Electrochimica Acta最新文献_第3页

Two p-tert-butylthiacalix[4]arene-supported bismuth cluster compounds for ultrahigh efficiency detection of trace-level Cd2+ and Pb2+ 两种对叔丁基硫杯[4]芳烃负载铋簇化合物，用于超高效率检测痕量Cd2+和Pb2+

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-16 DOI: 10.1016/j.electacta.2025.148023

Chang Liu , Tianlong Shan , Hongda Li , Sitong Wu , Meng Zhao , Guannan Wang , Rui Zhang

Heavy metal ions (HMIs) in the environment pose a significant threat to both environmental quality and human health. Consequently, monitoring HMIs concentrations is an essential yet challenging endeavor. Electrochemical sensing emerges as an effective method for detecting HMIs due to its high reliability and sensitivity. According to the hard/soft acid/base theory, porous metal-organic complexes containing S, O or N hybrid atoms provide the binding sites that facilitate the trapping of HMIs within cavities during the electrochemical deposition process, thereby enhancing detection sensitivity. In this study, we employed p‑tert-butylthiacalix[4]arene ligands (H₄TC4A) to rationally design two Bi(III) clusters compounds: [Bi₄(TC4A)₂(µ₄O)]·2NO₃·3DMF·3MeOH (Bi₄-TC4A) and [Bi₈(TC4A)₅(en)₂(µ₃OH)₂(µ₄OH)₂]·5DMF·2MeOH (Bi₈-TC4A). Furthermore, we constructed two Bi(III)-based electrochemical sensors, Bi₄-TC4A/GCE and Bi₈-TC4A/GCE, for the detection of Cd²⁺ and Pb²⁺ ions. Compared to Bi₄-TC4A, Bi₈-TC4A contains eight Bi(Ⅲ) cations and five sulfur-containing TC4A^4- ligands, which significantly enhance the enrichment and adsorption of HMIs for electrochemical sensing applications. Notably, the linear ranges for Cd²⁺ and Pb²⁺ on the Bi₈-TC4A/GCE were found to be 0.01–1.1 mg·L^-1 and 0.01–1.4 mg L^-1 with the detection limits of 1.4 and 1.7 μg L^-1, respectively, which are lower than those specified by World Health Organization guidelines. This work offers valuable insights into utilizing well-designed Bi(III) cluster-based sensors for highly sensitive electrochemical detection of HMIs with low detection limits.

环境中的重金属离子对环境质量和人类健康构成重大威胁。因此，监控人机界面…

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引用次数: 0

Flower-like Ni/NiO heterointerfaces supported by amino-functionalized carbon nanotubes for enhanced lithium storage 氨基功能化碳纳米管支持的花状Ni/NiO异质界面增强锂存储

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-16 DOI: 10.1016/j.electacta.2025.148028

Xiuya Guo , Xinyi Wang , Jiaqi Cui , Haoda Wu , Chenyu Zhao , Zhongshan Liu , Yanmin Qin , Zheng Fang , Chunmin Li

A flower-like nickel/nickel oxide composite supported by amino-functionalized carbon nanotubes (Ni/NiO@ACNTs/C) was synthesized through a hydrothermal process followed by carbothermal reduction. Structural analyses confirm that hierarchical nickel oxide nanosheets uniformly grow on the ACNTs/C, while metallic nickel is generated in situ. The carbon nanotube network builds a three-dimensional conductive framework that enables uniform nucleation of nickel oxide and rapid electron transport, and the metallic nickel further improves conductivity and interfacial activity. Electrochemical tests show that the composite delivers a high reversible capacity of 1136 mAh g^-1 at 0.1 A g^-1 and maintains 480 and 351.5 mAh g^-1 after 1000 and 2000 cycles at 1.0 and 5.0 A g^-1, respectively, with Coulombic efficiency above 99 %. Impedance and titration analyses reveal reduced charge-transfer resistance and enhanced lithium-ion diffusion, while cyclic voltammetry indicates combined diffusion-controlled and pseudocapacitive contributions. The improved performance arises from the coupled nickel/nickel oxide interface together with efficient ion-transport channels, improved electrolyte wetting, and structural buffering provided by the flower-like porous network. This work presents an effective structural design strategy for nickel oxide–based conversion anodes toward high-energy and long-lifespan lithium-ion batteries.

