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Spatially Distributed Inter-Bundle Damage Governs the Tensile Failure of Carbon Nanotube Yarns Within Polymer Matrices 碳纳米管纱线在聚合物基体中的拉伸破坏是由空间分布的束间损伤决定的
IF 12.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-10-15 DOI: 10.1016/j.carbon.2026.122218
Go Yamamoto, Sojun Nakano, Haruki Oyamada, Redha Akbar Ramadhan, Satoru Yoneyama, Yuki Sada, Akihisa Takeuchi, Masayuki Uesugi, Akira Kunitomo, Nozomu Shigemitsu
Carbon nanotube (CNT) yarns exhibit tensile strengths comparable to or even exceeding those of high-strength polyacrylonitrile-based carbon fibers. However, the mechanisms governing the tensile failure of CNT yarns embedded in polymer matrices remain poorly understood. Therefore, in this study, the tensile failure mechanisms of CNT yarns embedded in polymer matrices were investigated using synchrotron radiation X-ray computed tomography (XCT) combined with digital volume correlation (DVC) and Raman spectroscopy upon tensile loading. DVC revealed heterogeneous strain fields within the surrounding epoxy matrix, including localized strain concentrations associated with damage sites and strain perturbations in apparently intact regions where no damage was detectable via 0.50 μm/pixel XCT. Subsequent 32 nm/pixel XCT confirmed the presence of previously undetected damage. Raman spectroscopy further revealed the heterogeneous axial-strain distributions and persistent load-bearing capacities of the damaged regions of the yarn. Therefore, load transfer between the CNT bundles progressively deteriorated in a spatially distributed manner rather than via damage localization into a single dominant fracture site. The combined observations indicated that the tensile failure of the polymer-embedded CNT yarns was governed by the progressive accumulation of spatially distributed inter-bundle damage and associated deterioration of load transfer between the CNT bundles. This failure mode fundamentally differed from that of a conventional brittle fiber, in which failure is typically characterized by localized fracture, followed by recovery of axial stress and subsequent fragmentation. These findings provide mechanistic insights for developing failure and strength prediction frameworks for hierarchical CNT-yarn composite systems.
碳纳米管(CNT)纱线具有与高强度聚丙烯腈基碳纤维相当甚至超过的抗拉强度。然而,控制碳纳米管纱线在聚合物基体中的拉伸失效的机制仍然知之甚少。因此,在本研究中,采用同步辐射x射线计算机断层扫描(XCT)结合数字体积相关(DVC)和拉曼光谱研究了嵌入聚合物基体的碳纳米管纱线在拉伸载荷下的拉伸破坏机制。通过0.50 μm/pixel的XCT,发现环氧树脂基体周围存在非均匀应变场,包括与损伤部位相关的局部应变浓度和未检测到损伤的明显完整区域的应变扰动。随后的32 nm/像素XCT证实了之前未检测到的损伤的存在。拉曼光谱进一步揭示了纱线损伤区域的非均匀轴向应变分布和持久承载能力。因此,碳纳米管束之间的载荷传递以空间分布的方式逐渐恶化,而不是通过损伤定位到单一的主要断裂部位。综合观察结果表明,聚合物嵌入碳纳米管纱线的拉伸破坏是由空间分布的碳纳米管束间损伤的逐渐累积和碳纳米管束间载荷传递的恶化所控制的。这种破坏模式与传统脆性纤维的破坏模式根本不同,传统脆性纤维的破坏典型特征是局部断裂,随后是轴向应力的恢复和随后的碎裂。这些发现为开发分层碳纳米管-纱线复合系统的失效和强度预测框架提供了机制见解。
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引用次数: 0
From surface roughness to interlayer engineering: Regulating interfacial thermal conductance in GaN/Diamond heterostructures 从表面粗糙度到层间工程:调节GaN/金刚石异质结构的界面热导率
IF 12.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-09-08 DOI: 10.1016/j.carbon.2026.122092
Yining Ou, Xiang Luo, Ning Hu, Bo Yang
For high−power gallium nitride (GaN) electronic devices, efficient thermal management strategies are crucial. Diamond possesses the highest thermal conductance among bulk materials and is considered an ideal heat dissipation substrate for high−power chips. However, the mechanisms of interfacial heat conduction in GaN/Diamond heterojunctions are not yet fully understood. In this study, we investigated the effect of surface roughness on the interfacial thermal conductance (ITC) using non−equilibrium molecular dynamics (NEMD) simulations. The results indicate that ITC generally decreases with increasing root−mean−square (RMS) roughness, while showing a positive correlation with the number of contacting atoms. Phonon density of states (PDOS) analysis indicates that there is no strictly monotonic relationship between PDOS overlap and ITC, suggesting that traditional descriptors such as RMS and phonon matching are insufficient to fully describe ITC in the GaN/Diamond system. To overcome this limitation, a graphite interlayer was introduced between GaN and diamond to achieve covalent bonding at the coherent interface. The results show that the graphite layer effectively mitigates phonon mismatch and enhances vibrational coupling, resulting in an ITC value nearly two orders of magnitude higher than that of the original interface. These findings can provide guidance for interface design between high−power chips and heat dissipation substrate.
