IF 11.6 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Carbon

Pub Date : 2026-01-02 DOI: 10.1016/j.carbon.2026.121228

Michal Langer , Lukáš Zdražil , Andrey L. Rogach , Silvio Osella , Michal Otyepka

Understanding the optical properties of luminescent carbon dots (CDs) at the electronic level is essential for engineering their light-responsive behavior. The localization of photoexcited species and the pathways of their de-excitation govern CD performance in sensing, bioimaging, and emerging photocatalytic applications. Yet, the underlying mechanisms remain unresolved. Here, we combine multiscale simulations with experiments on CDs synthesized from citric acid (CA) and ethylenediamine (EDA), precursors capable of forming the molecular fluorophore 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-α]pyridine-7-carboxylic acid (IPCA). All-atom molecular dynamics simulations in water reveal that CA–EDA oligomeric condensation products containing IPCA units spontaneously assemble into dynamic ∼2 nm nanoparticles with amorphous internal structures and stacked domains reminiscent of those observed in transmission electron microscopy images of CDs. Time-dependent density functional theory (TD-DFT) calculations show that photoexcited carriers are generated in these domains and remain spatially distributed, not confined to the CD core. Quenching experiments with Hg²⁺ confirm their accessibility to the environment. We therefore propose a structural model of fluorophore-rich domains embedded in an amorphous carbonaceous matrix, explaining the quasi-spherical morphology and characteristic blue photoluminescence. This model provides a mechanistic basis for fluorescence sensing and photocatalysis and establishes a framework for rational design of CDs with tailored photophysical and catalytic properties.

在电子水平上了解发光碳点（CDs）的光学特性对于设计其光响应行为至关重要。光激发物质的定位及其去激发途径决定了CD在传感、生物成像和新兴光催化应用中的性能。然而，潜在的机制仍未得到解决。本研究将多尺度模拟与实验相结合，研究了由柠檬酸（CA）和乙二胺（EDA）合成的CDs，这两种前体能够形成分子荧光基团5-氧-1,2,3,5-四氢咪唑[1,2-α]吡啶-7-羧酸（IPCA）。水中的全原子分子动力学模拟表明，含有IPCA单元的CA-EDA低聚缩合产物自发地组装成具有无定形内部结构和堆叠结构域的动态~ 2 nm纳米颗粒，使人联想到CDs的透射电子显微镜图像。时间依赖密度泛函理论（TD-DFT）计算表明，光激发载流子在这些域中产生，并保持空间分布，而不局限于CD核。Hg2+淬火实验证实了它们对环境的亲和性。因此，我们提出了一个嵌在非晶碳质基质中的富荧光团域的结构模型，解释了准球形形态和蓝色光致发光的特征。该模型为荧光传感和光催化提供了机理基础，并为合理设计具有定制光物理和催化性能的CDs建立了框架。

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引用次数: 0

Roles of precursor structure and hydrogen-donor solvents in the hydrogenation mechanism for mesophase pitch synthesis 前驱体结构和给氢溶剂在中间相沥青合成加氢机制中的作用

IF 11.6 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Carbon

Pub Date : 2025-12-31 DOI: 10.1016/j.carbon.2025.121214

Yan Yang , Qian Li , Fangfang Qin , Pingping Zuo , Shijie Qu , Wenzhong Shen

Hydrogenation polycondensation is effective for synthesizing coal-based mesophase pitch, yet its molecular-level reaction mechanisms remain elusive. This work investigated the interactions between coal tar pitch fractions (TS and TI-THFS) and hydrogen donor solvents (THN and DHN), successfully synthesizing high-quality mesophase pitch with 99.9 % optical anisotropy. This work revealed distinct molecular weight growth patterns: the TS fraction exhibited a regular 50x-24y-50x increment, while the TI-THFS fraction displayed a growth transition from 24y-50x-24y to 50x-50x. Crucially, the differing mechanisms were elucidated based on the structural characteristics of radical release. THN, by facilely liberating active hydrogen radicals, preferentially reacted with electron-rich aromatic rings to establish conjugated systems and incorporate aliphatic moieties. Conversely, DHN exhibited limited hydrogen-donating capability due to the difficulty in releasing hydrogen radicals, thus favoring dehydrogenative condensation reactions among pitch molecules. These findings provided fundamental insights into the mechanism of hydrogenation polycondensation at the molecular level, laying a theoretical groundwork for controlled mesophase pitch synthesis.