以氨基功能化碳纳米管（Ni/NiO@ACNTs/C）为载体，通过水热还原法制备了花状镍/氧化镍复合材料（Ni/NiO@ACNTs/C）。结构分析证实，层次化氧化镍纳米片在acnt /C上均匀生长，金属镍在原位生成。碳纳米管网络构建了三维导电框架，实现了氧化镍的均匀成核和电子的快速传递，金属镍进一步提高了电导率和界面活性。电化学测试表明，该复合材料在0.1 a g-1下可提供1136 mAh g-1的高可逆容量，在1.0和5.0 a g-1下循环1000次和2000次后分别保持480和351.5 mAh g-1，库仑效率超过99%。阻抗和滴定分析显示电荷转移电阻降低，锂离子扩散增强，而循环伏安法显示扩散控制和伪电容的共同贡献。性能的提高来自于耦合的镍/氧化镍界面以及高效的离子传输通道，改善的电解质润湿性以及由花状多孔网络提供的结构缓冲。这项工作提出了一种有效的结构设计策略，用于高能和长寿命锂离子电池的镍基转换阳极。

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引用次数: 0

Predictive physical parameters for reproducible electrochemical detection of α-hemolysin with tBLMs on FTO substrates FTO底物上tBLMs可重复性电化学检测α-溶血素的预测物理参数

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-15 DOI: 10.1016/j.electacta.2025.148019

Gerda Ziziunaite , Gintaras Valincius , Aušra Valiūnienė

Tethered bilayer lipid membranes (tBLMs) are promising platforms for studying membrane–toxin interactions and developing biosensors for pore-forming agents such as α-hemolysin (αHL). However, the poor reproducibility of electrochemical impedance spectroscopy (EIS) responses across nominally identical tBLMs remains a major limitation. Here, we introduce the concept of effective defect density

N_{d e f}^{e f f}

, derived from EIS data under a fixed submembrane resistance, as a quantitative descriptor of membrane integrity and a predictive indicator of sensor performance. Using αHL as a model pore-forming toxin, we show that

N_{d e f}^{e f f}

, of pristine tBLMs strongly predicts the magnitude and reproducibility of toxin-induced disruption across multiple incubation times (5–60 min). Calibration curves constructed from these correlations enable the prediction of both expected response and associated uncertainty, allowing for self-calibration of individual tBLM sensors. Notably, tBLMs with medium-to-high initial defect densities yielded the lowest relative measurement errors, challenging the conventional preference for highly insulating membranes in biosensing applications. We further demonstrate that the equivalent membrane capacitance (C_mH), which can be directly extracted from raw EIS spectra without model fitting, also correlates with toxin response, offering a simpler, though slightly less precise, calibration metric. These findings establish

N_{d e f}^{e f f}

, and C_mH as robust, quantitative predictors of tBLM sensitivity to pore-forming toxins, providing a pathway toward rapid, self-calibrating biosensors capable of quantitative detection within minutes.

系留双分子层脂质膜（tBLMs）是研究膜-毒素相互作用和开发生物传感器（如α-溶血素（αHL））的有前途的平台。然而，电化学阻抗谱（EIS）在名义上相同的tblm上的响应重现性差仍然是一个主要限制。在这里，我们引入了有效缺陷密度ndefff的概念，该概念来源于固定亚膜电阻下的EIS数据，作为膜完整性的定量描述符和传感器性能的预测指标。利用αHL作为模型成孔毒素，我们发现原始tBLMs的ndefffndefff可以预测毒素诱导的破坏在多个孵育时间（5-60分钟）内的强度和可重复性。根据这些相关性构建的校准曲线能够预测预期响应和相关不确定性，从而允许单个tBLM传感器进行自校准。值得注意的是，具有中高初始缺陷密度的tblm产生了最低的相对测量误差，挑战了生物传感应用中对高度绝缘膜的传统偏好。我们进一步证明，等效膜电容（CmH）可以直接从原始EIS光谱中提取，而无需模型拟合，也与毒素响应相关，提供了一个更简单的校准度量，尽管精度略低。这些发现建立了ndefffndefff和CmH作为tBLM对孔隙形成毒素敏感性的可靠定量预测指标，为能够在几分钟内进行定量检测的快速、自校准生物传感器提供了途径。

