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Electrocatalysts work better in lean-electrolyte lithium‒sulfur batteries 电催化剂在贫电解质锂硫电池中效果更佳
IF 11.9 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-07-13 DOI: 10.1039/d4ta01997k
Jia-Jia Zhao, Zi-Xian Chen, Qian Cheng, Meng Zhao, Xinzhi Ma, Xue-Qiang Zhang, Jia-Qi Huang, Bo-Quan Li
Reducing electrolyte usage constitutes the prerequisite to construct high-energy-density lithium‒sulfur (Li‒S) batteries. However, the cathode kinetics is severely blocked under lean-electrolyte conditions. Electrocatalysts have been widely employed to boost the cathode kinetics, yet their effectiveness under lean-electrolyte conditions remains unclear. Herein, the cathode kinetics promotion effectiveness of electrocatalysts is systematically evaluated in lean-electrolyte Li‒S batteries. The kinetics promotion effects on both liquid‒liquid and liquid‒solid conversions are more prominent at higher sulfur concentrations using the titanium nitride (TiN) electrocatalyst. Similarly, discharge capacity increment and cell polarization decrease afforded by the TiN electrocatalyst are more significant in lean-electrolyte Li‒S batteries than the flooded-electrolyte ones. Polarization decoupling analysis further identifies activation polarization as the main challenge under lean-electrolyte conditions, which can be effectively overcome by the TiN electrocatalyst. Moreover, the energy density of 2 Ah Li–S pouch cells increases by 19% using TiN electrocatalyst. This work elucidates electrocatalysts are more effective in lean-electrolyte Li–S batteries and highlights advanced electrocatalyst design for high-energy-density Li–S batteries.
减少电解质用量是制造高能量密度锂硫(Li-S)电池的先决条件。然而,在贫电解质条件下,阴极动力学会受到严重阻碍。电催化剂已被广泛用于提高阴极动力学,但其在贫电解质条件下的有效性仍不明确。本文系统评估了电催化剂在贫电解质锂-S 电池中的阴极动力学促进效果。使用氮化钛(TiN)电催化剂时,硫浓度越高,液-液和液-固转换的动力学促进效果越明显。同样,在贫电解质锂-S 电池中,氮化钛电催化剂带来的放电容量增加和电池极化降低比淹没电解质电池更为显著。极化解耦分析进一步确定活化极化是贫电解质条件下的主要挑战,而 TiN 电催化剂可有效克服这一挑战。此外,使用 TiN 电催化剂后,2 Ah 锂-S 袋式电池的能量密度提高了 19%。这项工作阐明了电催化剂在贫电解质锂-S 电池中更有效的作用,并强调了针对高能量密度锂-S 电池的先进电催化剂设计。
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引用次数: 0
F-coordinated Single-atom Ru Species: Efficient and Durable Catalysts for Photo-Thermal Synergistic Catalytic CO2 Hydrogenation to Methane F 配位单原子 Ru 物种:光热协同催化 CO2 加氢制甲烷的高效持久催化剂
IF 11.9 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-07-13 DOI: 10.1039/d4ta02984d
Yunxiang Tang, Hao Wang, Chan Guo, Lige Wang, Tingting Zhao, Zhengyi Yang, Shikang Xiao, Jiurong Liu, Yanyan Jiang, Yufei Zhao, Xiaodong Wen, Fenglong Wang
Elucidating the correlation between coordination structures and catalytic performances of single-atom active site is imperative for the precise design of highly efficient catalysts; however, the feasible regulation of coordination environment in single-atom catalysts presents a formidable challenge. Herein, we fabricate single-atom Ru-based catalysts with Ru-F4 and Ru-O4 configurations (named as Ru-F4 SAs/PA and Ru-O4 SAs/PA, respectively), showcasing fine-tuning of the coordination structure of Ru sites can significantly enhance performances for CO2 hydrogenation to methane under mild conditions in a photo-thermal synergistic catalytic process. Comparative studies reveal that Ru-F4 SAs/PA outperformed Ru-O4 SAs/PA counterparts, giving a superior CO2 methanation performances with CH4 production rate of 47.4 mmol gcat−1 h−1 and CH4 selectivity of 93.8% at 200 ℃ in the presence of light irradiation (200-1100 nm, 1.9 W cm−2) under atmospheric pressure. Theoretical investigations unravel that the transition from Ru-O4 to Ru-F4 coordination environments optimizes the electronic states, thereby enhancing the adsorption of reactants and intermediates. Moreover, the optimized electronic structure promotes the production and transformation of key intermediate species, lowers the energy barrier for CO2 conversion, and thus elevates the catalytic activity. This comprehensive study not only clarifies the relationship between the coordination structures of active sites and catalytic performance at atomic-level but also offers a novel paradigm for the design of efficient CO2 conversion catalysts.