加氢缩聚是合成煤基中间相沥青的有效方法，但其分子水平的反应机理尚不清楚。研究了煤沥青馏分（TS和TI-THFS）与氢给体溶剂（THN和DHN）之间的相互作用，成功合成了光学各向异性为99.9%的高质量中间相沥青。这项工作揭示了不同的分子量增长模式：TS组分表现出规律的50x-24y-50x增长，而TI-THFS组分表现出从24y-50x-24y到50x-50x的增长转变。重要的是，基于自由基释放的结构特征，阐明了不同的机制。THN通过容易释放活性氢自由基，优先与富电子芳香环反应，建立共轭体系并结合脂肪族基团。相反，DHN由于难以释放氢自由基，其供氢能力有限，有利于沥青分子间的脱氢缩合反应。这些发现从分子水平上对加氢缩聚机理有了基本的认识，为可控中间相沥青合成奠定了理论基础。

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引用次数: 0

Partial exfoliation of carbon nanofibers to enhance Ni-N-C active sites for oxygen evolution reaction 碳纳米纤维部分剥落增强Ni-N-C析氧反应活性位点

IF 11.6 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Carbon

Pub Date : 2025-12-31 DOI: 10.1016/j.carbon.2025.121226

Carlos Serrano-Alcalde, Beatrice Ricciardi, Sara Pérez-Rodríguez, María J. Lázaro, David Sebastián

Carbon nanofibers (CNF) are promising substrates for Ni–N–C electrocatalysts in the oxygen evolution reaction (OER) due to their high electrical conductivity and remarkable resistance to oxidative degradation under harsh anodic conditions. However, this highly graphitic character limits the incorporation of single-atom species. Here, we introduce a partial exfoliation strategy via controlled oxidation (Tour method) of CNF to engineer surface defects and enhance Ni–N incorporation. This route partially exfoliates the CNF surface, increasing defect density and surface accessibility, as confirmed by electrochemical characterization, without compromising the structural integrity of nanofilaments. The controlled modification enables up to a tenfold increase in Ni-N coordination sites, as quantified by XPS, while HAADF-STEM confirms the presence of atomically dispersed Ni sites, with an enhancement of oxygen evolution current density above six-fold relative to the unmodified substrate. A trade-off situation is required between sufficient oxidation to host active sites, and excessive exfoliation leading to partial destruction of the surface. Interestingly, the faradaic efficiency remains above 90 % towards oxygen evolution, demonstrating that defect engineering through partial exfoliation effectively balances structural integrity and active site exposure. Durability experiments reveal robust performance of the most performing catalyst, with the transformation of partial content of Ni-N sites into NiOOH. This approach highlights the tunability of carbon matrices to optimize catalytic performance through controlled defect generation.

碳纳米纤维（CNF）由于其高导电性和在恶劣阳极条件下的抗氧化降解能力而成为Ni-N-C电催化剂在析氧反应（OER）中很有前途的底物。然而，这种高度石墨化的特性限制了单原子物质的掺入。在这里，我们介绍了一种通过CNF控制氧化（Tour法）的部分剥离策略来设计表面缺陷并增强Ni-N的结合。电化学表征证实，这种方法可以部分剥离CNF表面，增加缺陷密度和表面可达性，同时不影响纳米丝的结构完整性。通过XPS量化，受控修饰使Ni- n配位位点增加了10倍，而HAADF-STEM证实了原子分散的Ni位点的存在，相对于未修饰的底物，析氧电流密度增加了6倍以上。在充分氧化以承载活性位点和过度剥落导致表面部分破坏之间需要权衡。有趣的是，法拉第析氧效率保持在90%以上，这表明通过部分剥落的缺陷工程有效地平衡了结构完整性和活性位点暴露。耐久性实验表明，性能最好的催化剂具有稳定的性能，可以将部分Ni-N位点转化为NiOOH。这种方法强调了碳基质的可调性，通过控制缺陷的产生来优化催化性能。

