Journal of Energy Chemistry最新文献_第7页

Feature selection strategy optimization for lithium-ion battery state of health estimation under impedance uncertainties 阻抗不确定情况下锂离子电池健康状态估计的特征选择策略优化

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-27 DOI: 10.1016/j.jechem.2024.09.032

Xinghao Du , Jinhao Meng , Yassine Amirat , Fei Gao , Mohamed Benbouzid

Battery health evaluation and management are vital for the long-term reliability and optimal performance of lithium-ion batteries in electric vehicles. Electrochemical impedance spectroscopy (EIS) offers valuable insights into battery degradation analysis and modeling. However, previous studies have not adequately addressed the impedance uncertainties, particularly during battery operating conditions, which can substantially impact the robustness and accuracy of state of health (SOH) estimation. Motivated by this, this paper proposes a comprehensive feature optimization scheme that integrates impedance validity assessment with correlation analysis. By utilizing metrics such as impedance residuals and correlation coefficients, the proposed method effectively filters out invalid and insignificant impedance data, thereby enhancing the reliability of the input features. Subsequently, the extreme gradient boosting (XGBoost) modeling framework is constructed for estimating the battery degradation trajectories. The XGBoost model incorporates a diverse range of hyperparameters, optimized by a genetic algorithm to improve its adaptability and generalization performance. Experimental validation confirms the effectiveness of the proposed feature optimization scheme, demonstrating the superior estimation performance of the proposed method in comparison with four baseline techniques.

电池健康评估和管理对于电动汽车中锂离子电池的长期可靠性和最佳性能至关重要。电化学阻抗光谱（EIS）为电池降解分析和建模提供了宝贵的见解。然而，以往的研究并未充分考虑阻抗的不确定性，尤其是在电池工作条件下，这会严重影响健康状况（SOH）估算的稳健性和准确性。受此启发，本文提出了一种将阻抗有效性评估与相关性分析相结合的综合特征优化方案。通过利用阻抗残差和相关系数等指标，本文提出的方法能有效过滤无效和不重要的阻抗数据，从而提高输入特征的可靠性。随后，构建了极端梯度提升（XGBoost）建模框架，用于估计电池退化轨迹。XGBoost 模型包含多种超参数，并通过遗传算法进行了优化，以提高其适应性和泛化性能。实验验证证实了所提出的特征优化方案的有效性，表明与四种基准技术相比，所提出的方法具有更优越的估算性能。

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引用次数: 0

Atomically precise M-N-C electrocatalysts for oxygen reduction: Effects of inter-site distance, metal–metal interaction, coordination environment, and spin states 用于氧还原的原子精确 M-N-C 电催化剂：位间距、金属-金属相互作用、配位环境和自旋态的影响

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-26 DOI: 10.1016/j.jechem.2024.08.068

Junfeng Huang , Saira Ajmal , Anuj Kumar , Jianwen Guo , Mohammed Mujahid Alam , Abdullah G. Al-Sehemi , Ghulam Yasin

Inspired by molecular catalysts, researchers developed atomically precise nitrogen-coordinated single or dual metal sites imbedded in graphitized carbon (M-N-C) to fully utilize metallic sites for O₂ activation. These catalysts performed remarkably well in the electrocatalytic oxygen reduction reaction (ORR) due to their distinct coordination and electrical structures. Nonetheless, their maximum efficacy in practical applications has yet to be achieved. This agenda identifies tailoring the coordination environment, spin states, intersite distance, and metal–metal interaction as innovative approaches to regulate the ORR performance of these catalysts. However, it is necessary to undertake a precise assessment of these methodologies and the knowledge obtained to be implemented in the design of future M-N-C catalysts for ORR. Therefore, this review aims to analyze recent progress in M-N-C ORR catalysts, emphasizing their innovative engineering with aspects such as alteration in intersite distance, metal–metal interaction, coordination environment, and spin states. Additionally, we critically discuss how to logically monitor the atomic structure, local coordination, spin, and electronic states of M-N-C catalysts to modulate their ORR activity. We have also highlighted the challenges associated with M-N-C catalysts and proposed suggestions for their future design and fabrication.