对于高功率氮化镓(GaN)电子器件,高效的热管理策略至关重要。金刚石在块状材料中具有最高的导热性,被认为是高功率芯片的理想散热基板。然而,氮化镓/金刚石异质结的界面热传导机制尚不完全清楚。在这项研究中,我们使用非平衡分子动力学(NEMD)模拟研究了表面粗糙度对界面热导率(ITC)的影响。结果表明,ITC随RMS粗糙度的增大而减小,与接触原子数呈正相关。声子态密度(PDOS)分析表明,PDOS重叠与ITC之间不存在严格的单调关系,这表明传统的描述词如RMS和声子匹配不足以完全描述GaN/Diamond体系中的ITC。为了克服这一限制,在GaN和金刚石之间引入石墨中间层,以在相干界面上实现共价键。结果表明,石墨层有效地减轻了声子失配,增强了振动耦合,使得ITC值比原界面提高了近两个数量级。这些研究结果可为大功率芯片与散热基板之间的接口设计提供指导。
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引用次数: 0
Bayesian model selection for graphite oxidation by molecular oxygen informed by new data 基于新数据的石墨分子氧氧化贝叶斯模型选择
IF 12.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-08-01 Epub Date: 2026-07-16 DOI: 10.1016/j.carbon.2026.121877
Kaan Kirmanoglu, Nicholas A. Anderson, Francesco Panerai, Kelly A. Stephani, Jonathan B. Freund
Flow tube experiments and Bayesian model selection and calibration methods are used to assess kinetics models for graphite oxidation at pressures of 33 and 330 Pa and temperatures from 1100 to 2284 K. Bayesian methods, which are well established but not commonly used for carbon oxidation modeling, are employed to select and calibrate models based on the novel experiments. The experiments isolate high-temperature gas-surface interactions and mass loss, enabling low-computational-cost model evaluations, extensive statistical sampling, and inference methods, which evaluate oxidation rate models even though oxidation rates themselves are not directly measured. Influential reaction parameters are selected by global sensitivity analysis and parameter influence criteria. Bayesian inference is used for both parameter calibration and model class selection among three candidate model classes proposed for air–carbon ablation. The two classes with dual adsorption mechanisms, in which oxygen can adsorb strongly or weakly, are shown to be more plausible than the model with a single adsorption mechanism, though both are supported equally. All models predict that CO production increases with temperature until a peak is reached. Models with dual adsorption mechanisms differ by their prediction of CO and CO2 product ratios. Posterior distributions of calibration parameters are constructed to quantify parameter uncertainties and model errors for uncertainty quantification when using these models.