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引用次数: 0

Inkless, dry printing nanographene via in-Situ Coordinated laser ablation and sintering processes 采用原位激光烧蚀和烧结工艺进行无墨、干式纳米石墨烯印刷

IF 11.6 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Carbon

Pub Date : 2025-12-31 DOI: 10.1016/j.carbon.2025.121223

Adib Taba , Matthew G. Boebinger , Masoud Mahjouri-Samani

Printing carbon, such as graphene and other carbon structures, for flexible and printed electronics currently relies on either ink-based printing, laser-induced forward transfer (LIFT), or laser-induced graphitization (LIG) to convert carbon-rich precursor materials, such as polymers, to graphene-like carbon structures. Liquid inks contain toxic solvents, surfactants, and stabilizing additives that degrade electrical conductivity and require high-temperature post-processing. On the other hand, LIG is limited by the substrate. This study introduces an additive manufacturing method for dry-printing carbon nanomaterials, ranging from amorphous carbon to crystalline graphene-like structures, on various substrates. The system utilizes laser ablation of a solid graphite target to create pure carbon nanoparticles in situ and on demand. An inert gas carries the nanoparticles onto the substrate, where they can be deposited either as amorphous structures or laser-sintered in real time to form various graphitic structures. The study of laser processing parameters, specifically fluence and pulse repetition frequency, revealed three unique regimes of nanostructure evolution that influence the morphological and electrical properties of these printed structures. Raman spectroscopy confirmed graphitization with a resistivity slightly higher than that of the bulk graphite target. The conductivity/resistivity could be tuned as a function of sintering laser power. Scanning transmission electron microscopy (STEM) revealed that turbostratic nanographene formed with an interlayer spacing of 0.40 nm. Despite ink-based printing methods, such as screen printing, inkjet printing (IJP), and aerosol jet printing (AJP), this eco-friendly and green manufacturing technique could eliminate toxic chemicals, reduce environmental impact, and enable single-step fabrication of carbon-based devices for applications in wearable sensors, energy storage, flexible electronics, and Internet of Things (IoT) devices.

印刷碳，如石墨烯和其他碳结构，用于柔性和印刷电子产品，目前依赖于油墨印刷，激光诱导正向转移（LIFT）或激光诱导石墨化（LIG）将富含碳的前驱材料，如聚合物，转化为石墨烯样碳结构。液体油墨含有有毒溶剂、表面活性剂和稳定添加剂，这些添加剂会降低电导率，需要高温后处理。另一方面，LIG受到衬底的限制。本研究介绍了一种增材制造方法，用于在各种衬底上干法印刷碳纳米材料，从无定形碳到晶体石墨烯样结构。该系统利用激光烧蚀固体石墨靶，在原位按需制造纯碳纳米颗粒。惰性气体将纳米颗粒携带到衬底上，在那里它们可以作为非晶结构沉积，也可以实时激光烧结形成各种石墨结构。激光加工参数的研究，特别是影响和脉冲重复频率，揭示了三种独特的纳米结构演变机制，影响这些印刷结构的形态和电学性能。拉曼光谱证实石墨化，其电阻率略高于块体石墨靶。电导率/电阻率可以作为烧结激光功率的函数进行调谐。扫描透射电镜（STEM）显示，形成的涡层纳米石墨烯层间距为0.40 nm。尽管基于油墨的印刷方法，如丝网印刷、喷墨印刷（IJP）和气溶胶喷射印刷（AJP），这种环保和绿色的制造技术可以消除有毒化学物质，减少对环境的影响，并使碳基设备的单步制造应用于可穿戴传感器、能源存储、柔性电子产品和物联网（IoT）设备。

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引用次数: 0

Stretch-tunable buckled carbon nanotube sheets for reversible, on-demand, and temperature-free VOC capture and synchronized release 拉伸可调扣碳纳米管片可逆，按需，无温度VOC捕获和同步释放