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引用次数: 0

A regenerable tin gas diffusion electrode as a durable and cost-effective cathode for large-scale CO2 reduction with enhanced viability via brine co-electrolysis 可再生锡气体扩散电极作为一种耐用且经济高效的阴极，可通过盐水共电解大规模减少二氧化碳

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-15 DOI: 10.1016/j.electacta.2025.148018

Anoop Naikkath , Kothandaraman Ramanujam , Ramanathan Srinivasan

The industrial implementation of the electrochemical CO₂ reduction reaction (CO₂RR) has been a topic of interest for decades. However, commercial scale-up of CO₂ electrolysis is hindered by poor electrode stability, low efficiency at high current densities, and high operational costs. In this work, a binder-free Sn-based gas diffusion electrode (Sn-GDE), developed via a novel three-step methodology, achieves remarkable formate selectivity >70% at 500 mA cm⁻². An in-situ reactivation protocol enables stable operation for over 120 h at 100 mA cm⁻² without flooding, while maintaining formate selectivity above 75%. Notably, through a tailored cell design, we also achieved over 35% single-pass conversion across all current densities in a flow-through configuration, representing one of the highest reported performances in the literature to date for the CO₂RR to formate on Sn systems. Given the substantial energy penalty imposed by the oxygen evolution reaction (OER) at the anode, we demonstrate the replacement of the OER with the chloride oxidation reaction (COR), offering a more energy-efficient route for the process. The COR achieves over 66% hypochlorite efficiency at the anode without affecting cathodic performance, presenting a commercially viable path reinforced by the well-established chlor-alkali industry. A technoeconomic analysis of a 3000 TPD formic acid plant shows that replacing the traditional OER with COR increased the gross margin from 12% to 32% at 200 mA cm⁻². Furthermore, Monte Carlo simulations reveal that this substitution increases the probability of profitability to ∼55%, compared with only 19% with the OER. These findings highlight the tremendous potential of our newly developed Sn-GDE design when integrated with COR-driven CO₂ electrolysis to enable stable, scalable and economically viable CO₂ utilization.

几十年来，电化学CO₂还原反应（CO2RR）的工业实施一直是人们感兴趣的话题。然而，CO 2电解的商业化规模受到电极稳定性差、高电流密度下效率低和操作成本高的阻碍。在这项工作中，一种无粘结剂的锡基气体扩散电极（Sn-GDE），通过一种新颖的三步法开发，在500毫安厘米（⁻²）下实现了70%的甲酸选择性。在100毫安厘米（⁻²）下稳定运行120小时以上，同时甲酸选择性保持在75%以上。值得注意的是，通过量身定制的电池设计，我们还在流过配置的所有电流密度下实现了超过35%的单次转换，这是迄今为止文献中CO2RR在Sn系统上形成的最高性能之一。考虑到阳极的析氧反应（OER）带来的大量能量损失，我们证明了用氯化物氧化反应（COR）取代OER，为该过程提供了更节能的途径。在不影响阴极性能的情况下，COR在阳极上实现了超过66%的次氯酸盐效率，为成熟的氯碱工业提供了一条商业上可行的途径。对一个3000 TPD甲酸厂的技术经济分析表明，用COR代替传统的OER使毛利率从12%增加到32% （200 mA cm⁻²）。此外，蒙特卡罗模拟显示，这种替代将盈利能力的概率提高到约55%，而OER仅为19%。这些发现凸显了我们新开发的Sn-GDE设计与co驱动的二氧化碳电解相结合的巨大潜力，可以实现稳定、可扩展和经济上可行的二氧化碳利用。