采用流管实验和贝叶斯模型选择和校准方法,对压力为33和330 Pa,温度为1100至2284 K的石墨氧化动力学模型进行了评估。采用贝叶斯方法对碳氧化模型进行选择和校正,贝叶斯方法在碳氧化模型中应用较为成熟,但并不常用。实验分离了高温气体表面相互作用和质量损失,实现了低计算成本的模型评估,广泛的统计抽样和推理方法,即使氧化速率本身没有直接测量,也可以评估氧化速率模型。通过全局灵敏度分析和参数影响准则选择有影响的反应参数。采用贝叶斯推理对空气-碳烧蚀的三个候选模型进行了参数标定和模型类别选择。两类具有双重吸附机制的模型,即氧可以强吸附或弱吸附,比具有单一吸附机制的模型更合理,尽管两者都得到同样的支持。所有模型都预测CO产量会随着温度的升高而增加,直到达到峰值。具有双重吸附机制的模型在预测CO和CO2生成物比率方面存在差异。建立了标定参数的后验分布来量化参数的不确定性和模型误差,以便在使用这些模型时对不确定性进行量化。
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引用次数: 0
Outside Front Cover - Journal name, Cover image, Volume issue details, ISSN, Cover Date, Elsevier Logo and Society Logo if required 外部封面-期刊名称,封面图片,卷刊细节,ISSN,封面日期,爱思唯尔标志和学会标志(如果需要)
IF 12.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-08-01 Epub Date: 2026-07-25 DOI: 10.1016/S0008-6223(26)00688-3
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引用次数: 0
Corrigendum to “Optical modeling, solver, and design of macroscopic single-enantiomer carbon nanotube film and reconfigurable chiral photonic device” [Carbon 235 (2025) 120016] “宏观单对映体碳纳米管薄膜和可重构手性光子器件的光学建模、求解器和设计”的勘误表[碳235 (2025)120016]
IF 12.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-08-01 Epub Date: 2026-07-11 DOI: 10.1016/j.carbon.2026.121847
Jichao Fan, Benjamin Hillam, Cheng Guo, Hiroyuki Fujinami, Koki Shiba, Haoyu Xie, Ruiyang Chen, Kazuhiro Yanagi, Weilu Gao
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引用次数: 0
Iodine-mediated in-situ growth of graphene-like films on copper powders enabling synergistic thermal, electrical, and mechanical performance 碘介导的类石墨烯薄膜在铜粉上的原位生长,实现了协同的热、电和机械性能
IF 12.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-08-01 Epub Date: 2026-07-17 DOI: 10.1016/j.carbon.2026.121897
Weiyi Yang, Pin Tian, Jingmei Tao, Xiaofeng Chen, Jianhong Yi
In-situ graphene-like (GL) reinforced Cu-matrix composites that simultaneously combine high thermal and electrical conductivities with enhanced strength are of significant interest for advanced thermal-management and electrical-conduction applications. Here, we report a low-temperature in-situ growth route for GL/Cu composites, using graphene nanosheets derived from sucrose carbonization serve as precursor. An iodine-mediated adsorption-catalysis mechanism is proposed to govern the uniform anchoring and subsequent structural evolution of graphene nanosheets on Cu powders. The formation of a CuI interfacial layer promotes the strong adsorption of graphene nanosheets. Subsequently, during the 600 °C thermal treatment, the CuI layer facilitates in-situ conversion of graphene nanosheets into continuous, sp2-rich GL films tightly bonded to Cu (111), (220), and (200) crystallographic planes. This interfacial carbon evolution effectively suppresses interfacial thermal and electrical resistance while maintaining robust interfacial bonding. After consolidation by pressing, sintering, and hot rolling, the resulting bulk GL/Cu composites exhibit a synergistic combination of transport and mechanical properties. A high thermal conductivity of 421 W m−1 K−1 at 25 °C and 404 W m−1 K−1 at 300 °C were achieved, corresponding to an ∼42% enhancement in thermal-conductivity efficiency by 0.31 vol % GL. Notably, the electrical conductivity remains at 97% IACS, without degradation relative to pure Cu, while the tensile strength reaches 290 MPa, representing an increase of ∼35% compared with pure Cu (215 MPa). This work elucidates an interfacial-catalysis-driven mechanism for the in-situ evolution of GL on copper and demonstrates its effectiveness in achieving synergistic optimization of thermal, electrical, and mechanical properties in Cu-matrix composites.