IF 11.6 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Carbon

Pub Date : 2025-12-31 DOI: 10.1016/j.carbon.2025.121224

Hyunsoo Kim , Minwoo Kim , Solpa Lee , Juchan Ha , Ryun Kang , Inje Lim , Jun-Ge Liang , Yang Li , Cong Wang , Yongwoo Jang

The analysis and manipulation of volatile organic compounds (VOCs) are essential in various fields, including healthcare, food safety, and environmental monitoring. However, the typically low concentrations of VOC require efficient preconcentration and rapid controlled release methods to deliver high detection sensitivity and temporal resolution. Conventional sorbents, such as activated carbon, zeolite, and silica gel, offer excellent adsorption capacities but depend on thermal desorption, which is energy-intensive and diffusion-limited, and often leads to delayed and unsynchronized analyte release. Herein, we present a bioinspired VOC-management strategy that mimics the buckled leaf morphology of Plectranthus tomentosa, which is known for its ability to retain and release scent upon mechanical stimulation. A stretch-tunable hierarchical micro/nanoporous structure was fabricated using multi-walled carbon nanotube (MWCNT) sheets laminated onto an elastomeric substrate. The MWCNT sheets provide a high surface area, tunable porosity, and mechanical flexibility, which enables the reversible adsorption and stretch-triggered desorption of VOCs. The buckled structure collapses when full uniaxial strain is applied, resulting in the rapid and thermally independent release of adsorbed VOCs. Complete desorption was achieved within 60 s in the absence of thermal input. When applied to a gas sensor system, stretch-triggered VOC release produced an 11-fold increase in response speed compared to passive desorption, while maintaining stable performance over 1000 stretch–release cycles. This synchronized, mechanically activated release mechanism significantly improves temporal control over VOC delivery and offers a temperature-free, on-demand solution for advanced odor sensing. The developed approach exhibits strong potential for integration into portable and wearable VOC-detection platforms.

挥发性有机化合物（VOCs）的分析和处理在各个领域都是必不可少的，包括医疗保健、食品安全和环境监测。然而，典型的低浓度VOC需要有效的预浓缩和快速控制释放方法，以提供高检测灵敏度和时间分辨率。传统的吸附剂，如活性炭、沸石和硅胶，具有优异的吸附能力，但依赖于热解吸，这是能源密集型和扩散受限的，并且经常导致延迟和不同步的分析物释放。在此，我们提出了一种生物启发的voc管理策略，该策略模仿了Plectranthus tomentosa的弯曲叶片形态，该叶片以其在机械刺激下保留和释放气味的能力而闻名。将多壁碳纳米管（MWCNT）片层合在弹性衬底上，制备了一种可拉伸可调的分层微孔/纳米孔结构。MWCNT片材具有高表面积、可调孔隙率和机械灵活性，可实现挥发性有机化合物的可逆吸附和拉伸解吸。当施加全单轴应变时，屈曲结构坍塌，导致吸附的挥发性有机化合物迅速和热无关地释放。在没有热输入的情况下，完全脱附在60 s内完成。当应用于气体传感器系统时，与被动解吸相比，拉伸触发VOC释放产生的响应速度提高了11倍，同时在1000次拉伸释放循环中保持稳定的性能。这种同步的、机械激活的释放机制显著改善了对挥发性有机化合物释放的时间控制，并为先进的气味传感提供了无温度、按需的解决方案。所开发的方法显示出集成到便携式和可穿戴voc检测平台的强大潜力。

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引用次数: 0

Tailored porous carbon fibers via fluorination–defluorination and their potential application as EMI shielding: a new route without stabilization or activation 经氟化-去氟化的定制多孔碳纤维及其作为电磁干扰屏蔽的潜在应用：一种无需稳定或激活的新途径

IF 11.6 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Carbon

Pub Date : 2025-12-30 DOI: 10.1016/j.carbon.2025.121217

Chaehun Lim , Seongjae Myeong , Sangyeop Lee , Yunhua Yu , Xiaoping Yang , Young-Seak Lee