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引用次数: 0

Operando confocal microscopy and visualization of strain distributions in sulfide solid electrolyte sheets with non-woven fabric scaffolds during lithium stripping/plating 用Operando共聚焦显微镜观察含无纺布支架的硫化固体电解质片在锂剥离/镀过程中的应变分布

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-15 DOI: 10.1016/j.electacta.2025.148017

Misae Otoyama, Yushi Fujita, Tomonari Takeuchi, Kentaro Kuratani, Toyoki Okumura

Sheet-type all-solid-state lithium metal batteries (ASSLMBs) with solid electrolyte (SE) thin films have attracted considerable attention owing to their high energy density. However, crack formation and propagation in SE layers during lithium stripping/plating hinder their practical applications. This study focused on strength of SE sheet to prevent such mechanical issues and enhance lithium stripping/plating performance. A free-standing SE sheet was prepared by coating a slurry of Li₆PS₅Cl onto a non-woven fabric (NWF) scaffold to enhance strength and bendability compared with an NWF-free SE sheet. Lithium symmetric cells using the scaffold-assisted SE sheet demonstrated superior lithium stripping/plating performance. Operando confocal microscopy on the cross-sections of the cells enabled a comparison of morphological changes in the SE sheets during lithium stripping/plating. The NWF-free sheet exhibited crack formation and propagation just before short-circuiting, whereas no large cracks appeared in the SE sheet with NWF, indicating that NWF-scaffold structures effectively prevent crack formation. Moreover, digital image correlation (DIC) analysis of the operando microscopy images revealed that regions of high strain spread locally within the NWF-free SE sheet, whereas the scaffold-assisted SE sheet showed low and uniformly distributed strain. Overall, this study visually and quantitatively demonstrates, for the first time, that NWF scaffolds can obtain uniform strain distribution and prevent crack formation during lithium stripping/plating, as confirmed by DIC analysis. These findings highlight the potential of scaffold-assisted SE thin sheets as flexible separators for ASSLMBs.

具有固体电解质（SE）薄膜的片状全固态锂金属电池（asslmb）因其高能量密度而受到广泛关注。然而，锂剥离/镀过程中SE层中裂纹的形成和扩展阻碍了SE层的实际应用。本研究的重点是硒板的强度，以防止此类机械问题，并提高锂剥离/镀性能。将Li6PS5Cl浆液涂覆在无纺布（NWF）支架上，制备了独立的SE片材，与无NWF的SE片材相比，其强度和可弯曲性得到了提高。使用支架辅助SE片材的锂对称电池表现出优越的锂剥离/镀性能。在细胞横截面上的Operando共聚焦显微镜可以比较锂剥离/电镀过程中SE片的形态学变化。无NWF的板在短路前出现了裂纹的形成和扩展，而有NWF的SE板没有出现大的裂纹，说明NWF支架结构有效地防止了裂纹的形成。此外，对operando显微镜图像进行数字图像相关（DIC）分析发现，在无nwf的SE片内，高应变区域局部分布，而支架辅助的SE片则显示低应变且均匀分布。总体而言，本研究首次从视觉和定量上证明了NWF支架在锂剥离/镀过程中可以获得均匀的应变分布并防止裂纹的形成，DIC分析也证实了这一点。这些发现突出了支架辅助SE薄片作为asslmb柔性分离器的潜力。

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引用次数: 0

Polyethyleneimine-bound [FeFe]-hydrogenase mimics as bioinspired diiron electrocatalysts for hydrogen evolution reaction 聚亚胺结合[FeFe]-氢化酶模拟生物激发双铁电催化剂的析氢反应

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-15 DOI: 10.1016/j.electacta.2025.148024