原位类石墨烯(GL)增强cu基复合材料同时结合了高导热性和导电性以及增强的强度,对于先进的热管理和导电应用具有重要意义。在这里,我们报道了GL/Cu复合材料的低温原位生长路线,使用蔗糖碳化衍生的石墨烯纳米片作为前驱体。提出了一种碘介导的吸附催化机制来控制石墨烯纳米片在铜粉上的均匀锚定和随后的结构演变。CuI界面层的形成促进了石墨烯纳米片的强吸附。随后,在600 °C的热处理过程中,CuI层有助于将石墨烯纳米片原位转化为连续的、富含sp2的GL膜,并与Cu(111)、(220)和(200)晶体平面紧密结合。这种界面碳演化有效地抑制了界面的热阻和电阻,同时保持了牢固的界面结合。经过压制、烧结和热轧固结,得到的块状GL/Cu复合材料表现出输运和力学性能的协同组合。高导热系数的421 W  −1 K−1 25 °C和404 W  −1 K−1 300 °C实现,对应于增强导热效率0.31∼42% 卷% GL。值得注意的是,导电率仍在97% IACS,没有退化相对于纯铜,而抗拉强度达到290 MPa,代表增加∼35%纯铜(215 MPa)。这项工作阐明了界面催化驱动的GL在铜表面的原位演化机制,并证明了其在实现cu基复合材料的热、电和力学性能协同优化方面的有效性。
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引用次数: 0
VICIOXITE: A CARBON MATERIAL CONTAINING ADJACENT OH GROUPS FOR CO2 AND H2O CAPTURE 水蛭石:含有相邻oh基团的碳材料,用于捕获二氧化碳和水
IF 12.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-07-01 Epub Date: 2026-06-22 DOI: 10.1016/j.carbon.2026.121741
Kota Kondo , Itsuki Takahashi , Kai Kan , Kazuma Gotoh , Tetsuro Soejima , Sota Nakamura , Satoshi Sato , Tomonori Ohba , Yasuhiro Yamada
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引用次数: 0
Construction of NiSe2/Ni3B2O6 heterostructures on electrospun carbon nanofibers for high-performance supercapacitor and hydrogen evolution reaction 高性能超级电容器用静电纺碳纳米纤维上nis2 /Ni3B2O6异质结构的构建及析氢反应
IF 12.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-07-01 Epub Date: 2026-06-10 DOI: 10.1016/j.carbon.2026.121760
Guanghui Li, Lanrui Yin, Xingmei Duan, Changfu Zhuang, Yimo Xiang, Di Tian
Heterostructured engineering is driving advancements in supercapacitor and hydrogen evolution reaction (HER). In this work, a NiSe2/Ni3B2O6 heterostructure on electrospun carbon nanofibers was fabricated as a dual-functional material. The NiSe2/Ni3B2O6 heterojunction with favorable electronic distribution and the well-dispersed active sites supported by electrospun carbon nanofibers, facilitate conductivity, stability and reaction kinetics. CCo@NiSe@NiBO, belonging to an energy storage mechanism dominated by diffusion control, showed a specific capacitance of 984.0 F g−1, and a capacitance retention of 42.68 % when the current density increases by 20 times, which exceeds that of many reported Ni based selenides and borides. Meanwhile, CCo@NiSe@NiBO as a HER catalyst achieved overpotentials of 227 mV at 10 mA cm−2 and Tafel slopes of 91.2 mV dec−1. DFT calculations revealed its optimized adsorption energy of OH− for CCo@NiSe@NiBO. In addition, a CCo@NiSe@NiBO//active carbon hybrid device displayed an energy density of 35.58 Wh kg−1 as well as 91.88 % of its initial capacitance after 10,000 cycles. It was successfully integrated into the circuit. This work emphasizes the advantages of electrospun nanofibers in constructing heterostructures and establishes heterostructured engineering as a powerful strategy for advancing energy storage devices and catalysis.
异质结构工程正在推动超级电容器和析氢反应(HER)的发展。本文在电纺碳纳米纤维上制备了nis2 /Ni3B2O6异质结构的双功能材料。nis2 /Ni3B2O6异质结具有良好的电子分布和分散良好的活性位点,在电纺碳纳米纤维的支撑下,促进了电导率、稳定性和反应动力学。CCo@NiSe@NiBO属于扩散控制为主的储能机制,当电流密度增加20倍时,其比电容为984.0 F g−1,电容保持率为42.68 %,超过了目前报道的许多Ni基硒化物和硼化物。同时,CCo@NiSe@NiBO作为HER催化剂在10 mA cm−2时的过电位为227 mV, Tafel斜率为91.2 mV dec−1。DFT计算显示了CCo@NiSe@NiBO对OH−的最佳吸附能。此外,CCo@NiSe@NiBO//活性炭混合装置在10,000次循环后显示出35.58 Wh kg−1的能量密度和91.88 %的初始电容。它被成功地集成到电路中。这项工作强调了静电纺纳米纤维在构建异质结构方面的优势,并将异质结构工程作为推进储能设备和催化的有力策略。