The effects of the fluorination–defluorination reaction on carbon fiber production were demonstrated for the first time in this study. Polyacrylonitrile (PAN) and mesophase pitch (MP) precursor fibers were fluorinated at room temperature for 10–60 min, followed by thermal defluorination to generate carbon fibers. Fluorination of PAN fibers caused structural distortion through cleavage of the C ≡ N bond, while fluorination of MP fibers induced structural changes into a CF_X configuration. The resulting carbon fibers, obtained after defluorination, retained their fibrous morphology and exhibited a high specific surface area without requiring any stabilization or activation steps. Specifically, the MP-based carbon fiber fluorinated for 10 min exhibited superior crystallinity and the highest specific surface area of 256.3 m²/g, featuring a hollow fiber structure. In contrast, the PAN-based carbon fiber showed a hard carbon structure with a maximum specific surface area of 130.1 m²/g and an amorphous morphology. Pore formation and stabilization mechanisms were proposed based on the characteristics of the fluorinated and defluorinated fibers. Additionally, the effectiveness of carbon fibers produced through the fluorination–defluorination process was confirmed by EMI shielding experiments. This study marks a considerable advancement in producing porous carbon fibers without the need for stabilization or activation, demonstrating practical applicability.

本研究首次论证了氟化-脱氟反应对碳纤维生产的影响。将聚丙烯腈（PAN）和中间相沥青（MP）前驱体纤维在室温下氟化10-60 min，然后进行热脱氟制备碳纤维。PAN纤维的氟化通过C≡N键的裂解引起结构畸变，而MP纤维的氟化引起结构变化为CFX构型。除氟后得到的碳纤维保留了其纤维形态，并表现出高比表面积，无需任何稳定或活化步骤。其中，氟化10 min的mp基碳纤维结晶度优异，比表面积最高，达到256.3 m2/g，具有中空纤维结构。pan基碳纤维表现为硬碳结构，最大比表面积为130.1 m2/g，呈非晶形态。根据氟化和脱氟纤维的特性，提出了孔隙形成和稳定机理。此外，通过电磁干扰屏蔽实验证实了通过氟化-脱氟工艺生产的碳纤维的有效性。这项研究标志着在不需要稳定化或活化的情况下生产多孔碳纤维方面取得了相当大的进步，证明了实际的适用性。

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引用次数: 0

Heterojunction and N vacancies of C3N4-EW regulate the electronic structure of Pd to promote the semihydrogenation of phenylacetylene C3N4-EW的异质结和N空位调节Pd的电子结构，促进苯乙炔的半氢化反应

IF 11.6 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Carbon

Pub Date : 2025-12-30 DOI: 10.1016/j.carbon.2025.121219

Xianlang Chen , Yuyao Wang , Chengkang Zhou , Chunhua Chen , Yuqi Kang , Fuxiang Fan , Yijing Gao , Tongyang Song , Rongrong Li

Developing the catalysts to enhance the activity and selectivity of semihydrogenation of alkyne has enormous potential in fine chemical industry, but still full of significant challenges. In this work, the Pd/C₃N₄-EW catalyst with heterojunction and N vacancies was prepared by two-step calcination method and impregnation method. When the semihydrogenation of phenylacetylene was used as the probe reaction, the Pd/C₃N₄-EW demonstrated excellent conversion and selectivity, and achieved low activation energy (E_a = 25.7 kJ mol⁻¹) and high turnover frequency value (TOF = 5388.3 h⁻¹). This catalyst has high activity and selectivity after six cycles, and has a wide range of applications in alkynes. The superior activity of Pd/C₃N₄-EW was mainly due to the heterojunction and N vacancies structure of the catalyst, which enhance the dispersion of Pd metal active sites, regulate the electronic structure of Pd, and enhance material transport. Particularly, experiments and density functional theory (DFT) calculations indicated that more electron transfer from Pd to C₃N₄-EW on the Pd/C₃N₄-EW, resulting in Pd having a more electron-deficient structure. Therefore, the adsorption of phenylacetylene and H₂ by Pd active sites can be increased, which is beneficial for the activation of H₂ and thereby promotes the selective hydrogenation of phenylacetylene.