Pei-Hua Zhao , Zhen Guo , Yu-Long Sun , Yan-Nan Liu , Xing-Bin Jing , Li Guo

In recent years, extensive attentions have been paid to integrating transition-metal molecular catalysts into polymer scaffolds, aiming to simulate the outer coordination sphere of [FeFe]-hydrogenase active sites and to enhance the efficiency and stability of hydrogenase-inspired molecular catalysts for hydrogen evolution reaction (HER). In this study, two new pyrene-containing diiron molecular compounds [Fe₂{(μ-CH₂)₂CHC[O]R}(CO)₅{Ph₂PNH(pyrene)}] (R = N-oxylphthalimide (1) or CONH(CH₂)₃NMe₂ (2)) as polymer-free [FeFe]-hydrogenase mimics and their polyethyleneimine (PEI)-covalently-attached metallopolymers denoted as 1a-c (wherein, the molecular weights (Mw) of the used PEI are 1800, 10,000, and 18,000 g mol^-1) as PEI-bound [FeFe]-hydrogenase mimics were prepared as bioinspired homogeneous HER electrocatalysts. Furthermore, the simple immobilization of 1a-c and 2 onto pristine multi-walled carbon nanotubes (MWCNTs) through π–π stacking interactions resulted in the formation of their CNT-supported hybrids labeled as 1a-c/MWCNT and 2/MWCNT as bioinspired heterogeneous HER electrocatalysts. More importantly, the homo- and heterogeneous electrochemistry of PEI-bound mimics 1a-c and polymer-free mimic 2 is studied and compared using various electrochemical techniques, showing that 1a-c has more efficient electrocatalytic HER performance relative to 2 in whether MeCN solution with trifluoroacetic acid (TFA, 0–10 mA) or 0.1 M phosphate buffer solution (PBS, pH of 7). Additionally, the low heterogeneous stability of representative CNT-supported hybrid 1b/MWCNT in neutral buffer solution is attributed to the electrochemical degradation of diiron-based metallopolymer 1b supported on MWCNTs as indicated by post-electrolysis analysis.

近年来，将过渡金属分子催化剂集成到聚合物支架中，以模拟[FeFe]-氢化酶活性位点的外配位球，提高氢化酶激发的析氢反应（HER）分子催化剂的效率和稳定性受到广泛关注。在这项研究中，制备了两种新的含芘的双铁分子化合物[Fe2{(μ-CH2)2CHC[O]R}(CO)5{Ph₂PNH（芘）}](R = n -氧基酞酰亚胺（1)或CONH（CH₂）₃NMe₂(2)）作为无聚合物的[FeFe]氢化酶模拟物，并将它们的聚亚胺(PEI)-共价键连接的金属聚合物表示为1a-c（其中，所使用PEI的分子量（Mw）分别为1800、10000和18000 g mol-1）作为PEI结合的[FeFe]氢化酶模拟物作为仿生均相HER电催化剂。此外，通过π -π堆叠相互作用将1a-c和2简单地固定在原始的多壁碳纳米管（MWCNTs）上，形成了它们的碳纳米管负载的杂化物，标记为1a-c/MWCNT和2/MWCNT，作为仿生异相HER电催化剂。更重要的是，研究了pei结合的模拟物1a-c和无聚合物模拟物2的同质和非均相电化学，并使用各种电化学技术进行了比较，结果表明，无论是在三氟乙酸（TFA, 0-10 mA）或0.1 M磷酸盐缓冲溶液（PBS， pH为7）的MeCN溶液中，1a-c都比2具有更有效的电催化HER性能。此外，电解后分析表明，具有代表性的碳纳米管负载的杂化1b/MWCNT在中性缓冲溶液中的非均相稳定性较低，归因于MWCNTs负载的二铁基金属聚合物1b的电化学降解。

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引用次数: 0

MOF-74-inspired metal-organic complex as an efficient peroxidase-mimicking electrocatalyst for ultrasensitive hydrogen peroxide sensing mof -74激发的金属有机配合物作为超灵敏过氧化氢传感的高效过氧化物酶模拟电催化剂