{"title":"Construction of NiSe2/Ni3B2O6 heterostructures on electrospun carbon nanofibers for high-performance supercapacitor and hydrogen evolution reaction","authors":"Guanghui Li,&nbsp;Lanrui Yin,&nbsp;Xingmei Duan,&nbsp;Changfu Zhuang,&nbsp;Yimo Xiang,&nbsp;Di Tian","doi":"10.1016/j.carbon.2026.121760","DOIUrl":"10.1016/j.carbon.2026.121760","url":null,"abstract":"<div><div>Heterostructured engineering is driving advancements in supercapacitor and hydrogen evolution reaction (HER). In this work, a NiSe<sub>2</sub>/Ni<sub>3</sub>B<sub>2</sub>O<sub>6</sub> heterostructure on electrospun carbon nanofibers was fabricated as a dual-functional material. The NiSe<sub>2</sub>/Ni<sub>3</sub>B<sub>2</sub>O<sub>6</sub> heterojunction with favorable electronic distribution and the well-dispersed active sites supported by electrospun carbon nanofibers, facilitate conductivity, stability and reaction kinetics. CCo@NiSe@NiBO, belonging to an energy storage mechanism dominated by diffusion control, showed a specific capacitance of 984.0 F g<sup>−1</sup>, and a capacitance retention of 42.68 % when the current density increases by 20 times, which exceeds that of many reported Ni based selenides and borides. Meanwhile, CCo@NiSe@NiBO as a HER catalyst achieved overpotentials of 227 mV at 10 mA cm<sup>−2</sup> and Tafel slopes of 91.2 mV dec<sup>−1</sup>. DFT calculations revealed its optimized adsorption energy of OH<sup>−</sup> for CCo@NiSe@NiBO. In addition, a CCo@NiSe@NiBO//active carbon hybrid device displayed an energy density of 35.58 Wh kg<sup>−1</sup> as well as 91.88 % of its initial capacitance after 10,000 cycles. It was successfully integrated into the circuit. This work emphasizes the advantages of electrospun nanofibers in constructing heterostructures and establishes heterostructured engineering as a powerful strategy for advancing energy storage devices and catalysis.</div></div>","PeriodicalId":262,"journal":{"name":"Carbon","volume":"257 ","pages":"Article 121760"},"PeriodicalIF":12.7,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148566188","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
A physics-based analytical framework for quantum transport and leakage in sub-10 nm carbon nanotube transistors 亚10nm碳纳米管晶体管中量子输运和泄漏的物理分析框架
IF 12.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-07-01 Epub Date: 2026-06-13 DOI: 10.1016/j.carbon.2026.121747
Shengchuan Hu, Jiaji Liang, Haochen Zhao, Nan Wei, Yingjun Yang, Lianmao Peng, Xiuli Fu
As carbon nanotube field effect transistors (CNTFETs) are scaled into the sub-10 nm regime, device performance becomes increasingly constrained by the competition between electrostatic gate control and tunneling-induced leakage. Under such extreme scaling, the unique one-dimensional band structure of carbon nanotubes causes short-channel effects, phonon scattering, source-to-drain tunneling (SDT), band-to-band tunneling (BTBT), and ambipolar conduction to evolve and interact within the same bias-dependent energy landscape, and their interplay still lacks a clear physical interpretation. Here, we establish a physics-based analytical description that combines an explicit surface potential solution, quasi-two-dimensional electrostatic band modulation, and energy resolved transport analysis to capture the transport behavior of ultrascaled CNTFETs within a unified framework.
The analytical predictions show excellent agreement with experimental data and enable quantitative decomposition of multiple current components, thereby clarifying how the dominant leakage mechanism evolves with material properties, bias voltage, and device architecture, while explicitly capturing the competition between SDT and ambipolar conduction under different bias conditions. On this basis, we further investigate leakage-limited scaling strategies through bandgap engineering and electrostatic gate underlap (UL) design. Benchmarking against the International Roadmap for Devices and Systems (IRDS) indicates that optimized 5 nm gate-all-around CNTFETs can satisfy stringent leakage current constraints while maintaining strong on-state performance.
More broadly, this analytical description provides a physically transparent and computationally efficient theoretical foundation for clarifying leakage-limited scaling and guiding leakage-aware device optimization in carbon-based transistors.