受分子催化剂的启发，研究人员开发了原子精确的氮配位单金属位或双金属位嵌入石墨化碳（M-N-C），以充分利用金属位激活氧气。由于其独特的配位和电结构，这些催化剂在电催化氧还原反应（ORR）中表现出色。然而，它们在实际应用中的最大功效仍有待实现。本议程将调整配位环境、自旋态、位间距离和金属-金属相互作用作为调节这些催化剂 ORR 性能的创新方法。然而，有必要对这些方法和所获得的知识进行精确评估，以便在未来设计用于 ORR 的 M-N-C 催化剂时加以应用。因此，本综述旨在分析 M-N-C ORR 催化剂的最新进展，强调其在改变位间距离、金属-金属相互作用、配位环境和自旋状态等方面的创新工程。此外，我们还认真讨论了如何对 M-N-C 催化剂的原子结构、局部配位、自旋和电子状态进行逻辑监控，以调节其 ORR 活性。我们还强调了与 M-N-C 催化剂相关的挑战，并对其未来的设计和制造提出了建议。

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引用次数: 0

Boosting bidirectional sulfur conversion enabled by introducing boron-doped atoms and phosphorus vacancies in Ni2P for lithium-sulfur batteries 通过在锂硫电池的 Ni2P 中引入掺硼原子和磷空位，促进硫的双向转化

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-25 DOI: 10.1016/j.jechem.2024.09.027

Lin Peng , Yu Bai , Hang Li , Meixiu Qu , Zhenhua Wang , Kening Sun

Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost, yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish redox dynamics. Herein, we supply a strategy to optimize the electron structure of Ni₂P by concurrently introducing B-doped atoms and P vacancies in Ni₂P (V_p-B-Ni₂P), thereby enhancing the bidirectional sulfur conversion. The study indicates that the simultaneous introduction of B-doped atoms and P vacancies in Ni₂P causes the redistribution of electron around Ni atoms, bringing about the upward shift of d-band center of Ni atoms and effective d-p orbital hybridization between Ni atoms and sulfur species, thus strengthening the chemical anchoring for lithium polysulfides (LiPSs) as well as expediting the bidirectional conversion kinetics of sulfur species. Meanwhile, theoretical calculations reveal that the incorporation of B-doped atoms and P vacancies in Ni₂P selectively promotes Li₂S dissolution and nucleation processes. Thus, the Li-S batteries with V_p-B-Ni₂P-separators present outstanding rate ability of 777 mA h g⁻¹ at 5 C and high areal capacity of 8.03 mA h cm⁻² under E/S of 5 μL mg⁻¹ and sulfur loading of 7.20 mg cm⁻². This work elucidates that introducing heteroatom and vacancy in metal phosphide collaboratively regulates the electron structure to accelerate bidirectional sulfur conversion.

锂硫（Li-S）电池因其理论能量密度高、成本低而备受关注，但其进一步商业化却因臭名昭著的穿梭效应和缓慢的氧化还原动力学而受阻。在此，我们提供了一种优化 Ni2P 电子结构的策略，即在 Ni2P 中同时引入掺 B 原子和 P 空位（Vp-B-Ni2P），从而增强硫的双向转化。研究表明，在 Ni2P 中同时引入掺杂 B 原子和 P 空位会导致镍原子周围电子的重新分布，使镍原子的 d 带中心上移，镍原子与硫元素之间产生有效的 d-p 轨道杂化，从而加强了多硫化锂（LiPSs）的化学锚定，并加快了硫元素的双向转化动力学。同时，理论计算显示，Ni2P 中掺杂的 B 原子和 P 空位选择性地促进了 Li2S 的溶解和成核过程。因此，在 5 μL mg-1 的 E/S 和 7.20 mg cm-2 的硫载荷条件下，使用 Vp-B-Ni2P 隔离剂的锂-S 电池在 5 C 时具有 777 mA h g-1 的出色速率能力和 8.03 mA h cm-2 的高平均容量。这项工作阐明了在金属磷化物中引入杂原子和空位可协同调节电子结构，从而加速双向硫转化。