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-15 DOI: 10.1016/j.electacta.2025.148014

Linghui Tang, Yue Wang

Hydrogen peroxide (H₂O₂) is a widely used oxidizing agent in industrial processes, and a 3 wt% aqueous solution is commonly employed as a disinfectant. In this study, a metal–organic complex (DHTPN) was synthesized via a one-step coordination reaction between 2,5-dihydroxyterephthalic acid (DHTP) and NiCl₂. The resulting complex exhibits a fine-tuned lattice structure resembling MOF-74(Ni) and was comprehensively characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). When immobilized onto a glassy carbon electrode, the DHTPN-modified electrode functioned as an efficient electrochemical sensor for H₂O₂ detection. Under optimized conditions, the sensor exhibited a broad linear detection range from 10 μM to 13.32 mM and an ultralow detection limit of 3.3 μM. In addition, the device demonstrated excellent selectivity, reproducibility, and operational stability, along with a rapid response time of 3.5 s. Furthermore, the sensor was successfully applied to the quantitative analysis of commercial 3 wt% H₂O₂ disinfectant without any sample pretreatment, yielding accurate and reliable results. This work highlights the potential of metal–organic complexes as advanced electrode materials in electroanalytical chemistry and provides a promising platform for rapid, sensitive, and efficient H₂O₂ detection.

过氧化氢（H₂O₂）是工业过程中广泛使用的氧化剂，通常采用3wt %的水溶液作为消毒剂。本研究以2,5-二羟基对苯二甲酸（DHTP）和NiCl₂为原料，通过一步配位反应合成了金属有机配合物（DHTPN）。通过扫描电镜（SEM）、透射电镜（TEM）、傅里叶变换红外光谱（FTIR）和x射线光电子能谱（XPS）对该配合物进行了全面表征。当固定在玻碳电极上时，dhtpn修饰电极作为一种高效的电化学传感器检测H₂O₂。在优化条件下，传感器的线性检测范围为10 μM ~ 13.32 mM，超低检测限为3.3 μM。此外，该装置表现出优异的选择性，重复性和操作稳定性，以及3.5 s的快速响应时间。此外，该传感器成功地应用于商业3wt % H₂O₂消毒剂的定量分析，无需任何样品预处理，产生准确可靠的结果。这项工作突出了金属有机配合物作为电分析化学中先进电极材料的潜力，并为快速、灵敏、高效的h2o₂检测提供了一个有前途的平台。

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引用次数: 0

Enhanced photocathodic protection performance of calcinated WO3/BiVO4/Ti3C2 quantum dots heterojunction coating and its multifunctional applications 焙烧WO3/BiVO4/Ti3C2量子点异质结涂层的光电阴极保护性能及其多功能应用

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-15 DOI: 10.1016/j.electacta.2025.148012

Chenxiao Zhang , Yunhui Liu , Ting Zhang , Jishuang Wang , Xiaotong Yang , Xiaoyang Wang , Dongmei Zeng , Minmin Zou , You Zhang

The easily recombination of electron-hole pairs and the non-covalent bonds existing in traditional heterojunctions have affected the improvement of photocathodic protection (PCP) performance of BiVO₄ photoanodes. In this study, a compact interfacial contact between WO₃ and BiVO₄ was obtained through introducing the calcination process to construct a ternary heterojunction of WO₃/BiVO₄/Ti₃C₂ quantum dots (QDs) and the photoanode protective coating. Effects of the calcination process and the heterojunction on the PCP performance and its multi-functional applications of BiVO₄-based photocathodes were investigated. Results indicate the calcined WO₃/BiVO₄ heterojunction shows significantly improved PCP performance compared to the uncalcined heterojunction, with the photocurrent density rising from 42 μA/cm² to 84 μA/cm² and open circuit potential (OCP) dropping to −0.67 V vs Ag/AgCl, which can be ascribed to the enhanced contact and electron transfer between BiVO₄ and WO₃. Further, due to the high conductivity of Ti₃C₂ QDs and the electron storage capability of WO₃, the ternary heterojunction of calcined WO₃/BiVO₄/Ti₃C₂ QDs has obtained the best PCP performance and the dark-state protection ability, with the OCP value of −0.85 V vs Ag/AgCl under light and −0.4 V vs Ag/AgCl in the dark. Also, compared to pure BiVO₄, the calcined WO₃/BiVO₄/Ti₃C₂ QDs coating has achieved about twice higher of the deicing efficiency due to the photothermal performance of Ti₃C₂ QDs, indicating the promise of its application in cold environments. This study offers an effective strategy to achieve the BiVO₄-based PCP photoanode with improved performance and multi-functional applications through constructing calcined WO₃/BiVO₄/Ti₃C₂ QDs heterojunction.