阐明单原子活性位点配位结构与催化性能之间的相关性是精确设计高效催化剂的当务之急;然而,如何对单原子催化剂的配位环境进行可行的调控是一项艰巨的挑战。在此,我们制备了具有 Ru-F4 和 Ru-O4 构型的单原子 Ru 基催化剂(分别命名为 Ru-F4 SAs/PA 和 Ru-O4 SAs/PA),展示了微调 Ru 位点的配位结构可显著提高光热协同催化过程中温和条件下 CO2 加氢制甲烷的性能。对比研究发现,Ru-F4 SAs/PA 的性能优于 Ru-O4 SAs/PA,在常压下,光照射(200-1100 纳米,1.9 瓦 cm-2)条件下,Ru-F4 SAs/PA 在 200 ℃ 下的 CO2 甲烷化性能更优越,CH4 产率为 47.4 mmol gcat-1 h-1,CH4 选择性为 93.8%。理论研究发现,从 Ru-O4 配位环境过渡到 Ru-F4 配位环境优化了电子状态,从而增强了对反应物和中间产物的吸附。此外,优化的电子结构促进了关键中间产物的生成和转化,降低了二氧化碳转化的能量障碍,从而提高了催化活性。这项全面的研究不仅从原子层面阐明了活性位点配位结构与催化性能之间的关系,还为设计高效的二氧化碳转化催化剂提供了一种新的范式。
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引用次数: 0
Ferrocene-modified polymer-SWCNT composite films for high-performance flexible thermoelectric generators 用于高性能柔性热电发电机的二茂铁改性聚合物-SWCNT 复合薄膜
IF 11.9 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-07-13 DOI: 10.1039/d4ta02037e
Zelin Sun, Zhifeng Ma, Xuan Zhou, Yanzhao Wang, Jie Zhang, Wai-Yeung Raymond Wong
In this study, we explore a new design strategy for enhancing the thermoelectric performance of composites between poly(Fc-CPT)-based metallopolymers (Fc-P1, Fc-P2, and Fc-P3) and single-walled carbon nanotubes (SWCNTs) by modifying CPT-based polymer backbones with pendant redox ferrocene groups and thiophene functional groups. After optimizing the conditions, all three one-dimensional (1D) conjugated metallopolymers exhibit excellent thermoelectric performance by interacting well with SWCNT. The study provides insights into polymer-SWCNT composites through morphological analysis and theoretical calculations. The flexible OTEG incorporating Fc-P3-SWCNT composites achieves an impressive output power of 1.18 μW at T is 72 K, underscoring the potential of these materials in advancing organic thermoelectric technologies. These findings are expected to stimulate further interest and research in high-performance OTE materials.