开发提高炔烃半加氢反应活性和选择性的催化剂在精细化工领域具有巨大的潜力，但仍充满着重大的挑战。本文采用两步焙烧和浸渍法制备了具有异质结和N空位的Pd/C3N4-EW催化剂。以苯乙炔半加氢反应为探针反应时，Pd/C3N4-EW表现出良好的转化率和选择性，具有低活化能（Ea = 25.7 kJ mol−1）和高周转率值（TOF = 5388.3 h−1）。该催化剂经过6次循环后具有较高的活性和选择性，在炔烃中有广泛的应用。Pd/C3N4-EW具有优异的活性主要是由于催化剂的异质结和N空位结构增强了Pd金属活性位点的分散，调节了Pd的电子结构，促进了材料的输运。特别是，实验和密度泛函理论（DFT）计算表明，Pd/C3N4-EW上更多的电子从Pd转移到C3N4-EW，导致Pd具有更多的缺电子结构。因此可以增加Pd活性位点对苯乙炔和H2的吸附，有利于H2的活化，从而促进苯乙炔的选择性加氢。

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引用次数: 0

Fabrication of ultrahigh-strength aluminum matrix composites reinforced with high-content carbon nanotubes and ex-situ added alloying elements 高碳纳米管和非原位添加合金元素增强超高强度铝基复合材料的制备

IF 11.6 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Carbon

Pub Date : 2025-12-30 DOI: 10.1016/j.carbon.2025.121218

Yahang Wang , Zhendong Jia , Lin Cao , Jianghua Shen , Jinshan Li , Biao Chen

An ex-situ alloying approach was developed to tackle the uniform dispersion challenge of high-content carbon nanotubes (CNTs) in hard aluminum (Al) alloy powders that are difficult to deform during the high energy ball milling (HEBM) process. The approach includes (1) attaining uniform distribution of high-content CNTs in soft pure Al powders via HEBM, followed by (2) short-duration HEBM with elemental Zn/Mg/Cu powders. Microstructural analysis showed that the high-content CNTs promoted dynamic recrystallization in the Al matrix, leading to a heterogeneous grain structure consisting of fine-grained and coarse-grained zones. The high density of dislocations introduced by CNTs resulted in more and finer precipitates in the fine-grained zones. The synergistic enhancement between CNTs and precipitates in composite yielded an exceptionally high tensile strength of 855 MPa, which registered a new record among the bulk CNTs/Al composites in literature. The strengthening mechanisms were discussed based on thorough microstructure characterizations. This study proposes a paradigm for microstructure tailoring to fabricate Al alloy composites reinforced with high-content CNTs via optimized preparation techniques and precipitation engineering.

为了解决高能球磨（HEBM）过程中难以变形的高含量碳纳米管（CNTs）在硬铝（Al）合金粉末中的均匀分散问题，提出了一种非原位合金化方法。该方法包括：(1)通过HEBM在软纯Al粉末中均匀分布高含量的碳纳米管，然后(2)使用元素Zn/Mg/Cu粉末进行短时间HEBM。显微组织分析表明，高含量的CNTs促进了Al基体的动态再结晶，形成由细晶区和粗晶区组成的非均匀晶粒组织。CNTs引入的高密度位错导致细晶区析出更多更细的相。复合材料中CNTs与析出相之间的协同增强使复合材料的抗拉强度达到了855 MPa，创下了文献中大块CNTs/Al复合材料的新纪录。在深入的微观组织表征的基础上，探讨了强化机理。本研究提出了一种通过优化制备工艺和沉淀工程制备高含量碳纳米管增强铝合金复合材料的微观结构定制范式。

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引用次数: 0

Atomic-scale substitutional defect engineering for significant enhancement of thermal transport at GaN/diamond interfaces 氮化镓/金刚石界面热输运显著增强的原子尺度替代缺陷工程