传统异质结中存在的电子空穴对易重组和非共价键影响了BiVO4光阳极光电阴极保护性能的提高。本研究通过引入煅烧工艺，构建WO3/BiVO4/Ti3C2量子点（QDs）与光阳极保护涂层的三元异质结，获得了WO3与BiVO4之间紧密的界面接触。研究了煅烧工艺和异质结对bivo4基光电阴极PCP性能及其多功能应用的影响。结果表明，与未煅烧的异质结相比，焙烧后的WO3/BiVO4异质结的PCP性能显著提高，光电流密度从42 μA/cm²提高到84 μA/cm²，开路电位（OCP）降至−0.67 V vs Ag/AgCl，这是由于BiVO4与WO3之间的接触和电子转移增强所致。此外，由于Ti3C2量子点的高导电性和WO3的电子存储能力，煅烧的WO3/BiVO4/Ti3C2量子点的三元异质结获得了最佳的PCP性能和暗态保护能力，光下OCP值为−0.85 V vs Ag/AgCl，暗下OCP值为−0.4 V vs Ag/AgCl。此外，由于Ti3C2量子点的光热性能，与纯BiVO4相比，煅烧WO3/BiVO4/Ti3C2量子点涂层的除冰效率提高了约两倍，表明其在寒冷环境中的应用前景广阔。本研究通过构建焙烧WO3/BiVO4/Ti3C2量子点异质结，提供了一种提高性能和多功能应用的BiVO4基PCP光阳极的有效策略。

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引用次数: 0

Single-atom cobalt modified amorphous WO3·xH2O for enhanced electrochromic performance 单原子钴修饰的无定形WO3·xH2O增强电致变色性能

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-14 DOI: 10.1016/j.electacta.2025.148013

Haifeng Nan , Hu Xu , Runpan Nie , Yue Li , Gan-Ji Zhong , Jun Lei , Zhong-Ming Li

Amorphous tungsten trioxide electrochromic materials exhibit faster ion transport kinetics than crystalline structures. This makes them a highly promising material for smart windows, electrochromic batteries, and other cutting-edge fields. Nevertheless, the complex preparation process (high temperature and pressure), low spectral modulation ability, and poor durability severely limit their practical applications. Herein, based on the guidance of DFT calculations, amorphous Co-WO₃·xH₂O film was prepared by electrodeposition at room temperature and normal pressure. This synthesis employed a co-modification strategy involving single-atom Co doping and structural water, achieved by adjusting the components of precursor solution. Theoretical calculations and experimental results indicate that Co doping significantly improved the electronic conductivity of WO₃ and consequently elevated its electrochemical performance. The Co-WO₃·xH₂O film exhibited rapid response (1.3 s of bleaching time at 633 nm), durable cycling stability (merely 0.3 % capacity loss after 1000 cycles), and outstanding thermal management performance (9.1 °C lower than Low-e glass). Furthermore, Energyplus simulation indicates that our device has outstanding energy-saving capabilities in China and in most climate zones around the world. This simple strategy does not require complex high-temperature and high-pressure conditions, nor does it require a sealed environment. The excellent dual-band electrochromic smart window has great potential in reducing energy consumption in the interiors of buildings.