在本研究中,我们探索了一种新的设计策略,即通过用二茂铁基团和噻吩官能团修饰基于 CPT 的聚合物骨架,从而提高基于聚(Fc-CPT)的金属聚合物(Fc-P1、Fc-P2 和 Fc-P3)与单壁碳纳米管(SWCNT)之间的复合材料的热电性能。在优化条件后,这三种一维(1D)共轭金属聚合物都能与 SWCNT 很好地相互作用,从而表现出优异的热电性能。该研究通过形态分析和理论计算深入了解了聚合物-SWCNT 复合材料。采用 Fc-P3-SWCNT 复合材料的柔性 OTEG 在 T 72 K 时实现了 1.18 μW 的惊人输出功率,凸显了这些材料在推动有机热电技术发展方面的潜力。这些发现有望进一步激发人们对高性能有机热电材料的兴趣和研究。
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引用次数: 0
Template-Directed In-situ Grown Bimetallic Nanoarchitectures with Hydroxide Active Sites Enriched Multi-Charge Transfer Routes for Energy Storage 具有氢氧化物活性位点的模板导向原位生长双金属纳米结构丰富了用于储能的多电荷转移途径
IF 11.9 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-07-13 DOI: 10.1039/d4ta03412k
Dennyson Savariraj Antonysamy, Thondaiman Pugalenthiyar, Periyasamy Sivakumar, Manikandan Ramu, John D Rodney, Byung Chul Kim, Hyun Jung
Cobalt metal-organic frameworks were used as templates to obtain densely stacked two-dimensional ultrathin nanosheets of nickel/cobalt metal-organic frameworks on carbon cloth via in situ deposition at room temperature. The freestanding electrodes made of ultra-thin nanosheets and quasi-one-dimensional pores exhibited a unique electronic structure with Ni(OH)2 anchoring to the surface. With the distinctive structural superiority, multiple charge transfer routes, and Ni(OH)2 entities as active sites, the electrode showcased a towering areal capacity (Ca) of 2041 mC cm-2 (2 mA cm-2), a specific capacity of (Cs) 671 C g-1 and a volumetric capacitance (Cvc) of 1033 F cm-3 (2 A g-1) and a prolonged cycling life of 5000 cycles with an appreciable capacity retention of 91.5% in 6 M KOH. The asymmetric supercapacitor device assembled (CC/CoNi-MOF@Ni(OH)2//CC/O,N,S@AC) delivered a thumping specific capacity (Cs) of 284 C g-1, a specific capacitance (Csp) of 189 F g-1, a volumetric capacitance (Cvc) of 128 F cm-3, a maximum specific energy (Es) of 75.0 W h kg-1, an excellent specific power (Ps) of 17.13 kW kg-1, and withstood 10,000 charge/discharge cycles with a decline of 11.3% in the initial capacity. The proposed method with DFT analysis underpins a strategy to custom-design economically viable freestanding electrodes with a large surface area per volume/mass, synergy effect at the interface, and multiple charge transfer pathways for potential application in energy storage. KEYWORDS: Organic frameworks, multiple charge transfer, freestanding electrode, large surface area, synergy effect.
以钴金属有机框架为模板,通过室温下的原位沉积,在碳布上获得了密集堆叠的二维超薄镍/钴金属有机框架纳米片。由超薄纳米片和准一维孔隙构成的独立电极呈现出独特的电子结构,Ni(OH)2锚定在电极表面。凭借独特的结构优势、多种电荷转移途径和作为活性位点的 Ni(OH)2 实体,该电极显示出 2041 mC cm-2 (2 mA cm-2)的高面积容量(Ca)、671 C g-1 的比容量(Cs)和 1033 F cm-3 (2 A g-1)的体积电容(Cvc),以及在 6 M KOH 中 5000 次的循环寿命和 91.5% 的显著容量保持率。组装的不对称超级电容器装置(CC/CoNi-MOF@Ni(OH)2//CC/O,N,S@AC)的比容量(Cs)为 284 C g-1,比电容(Csp)为 189 F g-1,体积电容(Cvc)为 128 F cm-3,最大比能量(Es)为 75.0 W h kg-1,出色的比功率 (Ps) 为 17.13 kW kg-1,可承受 10,000 次充放电循环,初始容量下降了 11.3%。所提出的 DFT 分析方法为定制设计经济可行的独立电极提供了基础,这种电极具有单位体积/质量的大表面积、界面协同效应和多种电荷转移途径,有望应用于储能领域。关键词: 有机框架、多重电荷转移、独立电极、大表面积、协同效应。
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引用次数: 0
A functional silicon composite polymer electrolyte with hydrofluoric acid scavenging for quasi-solid-state lithium metal batteries 用于准固态锂金属电池的具有氢氟酸清除功能的硅复合聚合物电解质
IF 11.9 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-07-12 DOI: 10.1039/d4ta01849d
Li Zhao, Li Yang, Yu Cheng, Hong Zhang, Lulu Du, Wei Peng, Ahmed Eissa Abdelmaoula, Lin Xu
Lithium metal is considered as one of the most promising anode material candidates for high-energy-density batteries. However, the solid electrolyte interface (SEI) of the lithium metal surface is susceptible to corrosion by hydrofluoric acid (HF) and H2O, which hinders the practical application of lithium metal. In this work, a functional composite polymer electrolyte (FCPE) containing Si nanoparticles can scavenge HF and H2O to protect the SEI from corrosion. The Si nanoparticles in the FCPE react with HF to form SiF4, which reacts with H2O to produce LiF and LixSiOy without generating other harmful by-products. The LiF and LixSiOy are ionic conductors, which are deposited on the surface of lithium metal constructing an SEI layer with high ionic conductivity. The high ionic conductivity of the SEI can contribute to the induction of uniform Li-ion plating/stripping behavior, thereby preventing the growth of lithium dendrites. As a result, a Li‖Li symmetric cell with the FCPE under extreme conditions with a water content of 8078 ppm (VH2O:Vbase electrolyte = 1.0%) can cycle stably for 800 h. These results highlight that the FCPE can remove water impurities to maintain the excellent performance of lithium metal batteries and provide a direction for the development of polymer electrolytes.
