Journal of Colloid and Interface Science最新文献_第8页

Design and synthesis of FeS2/graphite sandwich structure with enhanced lithium-storage performance for lithium-ion and solid-state lithium batteries 为锂离子电池和固态锂电池设计并合成具有更强储锂性能的 FeS2/石墨夹层结构。

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science

Pub Date : 2024-11-10 DOI: 10.1016/j.jcis.2024.11.060

Qingtian Li , Tao Wang , Baiyu Guo , Xin Qiao , Xing Meng , Di Jin , Hailong Qiu

As a conversion-type cathode material, FeS₂ emerges as a promising candidate for the next generation of energy storage solutions, attributed to its cost-effectiveness, environment-friendliness and high theoretical capacity. However, several challenges hinder its practical application, including sluggish kinetics, insulating reaction products and significant volume fluctuation during cycling, which collectively compromise its rate capability and cycle stability. Herein, a well-designed sandwich structure of FeS₂ embedded between graphite layers (FeS₂/C) is obtained using a chloride intercalation and sulfidation strategy. The layered graphite-FeS₂-graphite configuration boosts the active sites and adsorption capacity of Li⁺, thereby guaranteeing a high reversible capacity. Furthermore, the graphitic carbon matrix serves a dual purpose: it enhances electronic conductivity and restrain the volume fluctuation of FeS₂ during long cycling. This combination ensures robust electrochemical kinetics, structural integrity and long life. Consequently, the FeS₂/C composites exhibit exceptional lithium storage performance, achieving capacities of 506.2 mAh g⁻¹ at 0.5 A/g and 277.2 mAh g⁻¹ at 5.0 A/g. Additionally, the FeS₂/C composites show promising potential as cathodes for all solid-state lithium batteries, showcasing high specific capacities of 658.0 mAh g⁻¹ at 0.1 A/g for the second cycle and maintaining a cycle performance of 288.5 mAh g⁻¹ after 800 cycles at 0.5 A/g. These values surpass the second discharge specific capacity of 96.1 mAh g⁻¹ and cycle capacity of 25.3 mAh g⁻¹ observed for Fe₂O₃/C composites. The discharge mechanism of FeS₂/C composites was further characterized through in-situ transmission electron microscope test. This work provides valuable insights for designing and synthesizing FeS₂, highlighting its potential for lithium ion storage and all solid-state lithium batteries.

作为一种转换型阴极材料，FeS2 因其成本效益高、环境友好和理论容量大而成为下一代储能解决方案的理想候选材料。然而，一些挑战阻碍了它的实际应用，包括缓慢的动力学、绝缘反应产物和循环过程中显著的体积波动，这些因素共同影响了它的速率能力和循环稳定性。在此，我们采用氯化物插层和硫化策略，获得了一种精心设计的嵌入石墨层之间的 FeS2 夹层结构（FeS2/C）。层状石墨-FeS2-石墨结构增强了活性位点和对 Li+ 的吸附能力，从而保证了高可逆容量。此外，石墨碳基质还具有双重作用：既能增强电子导电性，又能在长时间循环过程中抑制 FeS2 的体积波动。这种组合可确保稳定的电化学动力学、结构完整性和较长的使用寿命。因此，FeS2/C 复合材料表现出卓越的锂存储性能，在 0.5 A/g 和 5.0 A/g 的条件下，容量分别达到 506.2 mAh g-1 和 277.2 mAh g-1。此外，FeS2/C 复合材料还显示出作为所有固态锂电池阴极的巨大潜力，在 0.1 A/g 条件下的第二次循环中显示出 658.0 mAh g-1 的高比容量，并且在 0.5 A/g 条件下循环 800 次后仍能保持 288.5 mAh g-1 的循环性能。这些数值超过了在 Fe2O3/C 复合材料上观察到的 96.1 mAh g-1 的第二次放电比容量和 25.3 mAh g-1 的循环容量。通过原位透射电子显微镜测试，进一步确定了 FeS2/C 复合材料的放电机制。这项研究为设计和合成 FeS2 提供了宝贵的见解，凸显了其在锂离子存储和所有固态锂电池方面的潜力。

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引用次数: 0

High dielectric single-ion conducting interphase enables fast-charging lithium metal batteries 高介电性单离子导电中间相实现了锂金属电池的快速充电。