非晶三氧化钨电致变色材料表现出比晶体结构更快的离子传输动力学。这使它们成为智能窗户、电致变色电池和其他前沿领域非常有前途的材料。但其制备工艺复杂（高温高压）、光谱调制能力低、耐用性差，严重限制了其实际应用。本文在DFT计算的指导下，采用常温常压电沉积法制备了Co-WO3·xH2O非晶膜。该合成采用单原子Co掺杂和结构水共改性策略，通过调整前驱体溶液的组分来实现。理论计算和实验结果表明，Co掺杂能显著提高WO3的电导率，从而提高其电化学性能。Co-WO3·xH2O薄膜具有快速响应（633 nm下漂白时间为1.3 s）、持久的循环稳定性（1000次循环后容量损失仅为0.3%）和出色的热管理性能（比Low-e玻璃低9.1°C）。此外，Energyplus模拟表明，我们的设备在中国和世界上大多数气候带都具有出色的节能能力。这种简单的策略不需要复杂的高温高压条件，也不需要密封环境。出色的双波段电致变色智能窗在降低建筑内部能耗方面具有巨大的潜力。

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引用次数: 0

Enhanced ionic conductivity in PEO-based solid electrolytes via 3D hollow nanotube fillers for all-solid-state lithium batteries 全固态锂电池用三维空心纳米管填料增强peo基固体电解质的离子电导率

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-13 DOI: 10.1016/j.electacta.2025.148011

Jiahao Li , Yuhua Zhen , Gaohui Ren , Wenjie Yang , Yuanyue Qie , Xinyu Cai , Zheng Yan , Wei Xing , Hongxia Geng

Solid-state lithium metal batteries (SSLMBs) employing polymer electrolytes are considered highly promising for their superior safety and elevated energy density. However, their development is impeded by the inherently low ionic conductivity of polymer electrolytes and the poor interfacial stability at the lithium metal anode. To overcome these challenges, Li-doped three-dimensional ZnO (LZN) ceramic hollow tube networks were incorporated into a poly(ethylene oxide) (PEO)-based solid polymer electrolyte (SPE). The abundant oxygen vacancies and strong interactions with LiTFSI facilitate lithium salt dissociation, thereby generating a higher concentration of free Li⁺ ions and enhancing Li⁺ transport. Consequently, the optimized PL-20LZN composite polymer electrolyte membrane exhibits a high Li⁺ conductivity of 8.12 × 10^–4 S·cm^-1 at 60 °C. The solid-state LiFePO₄/Li cell maintains stable cycling performance over 400 cycles, with an average Coulombic efficiency of 99.8 %. Moreover, relative to the pure PEO electrolyte, the full cell employing a high-voltage LiNi_0.6Co_0.6Mn_0.6O₂ (NCM622) cathode exhibits notably enhanced cycling stability, suggesting that LZN hollow nanotubes play a key role in enhancing both interfacial and high-voltage stability.

采用聚合物电解质的固态锂金属电池（sslmb）因其优越的安全性和更高的能量密度而被认为是非常有前途的。然而，它们的发展受到聚合物电解质固有的低离子电导率和锂金属阳极界面稳定性差的阻碍。为了克服这些挑战，将li掺杂的三维ZnO （LZN）陶瓷空心管网络掺入聚环氧乙烷（PEO）基固体聚合物电解质（SPE）中。丰富的氧空位和与LiTFSI的强相互作用有利于锂盐解离，从而产生更高浓度的自由Li +离子，增强Li +的转运能力。因此，优化后的PL-20LZN复合聚合物电解质膜在60℃时具有8.12 × 10-4 S·cm-1的高电导率。固态LiFePO4/Li电池在400次循环中保持稳定的循环性能，平均库仑效率为99.8%。此外，与纯PEO电解质相比，采用高压LiNi0.6Co0.6Mn0.6O2 （NCM622）阴极的全电池具有明显增强的循环稳定性，这表明LZN空心纳米管在增强界面稳定性和高压稳定性方面发挥了关键作用。

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引用次数: 0