金属锂被认为是高能量密度电池最有前途的负极材料之一。然而,金属锂表面的固体电解质界面(SEI)易受氢氟酸(HF)和水的腐蚀,这阻碍了金属锂的实际应用。在这项研究中,含有硅纳米颗粒的功能复合聚合物电解质(FCPE)可以清除 HF 和 H2O,保护 SEI 不受腐蚀。FCPE 中的纳米硅粒子与 HF 反应生成 SiF4,SiF4 与 H2O 反应生成 LiF 和 LixSiOy,而不会产生其他有害的副产品。LiF 和 LixSiOy 是离子导体,它们沉积在锂金属表面,形成具有高离子导电性的 SEI 层。SEI 的高离子导电性有助于诱导锂离子均匀的电镀/剥离行为,从而防止锂枝晶的生长。因此,在水含量为 8078 ppm(VH2O:Vbase 电解质 = 1.0%)的极端条件下,使用 FCPE 的 "锂 "对称电池可以稳定循环 800 小时。
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引用次数: 0
Physically entangled multifunctional eutectogels for flexible sensors with mechanically robust 物理纠缠多功能共晶凝胶用于具有机械稳健性的柔性传感器
IF 11.9 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-07-12 DOI: 10.1039/d4ta02751e
Qianwen Lu, Hengfeng Li, Zhijian Tan
Ionically conducting eutectogels have gained popularity as temperature-tolerant and cost-effective substitutes for hydrogels and ionogels in flexible electronic devices. In this study, mechanically robust eutectogels with antibacterial properties were fabricated using a facile one-step process that relied solely on the physical entanglement of polymer chains. At low initiator concentrations, the vinyl monomers underwent radical polymerization in deep eutectic solvents (DESs), forming physically entangled and transparent eutectogels. The eutectogels exhibited excellent mechanical properties (tensile strength, elongation at break, and fracture energy of 8.04 MPa, 620.5%, and 28.69 ± 2.23 MJ m−3, respectively), a strong adhesion force, excellent ionic conductivity (0.43 ± 0.07 S m−1), and remarkable resistance to freezing and drying (−20 to 80 °C). Moreover, the eutectogels possessed superior self-healing abilities at room temperature without the need for external stimuli. As sensors, the fabricated eutectogels exhibited high sensitivity, thereby enabling the precise, real-time, and stable monitoring of human activities. The eutectogels have promising applications in wearable technology, healthcare devices, and human–computer interfaces.