随着碳纳米管场效应晶体管(cntfet)的尺寸扩展到10纳米以下,静电栅极控制和隧道感应泄漏之间的竞争日益限制了器件的性能。在这种极端尺度下,碳纳米管独特的一维带结构导致短通道效应、声子散射、源-漏隧道效应(SDT)、带-带隧道效应(BTBT)和双极性传导在相同的偏置依赖能量格局中演化和相互作用,它们的相互作用仍然缺乏明确的物理解释。在这里,我们建立了一个基于物理的分析描述,结合了显式表面电位解、准二维静电带调制和能量解析输运分析,以在统一的框架内捕获超尺度cntfet的输运行为。分析预测与实验数据非常吻合,能够对多个电流分量进行定量分解,从而阐明主要泄漏机制是如何随着材料特性、偏置电压和器件架构而演变的,同时明确地捕捉了不同偏置条件下SDT和双极性传导之间的竞争。在此基础上,我们通过带隙工程和静电栅极underlap (UL)设计进一步研究了限制泄漏的缩放策略。根据国际器件和系统路线图(IRDS)的基准测试表明,优化的5nm栅极全方位cntfet可以满足严格的泄漏电流限制,同时保持强大的on-state性能。更广泛地说,这种分析描述为澄清泄漏限制缩放和指导碳基晶体管的泄漏感知器件优化提供了物理透明和计算高效的理论基础。
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引用次数: 0
Carbon-on-carbon reconstruction in biomass-derived Ni/CA driven by concurrent amorphous coking and filamentous growth 由非晶结焦和丝状生长同时驱动的生物质衍生Ni/CA的碳对碳重构
IF 12.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-07-01 Epub Date: 2026-06-13 DOI: 10.1016/j.carbon.2026.121770
Jialin Zhang, Zihui Xiong, Zhaoyu Chen, Qiangqiang Ren, Limo He, Sheng Su, Yi Wang, Long Jiang, Jun Xu, Kai Xu, Song Hu, Jun Xiang
Biomass-derived carbon aerogels are attractive carbon supports, yet their structural evolution under coking environments remains poorly understood. Utilizing a waste-pomelo-peel derived Ni/carbon aerogel (Ni/CA) as a model system, this work investigates the co-evolution of deposited carbon species and the resulting reconstruction of the carbon framework during ethanol cracking to elucidate dynamic structural transformations. Time-on-stream characterization combined with density functional theory (DFT) calculations revealed the coexistence of two distinct carbon growth patterns. After 6 h at 700 °C, the total carbon deposition rate reached 0.503 g· gcat−1· h−1 with filamentous carbon (52.2%) ultimately exceeding amorphous carbon (47.8%). Initially, disordered amorphous carbon preferentially filled intrinsic micropores, whereas filamentous structures became increasingly dominant over time. Filamentous carbon grew via a Ni catalyzed tip growth mode, inducing pronounced framework reconstruction. DFT calculations suggested that representative carbon-containing states and C–C bonded configurations can be stabilized on Ni/carbon interfacial sites, providing energetic support for the experimentally observed persistence of deposited carbon. More importantly, filament entanglement generated secondary meso-/macroporous voids that partially compensated for the loss of intrinsic microporosity within the examined reaction window. These results demonstrate that carbon deposition on Ni/CA is not a purely deactivating process, but a dynamic carbon-on-carbon reconstruction involving competition between pore-blocking amorphous coking and filament-induced pore reorganization. The work provides a mechanistic understanding from a carbon materials perspective regarding deposited carbon evolution on biomass-derived carbon aerogels and clarifies how concurrent carbon growth pathways reshape pore hierarchy and interfacial accessibility within the examined reaction window under carbon-rich reaction conditions.
生物质衍生的碳气凝胶是很有吸引力的碳载体,但其在焦化环境下的结构演变仍然知之甚少。利用废柚子皮衍生的Ni/碳气凝胶(Ni/CA)作为模型系统,本研究研究了乙醇裂解过程中沉积碳物种的共同演化以及由此产生的碳框架重建,以阐明动态结构转变。流上时间表征结合密度泛函理论(DFT)计算揭示了两种不同碳生长模式的共存。在700 ℃下,经过6 h后,总碳沉积速率达到0.503 g·gcat−1·h−1,丝状碳(52.2%)最终超过非晶态碳(47.8%)。最初,无序无定形碳优先填充固有微孔,而随着时间的推移,丝状结构越来越占主导地位。丝状碳通过Ni催化的尖端生长模式生长,诱导明显的框架重建。DFT计算表明,典型的含碳态和C-C键构型可以在Ni/碳界面上稳定下来,为实验观察到的沉积碳的持久性提供了能量支持。更重要的是,细丝纠缠产生了次级中孔/大孔空隙,部分补偿了在所检测的反应窗口内固有微孔的损失。这些结果表明,Ni/CA上的碳沉积不是一个纯粹的失活过程,而是一个动态的碳对碳重建过程,涉及孔隙阻塞非晶结焦和长丝诱导的孔隙重组之间的竞争。这项工作从碳材料的角度提供了关于生物质衍生碳气凝胶沉积碳演化的机制理解,并阐明了在富碳反应条件下,在所研究的反应窗口内,同步碳生长途径如何重塑孔隙结构和界面可及性。
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引用次数: 0
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