IF 11.6 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Carbon

Pub Date : 2025-12-30 DOI: 10.1016/j.carbon.2025.121221

Feng Wang , Tao Hu , Xiaodan Yu , Xiaoxin Zhang , Zhongming Ren

We investigated the thermal transport at the GaN-diamond heterointerface at the nano-microscale using non-equilibrium molecular dynamics (NEMD) combined with first-principles calculations, with a focus on the tunability of interfacial thermal conductance (ITC) by defect engineering. Different types of vacancy defects (such as carbon vacancies and nitrogen vacancies) exhibit distinct trends in their tunability of ITC. Specifically, higher concentrations of carbon vacancies can enhance ITC by nearly 50 %. Due to different types of vacancy defects inducing differences in phonon participating at the interface, ultimately leading to change it. Meanwhile, different types of substitution defects also exhibit varying tunable effects on interfacial thermal transport. As the concentration of carbon atoms in diamond are replaced by gallium atoms (Ga_C) increases, the ITC rises significantly from 0.61 GW/m²K in the perfect interface to 9.61 GW/m²K, while carbon atoms in diamond substituted by nitrogen have a much weaker tunable effect on ITC. Moreover, to further explore the potential of Ga_C defects in regulating thermal conductance, we engineered defect distributions with varying depths and gradients at the interface, achieving up to 5 times enhancement of ITC. First-principles calculations at the interface, along with phonon density of states and phonon participation ratio, demonstrate that the substantial enhancement of ITC correlates with phonon frequency shifts and energy redistribution. And subsequent decomposition of the phonon heat current provides direct evidence for this conjecture. Our research provides valuable insights for defect engineering design to improve thermal management in gallium nitride-based electronic devices.

利用非平衡分子动力学（NEMD）结合第一性原理计算，研究了纳米尺度下gan -金刚石异质界面的热输运，并通过缺陷工程研究了界面热导率（ITC）的可调性。不同类型的空位缺陷（如碳空位和氮空位）在ITC的可调性上表现出不同的趋势。具体来说，更高的碳空位浓度可以使ITC提高近50%。由于不同类型的空位缺陷导致声子参与界面的差异，最终导致界面的改变。同时，不同类型的取代缺陷对界面热输运也表现出不同的可调效应。随着金刚石中碳原子被镓原子（GaC）取代浓度的增加，ITC从完美界面的0.61 GW/m2K显著上升到9.61 GW/m2K，而金刚石中碳原子被氮取代对ITC的可调作用要弱得多。此外，为了进一步探索GaC缺陷在调节热导率方面的潜力，我们在界面处设计了不同深度和梯度的缺陷分布，实现了ITC的5倍增强。界面上的第一性原理计算，以及声子态密度和声子参与比表明，ITC的显著增强与声子频移和能量再分配有关。随后对声子热流的分解为这一猜想提供了直接证据。我们的研究为改进氮化镓基电子器件的热管理缺陷工程设计提供了有价值的见解。

{"title":"Atomic-scale substitutional defect engineering for significant enhancement of thermal transport at GaN/diamond interfaces","authors":"Feng Wang , Tao Hu , Xiaodan Yu , Xiaoxin Zhang , Zhongming Ren","doi":"10.1016/j.carbon.2025.121221","DOIUrl":"10.1016/j.carbon.2025.121221","url":null,"abstract":"<div><div>We investigated the thermal transport at the GaN-diamond heterointerface at the nano-microscale using non-equilibrium molecular dynamics (NEMD) combined with first-principles calculations, with a focus on the tunability of interfacial thermal conductance (ITC) by defect engineering. Different types of vacancy defects (such as carbon vacancies and nitrogen vacancies) exhibit distinct trends in their tunability of ITC. Specifically, higher concentrations of carbon vacancies can enhance ITC by nearly 50 %. Due to different types of vacancy defects inducing differences in phonon participating at the interface, ultimately leading to change it. Meanwhile, different types of substitution defects also exhibit varying tunable effects on interfacial thermal transport. As the concentration of carbon atoms in diamond are replaced by gallium atoms (Ga<sub>C</sub>) increases, the ITC rises significantly from 0.61 GW/m<sup>2</sup>K in the perfect interface to 9.61 GW/m<sup>2</sup>K, while carbon atoms in diamond substituted by nitrogen have a much weaker tunable effect on ITC. Moreover, to further explore the potential of Ga<sub>C</sub> defects in regulating thermal conductance, we engineered defect distributions with varying depths and gradients at the interface, achieving up to 5 times enhancement of ITC. First-principles calculations at the interface, along with phonon density of states and phonon participation ratio, demonstrate that the substantial enhancement of ITC correlates with phonon frequency shifts and energy redistribution. And subsequent decomposition of the phonon heat current provides direct evidence for this conjecture. Our research provides valuable insights for defect engineering design to improve thermal management in gallium nitride-based electronic devices.</div></div>","PeriodicalId":262,"journal":{"name":"Carbon","volume":"248 ","pages":"Article 121221"},"PeriodicalIF":11.6,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880335","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}