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引用次数: 0

Synthesis of intermetallic PtCo fuel cell catalysts from bimetallic core@shell structured nanoparticles 利用双金属核@壳结构纳米颗粒合成金属间铂钴燃料电池催化剂

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-25 DOI: 10.1016/j.jechem.2024.09.028

Le Zhang, Lei Tong, Shuai Li, Chang-Song Ma, Kun-Ze Xue, Hai-Wei Liang

The high activity and stability of intermetallic PtCo nanocatalysts toward oxygen reduction reaction make them a top candidate as low-Pt cathode catalysts in proton exchange membrane fuel cells (PEMFCs). However, forming intermetallic structures typically requires high-temperature annealing, posing a challenge for achieving well-size control and highly ordered structures. Here we report the design and synthesis of bimetallic core@shell structured precursors for affording high-performance intermetallic PtCo catalysts. The fabrication of the core@shell precursor involves using a molecular ligand containing both sulfur and oxygen donors to selectively bind with Pt colloidal nanoparticles as the core and chelate Co ions as the shell. During high-temperature annealing, the ligand transforms into carbon coatings around alloy nanoparticles, preventing particle sintering; meanwhile, Co ions in the shell can easily diffuse into the Pt core, which helps to increase the thermodynamic driving force for forming intermetallic structures. These benefits enable us to obtain the catalyst with finely dispersed nanoparticles (∼3.5 nm) and a high ordering degree of 72%. With 0.1 mg_Pt/cm² cathode loading, the catalyst delivers superior performance and durability in PEMFCs, showing an initial mass activity of 0.56 A/mg_Pt, an initial power density of 1.05 W/cm² at 0.67 V (H₂-air), and a voltage loss of 26 mV at 0.8 A/cm² after the accelerated durability test.

金属间铂钴纳米催化剂对氧还原反应具有高活性和稳定性，因此是质子交换膜燃料电池（PEMFC）中低铂阴极催化剂的最佳候选材料。然而，形成金属间结构通常需要高温退火，这对实现良好的尺寸控制和高度有序的结构提出了挑战。在此，我们报告了双金属核@壳结构前驱体的设计与合成，以获得高性能的金属间铂钴催化剂。核@壳前驱体的制备包括使用一种同时含有硫和氧供体的分子配体，选择性地与作为核的铂胶体纳米粒子和作为壳的螯合钴离子结合。在高温退火过程中，配体会在合金纳米粒子周围形成碳涂层，从而防止粒子烧结；同时，外壳中的 Co 离子很容易扩散到铂核中，这有助于增加形成金属间结构的热力学驱动力。这些优点使我们能够获得分散度极小的纳米颗粒（∼3.5 nm）和高有序度（72%）的催化剂。该催化剂的阴极负载量为 0.1 mgPt/cm2，在 PEMFC 中具有优异的性能和耐久性，显示出 0.56 A/mgPt 的初始质量活性、0.67 V（H2-空气）时 1.05 W/cm2 的初始功率密度以及加速耐久性测试后 0.8 A/cm2 时 26 mV 的电压损失。

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引用次数: 0

Electronic modulation induced by coupling RuO2 with electron-donating Co3O4 for high-active and long-life rechargeable Zn-air batteries 通过将 RuO2 与电子捐赠型 Co3O4 相耦合诱导电子调制，实现高活性、长寿命的锌-空气充电电池

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-25 DOI: 10.1016/j.jechem.2024.09.029

Xuena Ma , Zhangxin Xu , Mingyang Liu , Panzhe Qiao , Qi Li , Ruihong Wang , Baojiang Jiang

