藻这种有趣的生物材料在体外和体内进行 HMs 生物修复提供了可行的策略。
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引用次数: 0
Chemical Prelithiated 3D Lithiophilic/-Phobic Interlayer Enables Long-Term Li Plating/Stripping. 化学预层化三维亲锂/疏锂中间膜可实现长期锂电镀/剥离。
IF 15.8 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1021/acsnano.4c04507
Sandro Schöner, Dana Schmidt, Xinchang Chen, Krzysztof Dzieciol, Roland Schierholz, Pengfei Cao, Ahmad Ghamlouche, Fabian Jeschull, Anna Windmüller, Chih-Long Tsai, Xunfan Liao, Hans Kungl, Gui-Ming Zhong, Yiwang Chen, Hermann Tempel, Shicheng Yu, Rüdiger-A Eichel

The up-to-date lifespan of zero-excess lithium (Li) metal batteries is limited to a few dozen cycles due to irreversible Li-ion loss caused by interfacial reactions during cycling. Herein, a chemical prelithiated composite interlayer, made of lithiophilic silver (Ag) and lithiophobic copper (Cu) in a 3D porous carbon fiber matrix, is applied on a planar Cu current collector to regulate Li plating and stripping and prevent undesired reactions. The Li-rich surface coating of lithium oxide (Li2O), lithium carboxylate (RCO2Li), lithium carbonates (ROCO2Li), and lithium hydride (LiH) is formed by soaking and directly heating the interlayer in n-butyllithium hexane solution. Although only a thin coating of ∼10 nm is created, it effectively regulates the ionic and electronic conductivity of the interlayer via these surface compounds and reduces defect sites by reactions of n-butyllithium with heteroatoms in the carbon fibers during formation. The spontaneously formed lithiophilic-lithiophobic gradient across individual carbon fiber provides homogeneous Li-ion deposition, preventing concentrated Li deposition. The porous structure of the composite interlayer eliminates the built-in stress upon Li deposition, and the anisotropically distributed carbon fibers enable uniform charge compensation. These features synergistically minimize the side reactions and compensate for Li-ion loss while cycling. The prepared zero-excess Li metal batteries could be cycled 300 times at 1.17 C with negligible capacity fading.

由于循环过程中的界面反应会造成不可逆的锂离子损耗,零过量锂(Li)金属电池的最新寿命仅限于几十次循环。在这里,一种由亲锂银(Ag)和疏锂铜(Cu)在三维多孔碳纤维基体中制成的化学预锂化复合中间膜被应用于平面铜集流器上,以调节锂的电镀和剥离,并防止发生不希望发生的反应。氧化锂(Li2O)、羧酸锂(RCO2Li)、碳酸锂(ROCO2Li)和氢化锂(LiH)的富锂表面涂层是通过在正丁基锂己烷溶液中浸泡并直接加热夹层形成的。虽然形成的涂层只有 10 纳米,但通过这些表面化合物可有效调节夹层的离子和电子导电性,并在形成过程中通过正丁锂与碳纤维中的杂原子反应减少缺陷位点。在单根碳纤维上自发形成的亲锂-疏锂梯度可提供均匀的锂离子沉积,防止锂离子集中沉积。复合夹层的多孔结构消除了锂沉积时的内置应力,各向异性分布的碳纤维实现了均匀的电荷补偿。这些特性协同作用,最大限度地减少了副反应,并补偿了循环过程中的锂离子损失。所制备的零附加锂金属电池可在 1.17 C 下循环 300 次,容量衰减可忽略不计。
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引用次数: 0
On-Wire Design of Axial Periodic Halide Perovskite Superlattices for High-Performance Photodetection. 用于高性能光电探测的轴向周期卤化物过氧化物超晶格的线上设计
IF 15.8 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1021/acsnano.4c05205
Qihang Lv, Xia Shen, Xuyang Li, You Meng, Kin Man Yu, Pengfei Guo, Liantuan Xiao, Johnny C Ho, Xidong Duan, Xiangfeng Duan

Precise synthesis of all-inorganic lead halide perovskite nanowire heterostructures and superlattices with designable modulation of chemical compositions is essential for tailoring their optoelectronic properties. Nevertheless, controllable synthesis of perovskite nanostructure heterostructures remains challenging and underexplored to date. Here, we report a rational strategy for wafer-scale synthesis of one-dimensional periodic CsPbCl3/CsPbI3 superlattices. We show that the highly parallel array of halide perovskite nanowires can be prepared roughly as horizontally guided growth on an M-plane sapphire. A periodic patterning of the sapphire substrate enables position-selective ion exchange to obtain highly periodic CsPbCl3/CsPbI3 nanowire superlattices. This patterning is further confirmed by micro-photoluminescence investigations, which show that two separate band-edge emission peaks appear at the interface of a CsPbCl3/CsPbI3 heterojunction. Additionally, compared with the pure CsPbCl3 nanowires, photodetectors fabricated using these periodic heterostructure nanowires exhibit superior photoelectric performance, namely, high ION/IOFF ratio (104), higher responsivity (49 A/W), and higher detectivity (1.51 × 1013 Jones). Moreover, a spatially resolved visible image sensor based on periodic nanowire superlattices is demonstrated with good imaging capability, suggesting promising application prospects in future photoelectronic imaging systems. All these results based on the periodic CsPbCl3/CsPbI3 nanowire superlattices provides an attractive material platform for integrated perovskite devices and circuits.

精确合成全无机卤化铅过氧化物纳米线异质结构和超晶格,并对化学成分进行可设计调控,对于定制其光电特性至关重要。然而,迄今为止,过氧化物纳米结构异质结构的可控合成仍具有挑战性,且尚未得到充分探索。在此,我们报告了一种在晶圆级合成一维周期性铯硼氯化物/铯硼碘化物超晶格的合理策略。我们的研究表明,高度平行的卤化物包晶纳米线阵列大致可以在 M 平面蓝宝石上以水平引导生长的方式制备。蓝宝石衬底的周期性图案化可实现位置选择性离子交换,从而获得高度周期性的 CsPbCl3/CsPbI3 纳米线超晶格。显微光致发光研究进一步证实了这种图案化,研究表明在 CsPbCl3/CsPbI3 异质结的界面上出现了两个独立的带边发射峰。此外,与纯 CsPbCl3 纳米线相比,利用这些周期性异质结构纳米线制造的光电探测器表现出更优越的光电性能,即离子/离子交换比高(104)、响应率高(49 A/W)和探测率高(1.51 × 1013 Jones)。此外,基于周期性纳米线超晶格的空间分辨可见光图像传感器具有良好的成像能力,在未来的光电子成像系统中具有广阔的应用前景。所有这些基于周期性 CsPbCl3/CsPbI3 纳米线超晶格的成果为集成过氧化物器件和电路提供了一个极具吸引力的材料平台。
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