离子导电共晶凝胶作为柔性电子设备中水凝胶和离子凝胶的耐温性和高性价比替代品,已越来越受欢迎。本研究采用简便的一步法工艺,完全依靠聚合物链的物理缠结,制造出了具有抗菌特性的机械坚固共晶凝胶。在低引发剂浓度下,乙烯基单体在深共晶溶剂(DES)中发生自由基聚合,形成物理缠结的透明共晶凝胶。这种共晶凝胶具有优异的机械性能(拉伸强度、断裂伸长率和断裂能分别为 8.04 MPa、620.5% 和 28.69 ± 2.23 MJ m-3)、强大的粘附力、出色的离子导电性(0.43 ± 0.07 S m-1)以及显著的耐冷冻和耐干燥性(-20 至 80 °C)。此外,共晶凝胶还具有卓越的室温自愈合能力,无需外部刺激。作为传感器,所制备的共晶凝胶具有高灵敏度,从而能够对人类活动进行精确、实时和稳定的监测。这种共晶凝胶有望应用于可穿戴技术、医疗保健设备和人机界面。
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引用次数: 0
Efficient and Stable Inorganic Perovskite Solar Cells Enabled by Lead Silicate Glass Layer 利用硅酸铅玻璃层实现高效、稳定的无机过氧化物太阳能电池
IF 11.9 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-07-12 DOI: 10.1039/d4ta04018j
Wanpeng Yang, Haixuan Yu, Zhiguo Zhang, Haodan Shi, Yong Hu, Junyi Huang, Zhirong Liu, Yan Shen, Mingkui Wang
Inorganic cesium lead triiodide perovskite (CsPbI3) exhibits remarkable potential in photovoltaic application due to its exemplary thermal stability. However, CsPbI3 is extremely sensitive to moisture which hinders its practical application in stable and high-efficiency photovoltaic devices. Here we show an effective method to enhance water resistance of CsPbI3 via an ultrathin hydrophobic lead silicate (PbSiO3) glass layer. The resulted CsPbI3 inorganic perovskite solar cells achieved a remarkably efficiency of 20.59% under standard test condition. More importantly, the unencapsulated devices possess outstanding moisture resilience which maintain about 92% of their initial efficiency even after being stored under 25±5% relative humidity (RH) for 600 hours.
无机三碘化铯铅过氧化物(CsPbI3)因其出色的热稳定性而在光伏应用中展现出非凡的潜力。然而,CsPbI3 对湿气极为敏感,这阻碍了它在稳定和高效光伏设备中的实际应用。在这里,我们展示了一种通过超薄疏水性硅酸铅(PbSiO3)玻璃层增强 CsPbI3 防水性的有效方法。所制备的 CsPbI3 无机包晶太阳能电池在标准测试条件下的效率达到了 20.59%。更重要的是,未封装器件具有出色的防潮性能,即使在 25±5% 的相对湿度(RH)条件下存放 600 小时,仍能保持约 92% 的初始效率。
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引用次数: 0
Impact of intermolecular packing on separation of chlorinated cyclic hydrocarbons by flexible hydrogen-bonded organic frameworks 分子间填料对柔性氢键有机框架分离氯化环烃的影响
IF 11.9 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-07-12 DOI: 10.1039/d4ta03910f
Peng Chong Xue, Siwen Hu, He Zhao, Meng Liang, Rui Wang, Jingjun Hao
The nonplanar phenothiazine derivative (PTTCN) was synthesized to construct adsorption hydrogen-bonded organic frameworks for separation of chlorinated cyclic hydrocarbons, chlorobenzene (ClBz) and chlorocyclohexane (ClCy). PTTCN can form two distinct organic frameworks in ClBz and ClCy through intermolecular hydrogen bonding. These frameworks exhibit different fluorescence colors, which can be attributed to variations in molecular conformations and packing patterns. Upon heating, both frameworks are capable of releasing the guests; however, their separation performances towards the ClBz/ClCy mixture differ significantly. Specifically, X-HOF-6a derived from ClBz selectively reabsorbs ClBz from the equimolar mixture accompanying with a gate-opening process and asmall change in intermolecular arrangement, resulting in a purity of 99.4%. Moreover, X-HOF-6a demonstrates excellent reusability. On the other hand, the intermolecular stacking type in X-HOF-7a derived from ClCy is very different from those in X-HOF-a and X-HOF-7, and then X-HOF-7a exhibits non-selective adsorption by capturing both ClCy and ClBz molecules simultaneously. The investigations suggest that selectivity is determined by the extent of alteration in intermolecular stacking upon guest adsorption, with higher selectivity observed for smaller changes.