Electronic-state modulation strategy offers great potential in designing RuO₂-based bifunctional-electrocatalysts for rechargeable Zn-air batteries (ZABs). Various three-dimensional (3D) transition metal oxides are attempted to couple with RuO₂ for constructing an appropriate RuOM interface. This work aims to construct Co₃O₄-RuO₂ heterostructures on carbon sheets (Co₃O₄/RuO₂/NCNS) for boosting electronic transfer and regulation. Experiments and theoretical calculations identify the electronic transfer from Co₃O₄ to RuO₂ that modulates the electronic structure of metal surfaces/interfaces. Specifically, it leads to the increase in Co³⁺ content, electron-rich state at RuO₂ surface and electronic accumulation at interfaces. Moreover, this electronic-state modulation optimizes the d-band center in Co₃O₄/RuO₂ that lowers the reaction barriers and endows interfaces as the biggest contributor to oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance. The Co₃O₄/RuO₂/NCNS shows a quite low potential difference of 0.62 V and remarkable durability for ORR/OER. Co₃O₄/RuO₂/NCNS-assembled ZABs exhibit an excellent specific capacity of 818.3 mA h g⁻¹ and a superior lifespan over 750 h.

电子状态调制策略为设计基于 RuO2 的可充电锌-空气电池（ZAB）双功能电催化剂提供了巨大的潜力。人们尝试将各种三维（3D）过渡金属氧化物与 RuO2 结合，以构建合适的 RuOM 界面。这项研究的目的是在碳片（Co3O4/RuO2/NCNS）上构建 Co3O4-RuO2 异质结构，以促进电子传输和调节。实验和理论计算发现，从 Co3O4 到 RuO2 的电子转移可调节金属表面/界面的电子结构。具体来说，它导致 Co3+ 含量的增加、RuO2 表面的富电子状态以及界面上的电子积聚。此外，这种电子状态调制优化了 Co3O4/RuO2 的 d 带中心，从而降低了反应壁垒，并使界面成为氧还原反应（ORR）和氧进化反应（OER）性能的最大贡献者。Co3O4/RuO2/NCNS 的电位差很低，仅为 0.62 V，而且在 ORR/OER 反应中具有显著的耐久性。Co3O4/RuO2/NCNS 组装的 ZAB 具有 818.3 mA h g-1 的出色比容量和 750 小时以上的超长寿命。

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引用次数: 0

Unlocking the stable interface in aqueous zinc-ion battery with multifunctional xylose-based electrolyte additives 用基于木糖的多功能电解质添加剂打开锌离子水电池的稳定界面

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-25 DOI: 10.1016/j.jechem.2024.09.030

Xiaoqin Li , Jian Xiang , Lu Qiu , Xiaohan Chen , Yinkun Zhao , Yujue Wang , Qu Yue , Taotao Gao , Wenlong Liu , Dan Xiao , Zhaoyu Jin , Panpan Li

The growth of dendrites and the side reactions occurring at the Zn anode pose significant challenges to the commercialization of aqueous Zn-ion batteries (AZIBs). These challenges arise from the inherent conflict between mass transfer and electrochemical kinetics. In this study, we propose the use of a multifunctional electrolyte additive based on the xylose (Xylo) molecule to address these issues by modulating the solvation structure and electrode/electrolyte interface, thereby stabilizing the Zn anode. The introduction of the additive alters the solvation structure, creating steric hindrance that impedes charge transfer and then reduces electrochemical kinetics. Furthermore, in-situ analyses demonstrate that the reconstructed electrode/electrolyte interface facilitates stable and rapid Zn²⁺ ion migration and suppresses corrosion and hydrogen evolution reactions. As a result, symmetric cells incorporating the Xylo additive exhibit significantly enhanced reversibility during the Zn plating/stripping process, with an impressively long lifespan of up to 1986 h, compared to cells using pure ZnSO₄ electrolyte. When combined with a polyaniline cathode, the full cells demonstrate improved capacity and long-term cyclic stability. This work offers an effective direction for improving the stability of Zn anode via electrolyte design, as well as high-performance AZIBs.