引用次数: 0

Single-atom Ni and Ni nanoparticle utilizing orbital hybridization induced dipole polarization for broadband electromagnetic absorption 利用轨道杂化诱导偶极极化进行宽带电磁吸收的单原子Ni和Ni纳米粒子

IF 11.6 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Carbon

Pub Date : 2025-12-30 DOI: 10.1016/j.carbon.2025.121216

Ziyang Dai , Ruotong Wang , Yudong Li , Xiaopeng Li , Qinghai Ma , Xing Liu

Utilizing the electronic configuration of single metal atoms has emerged as a viable method for boosting dipole polarization and augmenting the variety of electromagnetic attenuation pathways. However, to date, there has been no reported investigation into the synergistic effects of single atoms and nanoparticles on the performance of electromagnetic wave absorption materials. Herein, we develop a nanoconfinement-induced growth strategy to construct hierarchical MnO@C nanorods simultaneously anchored with Ni single atoms (Ni_SA) and Ni nanoparticles (Ni_NP), forming an atomic–nanostructure electromagnetic coupling network. The coexisting Ni_SA and Ni_NP species generate strong electronic at the interfacial region, promoting charge redistribution, and band structure modulation. Density functional theory calculations reveal that Ni_SA–Ni_NP co-existence induces electronic hybridization, thereby amplifying dipole polarization and enhancing dielectric loss. Consequently, the Ni_SA-Ni_NC/MnO@C composites achieve a reflection loss of −31.41 dB at 2.50 mm with an effective absorption bandwidth of 5.76 GHz, alongside durable anti-corrosion and thermal insulation. Simultaneously, the composites exhibit outstanding corrosion resistance and superior thermal insulation properties. This study develops a mechanistic framework linking atomic-scale electronic interactions to electromagnetic wave absorption performance, emphasizing the crucial role of synergistic modulation between single atoms and nanoparticles in the electromagnetic wave absorption material.

利用单金属原子的电子组态已成为增强偶极极化和增加电磁衰减途径多样性的可行方法。然而，到目前为止，还没有关于单原子和纳米粒子对电磁波吸收材料性能的协同效应的研究报道。在此，我们开发了一种纳米禁锢诱导生长策略，构建层次化MnO@C纳米棒，同时锚定Ni单原子（NiSA）和Ni纳米颗粒（NiNP），形成原子-纳米结构电磁耦合网络。共存的NiSA和NiNP在界面区产生强电子，促进电荷重分配和能带结构调制。密度泛函理论计算表明，NiSA-NiNP的共存引起了电子杂化，从而放大了偶极子极化，增加了介电损耗。因此，NiSA-NiNC/MnO@C复合材料在2.50 mm处的反射损耗为- 31.41 dB，有效吸收带宽为5.76 GHz，同时具有持久的防腐和隔热性能。同时，复合材料具有优异的耐腐蚀性和保温性能。本研究建立了一个将原子尺度的电子相互作用与电磁波吸收性能联系起来的机制框架，强调了电磁波吸收材料中单原子和纳米颗粒之间的协同调制的关键作用。

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引用次数: 0

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