合成了非平面吩噻嗪衍生物(PTTCN),用于构建吸附氢键有机框架,以分离氯化环烃、氯苯(ClBz)和氯环己烷(ClCy)。PTTCN 可通过分子间氢键在 ClBz 和 ClCy 中形成两种不同的有机框架。这些框架呈现出不同的荧光颜色,这可归因于分子构象和堆积模式的变化。加热时,这两种框架都能释放客体;然而,它们对 ClBz/ClCy 混合物的分离性能却大相径庭。具体来说,由 ClBz 衍生的 X-HOF-6a 可选择性地从等摩尔混合物中重新吸收 ClBz,同时伴随着门打开过程和分子间排列的微小变化,从而使纯度达到 99.4%。此外,X-HOF-6a 还具有极佳的重复使用性。另一方面,由 ClCy 衍生的 X-HOF-7a 中的分子间堆叠类型与 X-HOF-a 和 X-HOF-7 中的分子间堆叠类型截然不同,因此 X-HOF-7a 同时捕获 ClCy 和 ClBz 分子,表现出非选择性吸附。研究表明,选择性取决于客体吸附时分子间堆积的变化程度,变化越小,选择性越高。
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引用次数: 0
Conjugated microporous polytriphenylamine as high-performance anion-capture electrode for hybrid capacitive deionization with ultrahigh areal adsorption capacity 共轭微孔聚三苯胺作为高性能阴离子捕获电极,用于具有超高吸附容量的混合电容式去离子法
IF 11.9 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-07-12 DOI: 10.1039/d4ta04010d
Weiqing Kong, Xiaoyuan Lu, Xu Ge, Qingao Zhang, Xiaoyu Jin, Meng Zhang, Yuan-Yuan Feng
Conducting polymers with good electron conductivity and rich redox functional groups have attracted enormous attention as anode material for capacitive deionization (CDI) towards the relief of global freshwater scarcity. However, because of their intrinsically poor porosity and severe particle aggregation natures, previously used conducting polymers for CDI desalination have suffered from the disadvantage of rather low specific surface areas (<50 m2g−1), sluggish ion diffusion kinetics, limited desalination capacities, and low mass loadings (~1 mg cm−2) on electrodes. Herein, we synthesized an amino group-rich conjugated microporous polytriphenylamine (m-PTPA) and demonstrated for the first time its great potential as a high-performance anion-capture electrode material in CDI applications. m-PTPA possesses reversible redox property, predominant <2 nm microporous characteristics, and ultrahigh specific surface area (506 m2g−1), which ensured the fast ion transport within interconnected porous network, and maximized the exposure of electrochemical active sites to saline solution. Owing these novel features, the m-PTPA-based CDI device, with m-PTPA as anode at a high mass loading of 8.7 mg cm−2and activated carbon as cathode, exhibited high gravimetric/areal/volumetric-normalized salt adsorption capacities (47.21 mg g−1, 0.41 mg cm−2, 10.92 mg cm−3), fast adsorption rate (2.83 mg g−1min−1), low energy consumption, and excellent cycling stability. Besides, we also evaluated the competitive adsorption of some common anions existing in water, and probed the mechanism for Cladsorption on m-PTPA. We believe that this work paves a new way for the usage of conjugated microporous polymers as a new kind of CDI electrode materials.
导电聚合物具有良好的电子传导性和丰富的氧化还原官能团,作为电容式去离子(CDI)的阳极材料,在缓解全球淡水短缺问题方面引起了广泛关注。然而,由于其固有的孔隙率低和严重的颗粒聚集特性,以往用于 CDI 海水淡化的导电聚合物存在着比表面积低(50 m2g-1)、离子扩散动力学缓慢、海水淡化能力有限以及电极质量负荷低(约 1 mg cm-2)等缺点。m-PTPA 具有可逆氧化还原特性、2 nm 微孔特征和超高比表面积(506 m2g-1),可确保离子在相互连接的多孔网络中快速传输,并使电化学活性位点最大限度地暴露于盐溶液中。由于这些新特性,以 m-PTPA 为阳极(质量负荷高达 8.7 mg cm-2)、活性炭为阴极的 m-PTPA CDI 器件表现出较高的重度/实际/体积归一化盐吸附容量(47.21 mg g-1、0.41 mg cm-2、10.92 mg cm-3)、较快的吸附速率(2.83 mg g-1min-1)、较低的能耗和出色的循环稳定性。此外,我们还评估了 m-PTPA 对水中一些常见阴离子的竞争性吸附,并探究了 m-PTPA 吸附 Cl 的机理。我们相信,这项研究为共轭微孔聚合物作为一种新型 CDI 电极材料的应用开辟了一条新路。