枝晶的生长和锌阳极发生的副反应给水性锌离子电池（AZIB）的商业化带来了巨大挑战。这些挑战源于传质与电化学动力学之间的内在冲突。在本研究中，我们提出使用一种基于木糖（Xylo）分子的多功能电解质添加剂，通过调节溶解结构和电极/电解质界面来解决这些问题，从而稳定锌阳极。添加剂的引入改变了溶解结构，产生了立体阻碍，阻碍了电荷转移，进而降低了电化学动力学。此外，原位分析表明，重建的电极/电解质界面有利于 Zn2+ 离子稳定而快速地迁移，并抑制腐蚀和氢演化反应。因此，与使用纯 ZnSO4 电解液的电池相比，含有 Xylo 添加剂的对称电池在镀锌/剥离过程中的可逆性显著提高，使用寿命长达 1986 小时，令人印象深刻。当与聚苯胺阴极结合使用时，全电池的容量和长期循环稳定性都得到了提高。这项工作为通过电解质设计提高锌阳极的稳定性以及高性能 AZIB 提供了一个有效的方向。

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引用次数: 0

Multi boron-doping effects in hard carbon toward enhanced sodium ion storage 硬碳中的多硼掺杂效应可提高钠离子存储能力

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-24 DOI: 10.1016/j.jechem.2024.09.024

Peng Zheng , Wang Zhou , Ying Mo , Biao Zheng , Miaomiao Han , Qin Zhong , Wenwen Yang , Peng Gao , Lezhi Yang , Jilei Liu

Hard carbon (HC) has been considered as promising anode material for sodium-ion batteries (SIBs). The optimization of hard carbon’s microstructure and solid electrolyte interface (SEI) property are demonstrated effective in enhancing the Na⁺ storage capability, however, a one-step regulation strategy to achieve simultaneous multi-scale structures optimization is highly desirable. Herein, we have systematically investigated the effects of boron doping on hard carbon’s microstructure and interface chemistry. A variety of structure characterizations show that appropriate amount of boron doping can increase the size of closed pores via rearrangement of carbon layers with improved graphitization degree, which provides more Na⁺ storage sites. In-situ Fourier transform infrared spectroscopy/electrochemical impedance spectroscopy (FTIR/EIS) and X-ray photoelectron spectroscopy (XPS) analysis demonstrate the presence of more BC₃ and less B–C–O structures that result in enhanced ion diffusion kinetics and the formation of inorganic rich and robust SEI, which leads to facilitated charge transfer and excellent rate performance. As a result, the hard carbon anode with optimized boron doping content exhibits enhanced rate and cycling performance. In general, this work unravels the critical role of boron doping in optimizing the pore structure, interface chemistry and diffusion kinetics of hard carbon, which enables rational design of sodium-ion battery anode with enhanced Na⁺ storage performance.

硬碳（HC）一直被认为是钠离子电池（SIBs）的理想负极材料。优化硬碳的微观结构和固体电解质界面（SEI）特性已被证明能有效提高 Na+ 的存储能力，然而，一步到位的调节策略能同时实现多尺度的结构优化是非常可取的。在此，我们系统地研究了掺硼对硬碳微观结构和界面化学性质的影响。各种结构表征表明，适量的硼掺杂可以通过提高石墨化程度的碳层重排来增加封闭孔隙的尺寸，从而提供更多的 Na+ 储存位点。原位傅立叶变换红外光谱/电化学阻抗光谱（FTIR/EIS）和 X 射线光电子能谱（XPS）分析表明，BC3 结构增多，B-C-O 结构减少，从而增强了离子扩散动力学，形成了富含无机物的坚固 SEI，促进了电荷转移，实现了优异的速率性能。因此，优化了硼掺杂含量的硬碳阳极具有更高的速率和循环性能。总之，这项研究揭示了硼掺杂在优化硬碳的孔隙结构、界面化学和扩散动力学方面的关键作用，从而能够合理设计具有更强 Na+ 储存性能的钠离子电池阳极。

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引用次数: 0

Reversible phase transition poly(benzyl methacrylate)/ionic liquid electrolytes for effective overheating protection in lithium batteries 用于锂电池有效过热保护的可逆相变聚（甲基丙烯酸苄酯）/离子液体电解质

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-24 DOI: 10.1016/j.jechem.2024.09.026

Qian Yu , Wei Sun , Jialing Zhu , Haoxiang Li , Shuai Wang , Longqing Huang , Qian Qiu , Haoran Tian , He Miao , Fu Wang , Chunfei Zhang , Jinliang Yuan , Lan Xia

Battery safety is influenced by various factors, with thermal runaway being one of the most significant concerns. While most studies have concentrated on developing one-time, self-activating mechanism for thermal protection, such as temperature-responsive electrodes, and thermal-shutdown separators, these methods only provide irreversible protection. Recently, reversible temperature-sensitive electrolytes have emerged as promising alternatives, offering both thermo-reversibility and self-protective properties. However, further research is crucial to fully understand these thermal-shutdown electrolytes. In this study, we propose lower critical solution temperature (LCST) phase behavior poly(benzyl methacrylate)/imidazolium-based ionic liquid mixtures to prepare temperature-sensitive electrolytes that provide reversible thermal shutdown protection of batteries. This electrolyte features an appropriate protection temperature (∼105 °C) and responds quickly within a 1 min at 105 °C, causing cells to hardly discharge as the voltage suddenly drops to 3.38 V, and providing efficient thermal shutdown protection within 30 min. Upon cooling back to room temperature, the battery regains its original performance. Additionally, the electrolyte exhibits excellent cycling stability with the capacity retention of the battery is 91.6% after 500 cycles. This work provides a viable solution for preventing batteries from thermal runaway triggered by overheating.

电池安全受到各种因素的影响，其中热失控是最令人担忧的问题之一。虽然大多数研究都集中于开发一次性自激活热保护机制，如温度响应电极和热关断分离器，但这些方法只能提供不可逆的保护。最近，可逆温敏电解质作为一种有前途的替代品出现了，它同时具有热可逆性和自我保护特性。然而，进一步的研究对于全面了解这些热关断电解质至关重要。在本研究中，我们提出了较低临界溶液温度（LCST）相行为聚（甲基丙烯酸苄酯）/咪唑基离子液体混合物，用于制备温度敏感型电解质，为电池提供可逆的热关断保护。这种电解质具有适当的保护温度（∼105 °C），并能在 105 °C下的 1 分钟内快速反应，使电池在电压突然降至 3.38 V 时几乎不放电，并在 30 分钟内提供有效的热关断保护。冷却至室温后，电池即可恢复原有性能。此外，这种电解液还具有出色的循环稳定性，在循环 500 次后，电池容量保持率达到 91.6%。这项研究为防止电池因过热而引发热失控提供了可行的解决方案。

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引用次数: 0

Synergistically enhanced ORR and HER performance on Co-N-C coupled in-situ generated PtCo intermetallic 原位生成的铂钴金属间化合物上协同增强的 ORR 和 HER 性能

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-24 DOI: 10.1016/j.jechem.2024.09.023

Guanyu Luo, Min Song, Lulu An, Xiao Huang, Qian Zhang, Chenhao Zhang, Tao Shen, Shuang Wang, Deli Wang

Integrating multi-scale sites in a composite catalyst is vital to realize efficient electrocatalysis. Herein, a synergistic composite catalyst consisting of Co atomic sites and in-situ generated PtCo intermetallic compounds (IMCs) (o-PtCo@CoNC) is proposed through Co pre-anchoring and subsequent impregnation-reduction method. High loading of Co atoms provides a chance for in-situ generating PtCo ordered intermetallic compounds. The remaining Co single atoms and PtCo IMCs construct synergistic electrocatalytic micro-regions. Benefiting from the ordered structure, synergistic effect of PtCo IMCs and Co single atoms, o-PtCo@CoNC exhibits excellent electrocatalytic performance for oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) with mass activity of 1.21 A mg_Pt⁻¹ (at 0.9 V) and 5.70 A mg_Pt⁻¹ (at an overpotential of 100 mV), respectively. Besides, o-PtCo@CoNC delivers negligible loss of half-wave potential and overpotential during long-term stability test in acid solutions, with 13 mV decay after 50,000 potential cycles for ORR and a 2.7 mV decay after 20,000 potential cycles for HER. The integration strategy of single-atomic sites coupled IMCs paves the way for enhancing the activity and durability of Pt-based electrocatalysts.