{"title":"Conjugated microporous polytriphenylamine as high-performance anion-capture electrode for hybrid capacitive deionization with ultrahigh areal adsorption capacity","authors":"Weiqing Kong, Xiaoyuan Lu, Xu Ge, Qingao Zhang, Xiaoyu Jin, Meng Zhang, Yuan-Yuan Feng","doi":"10.1039/d4ta04010d","DOIUrl":"https://doi.org/10.1039/d4ta04010d","url":null,"abstract":"Conducting polymers with good electron conductivity and rich redox functional groups have attracted enormous attention as anode material for capacitive deionization (CDI) towards the relief of global freshwater scarcity. However, because of their intrinsically poor porosity and severe particle aggregation natures, previously used conducting polymers for CDI desalination have suffered from the disadvantage of rather low specific surface areas (&lt;50 m<small><sup>2</sup></small>g<small><sup>−1</sup></small>), sluggish ion diffusion kinetics, limited desalination capacities, and low mass loadings (~1 mg cm<small><sup>−2</sup></small>) on electrodes. Herein, we synthesized an amino group-rich conjugated microporous polytriphenylamine (m-PTPA) and demonstrated for the first time its great potential as a high-performance anion-capture electrode material in CDI applications. m-PTPA possesses reversible redox property, predominant &lt;2 nm microporous characteristics, and ultrahigh specific surface area (506 m<small><sup>2</sup></small>g<small><sup>−1</sup></small>), which ensured the fast ion transport within interconnected porous network, and maximized the exposure of electrochemical active sites to saline solution. Owing these novel features, the m-PTPA-based CDI device, with m-PTPA as anode at a high mass loading of 8.7 mg cm<small><sup>−2</sup></small>and activated carbon as cathode, exhibited high gravimetric/areal/volumetric-normalized salt adsorption capacities (47.21 mg g<small><sup>−1</sup></small>, 0.41 mg cm<small><sup>−2</sup></small>, 10.92 mg cm<small><sup>−3</sup></small>), fast adsorption rate (2.83 mg g<small><sup>−1</sup></small>min<small><sup>−1</sup></small>), low energy consumption, and excellent cycling stability. Besides, we also evaluated the competitive adsorption of some common anions existing in water, and probed the mechanism for Cl<small><sup>−</sup></small>adsorption on m-PTPA. We believe that this work paves a new way for the usage of conjugated microporous polymers as a new kind of CDI electrode materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141602699","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
In-depth understanding of the electrochemical energy storage efficiency between a series of new 3d-4d mixed metal polyoxometalates: Experimental and Theoretical Investigations 深入了解一系列新型 3d-4d 混合金属多氧甲基盐的电化学储能效率:实验与理论研究
IF 11.9 2区 材料科学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-07-12 DOI: 10.1039/d4ta03188a
Kalyankumar S. Morla, Dewendra Thakre, Tushar B. Deshmukh, Sunanda Malo, Subuhan Ahamed, R. K. Aparna, Subham Sahoo, Debajit Sarma, Kartik Chandra Mondal, Babasaheb R. Sankapal, Abhishek Banerjee