在复合催化剂中整合多尺度位点对于实现高效电催化至关重要。本文通过 Co 预锚定和随后的浸渍还原方法，提出了一种由 Co 原子位点和原位生成的铂钴金属间化合物（IMCs）（o-PtCo@CoNC）组成的协同复合催化剂。高含量的 Co 原子为原位生成铂钴有序金属间化合物提供了机会。剩余的 Co 单原子和 PtCo IMC 构建了协同电催化微区。得益于有序结构、PtCo IMCs 和 Co 单原子的协同效应，o-PtCo@CoNC 在氧还原反应（ORR）和氢进化反应（HER）中表现出优异的电催化性能，质量活性分别为 1.21 A mgPt-1（0.9 V 时）和 5.70 A mgPt-1（100 mV 过电位时）。此外，在酸溶液中进行长期稳定性测试时，o-PtCo@CoNC 的半波电位和过电位损失微乎其微，ORR 在 50,000 次电位循环后衰减 13 mV，HER 在 20,000 次电位循环后衰减 2.7 mV。单原子位点耦合 IMC 的集成策略为提高铂基电催化剂的活性和耐用性铺平了道路。

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引用次数: 0

Engineering nanoparticle structure at synergistic Ru-Na interface for integrated CO2 capture and hydrogenation 在 Ru-Na 协同界面上设计纳米粒子结构，实现二氧化碳捕获和氢化一体化

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-24 DOI: 10.1016/j.jechem.2024.09.025

Hanzi Liu, Ling Cen, Xinlin Xie, Lei Liu, Zhao Sun, Zhiqiang Sun

The development of dual functional material for cyclic CO₂ capture and hydrogenation is of great significance for converting diluted CO₂ into valuable fuels, but suffers from kinetic limitation and deactivation of adsorbent and catalyst. Herein, we engineered a series of RuNa/γ-Al₂O₃ materials, varying the size of ruthenium from single atoms to clusters/nanoparticles. The coordination environment and structure sensitivity of ruthenium were quantitatively investigated at atomic scale. Our findings reveal that the reduced Ru nanoparticles, approximately 7.1 nm in diameter with a Ru-Ru coordination number of 5.9, exhibit high methane formation activity and selectivity at 340 °C. The Ru-Na interfacial sites facilitate CO₂ migration through a deoxygenation pathway, involving carbonate dissociation, carbonyl formation, and hydrogenation. In-situ experiments and theoretical calculations show that stable carbonyl intermediates on metallic Ru nanoparticles facilitate heterolytic C–O scission and C–H bonding, significantly lowering the energy barrier for activating stored CO₂.

开发用于循环捕集和氢化二氧化碳的双功能材料对于将稀释的二氧化碳转化为有价值的燃料具有重要意义，但却受到动力学限制以及吸附剂和催化剂失活的困扰。在此，我们设计了一系列 RuNa/γ-Al2O3 材料，钌的大小从单个原子到团簇/纳米颗粒不等。我们在原子尺度上定量研究了钌的配位环境和结构敏感性。我们的研究结果表明，还原型 Ru 纳米粒子（直径约 7.1 nm，Ru-Ru 配位数为 5.9）在 340 °C 下具有很高的甲烷生成活性和选择性。Ru-Na 界面位点有助于二氧化碳通过脱氧途径迁移，包括碳酸盐解离、羰基形成和氢化。原位实验和理论计算表明，金属 Ru 纳米粒子上稳定的羰基中间体促进了异溶性 C-O 裂解和 C-H 键合，显著降低了激活储存的 CO2 的能量障碍。

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引用次数: 0