Transition-metal complexes, with their reversible redox properties, are the basis for electrochemical energy storage devices, such as rechargeable batteries and supercapacitors. In order to comprehend the variation in the electronic properties and electrochemical activity of concurrent transition elements existing in identical coordination environments, we have pursued extensive multi-method spectroscopic and electrochemical studies of three new isostructural 3d-4d mixed metal polyoxometalate complexes, viz. the vanado-molybdate Na2(NH4)5[(MoVI2O5)2(VIIIO2){O3PC(O)(CH2-4-C5NH4)PO32]•10H2O (1a), the chromo-molybdate (NH4)5[H2(MoVI2O5)2(CrIIIO2){O3P-C(O)(CH2-4-C5H4N)-PO3}2]•10H2O (2a) and the mangano-molybdate Na(NH4)6[H(MoVI2O5)2(MnIIIO2){O3P-C(O)(CH2-4-C5H4N)-PO3}2]•9H2O (3a). The structure of the polyanions have been determined using single-crystal X-ray diffraction studies, with all three polyanionic complexes having identical connectivity and arrangement in the solid-state. The electronic properties of the complexes have been analyzed thoroughly with electronic paramagnetic resonance (EPR) and X-ray photoelectronic spectroscopic (XPS) methods. EPR measurements for all three complexes are characterized by Δms = ±2 signals (forbidden half-field transition) at 77 K in solid state, confirming the existence of V(III), S = 1 for 1a; Cr(III), S = 3/2 for 2a; Mn(III), S = 2 for 3a. Using our original and novel binder-free approach to prepare supercapacitor electrodes, thorough comparative electrochemical energy storage studies have been performed on the three compounds using cyclic voltammetry, galvanostatic charge-discharge, electrochemical impedance spectroscopy, and cyclic stability tests. The oxo-vanado-molybdate complex has shown superior electrochemical performance, with respect to specific capacitances, energy density, power density, and electrochemical stability, followed by the oxo-chromo-molybdate and the oxo-mangano-molybdate complexes. The electrochemical performance trend has been corroborated from DFT calculations at B3LYP-D3(BJ)/Def2-SVP level of theory in a polar medium, with the same order of promptness of undergoing oxidation of the polyanionic species [M2+ to M3+; M = V (1') > Cr (2') > Mn (3'); ΔG(M3+-M2+) = +48 (1'), +58 (2'), +81 (3') kcal/mol], corroborating with experimental observations. The oxidation of these anionic species from 8- (MII) to 7- (MIII) has thus been computed to be highly favourable in the gas phase [~ -328 (1'), -311 (2'), -309 (3') kcal/mol]. The studies on the HOMO-LUMO structures of the complexes also corroborate the trend of the electrochemical behavior.
过渡金属配合物具有可逆氧化还原特性,是充电电池和超级电容器等电化学储能装置的基础。为了理解同时存在于相同配位环境中的过渡元素的电子特性和电化学活性的变化,我们采用多种方法对三种新的等结构 3d-4d 混合金属多氧化金属铝酸盐配合物,即钒钼酸盐 NaN2O4 和钼酸盐 NaN2O4,进行了广泛的光谱和电化学研究。钒钼酸盐 Na2(NH4)5[(MoVI2O5)2(VIIIO2){O3PC(O)(CH2-4-C5NH4)PO32]-10H2O (1a)、铬钼酸盐 (NH4)5[H2(MoVI2O5)2(CrIIIO2){O3P-C(O)(CH2-4-C5H4N)-PO3}2]-10H2O (2a) 和锰钼酸盐 Na(NH4)6[H(MoVI2O5)2(MnIIIO2){O3P-C(O)(CH2-4-C5H4N)-PO3}2]-9H2O (3a)。利用单晶 X 射线衍射研究确定了多阴离子的结构,所有这三种多阴离子配合物在固态中的连接和排列方式完全相同。利用电子顺磁共振(EPR)和 X 射线光电子能谱(XPS)方法对这些配合物的电子特性进行了深入分析。在 77 K 的固态下,所有三种配合物的电子顺磁共振测量值均为Δms = ±2(禁半场转变),证实了 1a 中存在 V(III),S = 1;2a 中存在 Cr(III),S = 3/2;3a 中存在 Mn(III),S = 2。利用我们独创的无粘结剂超级电容器电极制备方法,通过循环伏安法、电静态充放电法、电化学阻抗光谱法和循环稳定性测试,对这三种化合物进行了全面的电化学储能比较研究。在比电容、能量密度、功率密度和电化学稳定性方面,氧化-万那多-钼酸盐复合物显示出卓越的电化学性能,其次是氧化-铬-钼酸盐和氧化-锰-钼酸盐复合物。在极性介质中,B3LYP-D3(BJ)/Def2-SVP 理论水平的 DFT 计算证实了这一电化学性能趋势,多阴离子物种[M2+ 到 M3+;M = V (1') > Cr (2') > Mn (3'); ΔG(M3+-M2+) = +48 (1'), +58 (2'), +81 (3') kcal/mol],与实验观察结果相吻合。因此,计算得出这些阴离子物种从 8- (MII) 到 7- (MIII) 的氧化过程在气相中非常有利 [~ -328 (1'), -311 (2'), -309 (3') kcal/mol]。对复合物 HOMO-LUMO 结构的研究也证实了电化学行为的趋势。
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Journal of Materials Chemistry A
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