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science

Pub Date : 2024-11-10 DOI: 10.1016/j.jcis.2024.11.058

Guo Ai , Xiaojian Lian , Zhipeng Hu , Yong Lyu , Tiande Mo , Xiaochen Zhao , Xinggang Hou , Meng Sun , Hui Zhao , Ting Zhang , Wenfeng Mao

The poor stability and slow lithium ion (Li⁺) transfer kinetics of solid electrolyte interphase (SEI) pose significant challenges to lithium (Li) metal batteries. Although various SEI-related strategies have been developed, the Li⁺ transport properties and uniform Li deposition still require substantial improvement for fast-charging applications. Herein, we introduce a dielectric, single-ion-conductive artificial SEI (DS-SEI) composed of lithiated Nafion and BaTiO₃ (BTO) nanoceramics to address these issues. The lithiated Nafion stabilizes the Li anode with its elastic F-rich components and facilitates fast, single Li⁺ conduction through its anion-anchored structure. The high-dielectric BTO dynamically homogenizes the electric field (E-field) to promote uniform Li deposition, synergistically enhancing intrinsic single Li⁺ conductivity and Li⁺ desolvation/diffusion kinetics, thereby enabling fast charging of the Li anode. Consequently, the DS-SEI protected Li anode can cycle over 6800 h in a Li||Li cell at 10 mA cm⁻²/5 mAh cm⁻², over 400 cycles in a 2.75 mAh cm⁻² Li||LiFePO₄ cell at 1C, with 83.0 % capacity retention at 6C (16.5 mA cm⁻²), and maintain stable cycling in a 5.62 mAh cm⁻² Li||Li₆PS₅Cl|| LiNi_0.8Co_0.1Mn_0.1O₂ all solid-state cell. Our findings provide insights into the interfacial regulation of Li anode, paving the way for fast-charging Li metal batteries.

固态电解质相（SEI）稳定性差、锂离子（Li+）传输动力学缓慢，这给锂金属电池带来了巨大挑战。虽然已经开发出了各种与 SEI 相关的策略，但要实现快速充电应用，仍需大幅改善 Li+ 传输特性和锂的均匀沉积。为解决这些问题，我们在此介绍一种由锂化纳菲翁和 BaTiO3（BTO）纳米陶瓷组成的介电、单离子导电人工 SEI（DS-SEI）。锂化 Nafion 利用其富含 F 的弹性成分稳定锂阳极，并通过其阴离子锚定结构促进快速的单 Li+ 传导。高介电 BTO 动态均匀化电场（E-field），促进锂的均匀沉积，协同增强单锂+固有传导性和锂+解溶/扩散动力学，从而实现锂阳极的快速充电。因此，DS-SEI 保护的锂阳极可在 10 mA cm-2/5 mAh cm-2 下的锂电池中循环 6800 小时以上，在 1C 下的 2.75 mAh cm-2 Li||LiFePO4 电池中循环 400 次以上，在 6C 下（16.5 mA cm-2）容量保持率为 83.0%，并在 5.62 mAh cm-2 Li||Li6PS5Cl||LiNi0.8Co0.1Mn0.1O2 全固态电池中保持稳定循环。我们的发现为锂阳极的界面调控提供了见解，为锂金属电池的快速充电铺平了道路。

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引用次数: 0

An integrally formed Janus supramolecular bio-gel with intelligent adhesion for multifunctional healthcare 具有智能粘附性的整体成型 Janus 超分子生物凝胶，可用于多功能医疗保健。

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science

Pub Date : 2024-11-10 DOI: 10.1016/j.jcis.2024.11.056

Chenyang Tang , Yao Li , Xu Fei , Wenhui Zhao , Jing Tian , Longquan Xu , Yi Wang

Despite the rapid development of Janus adhesive hydrogels, most of them still entail complex fabrication processes and have the inherent flaws, such as fragility and instability, thereby restricting their biomedical applications. In this study, a novel Janus bio-gel with strong mechanical and intelligent adhesion functions is facilely fabricated through a gravity-driven settlement strategy, employing poly-cyclodextrin microspheres (PCDMs). This strategy takes advantage of the sedimentation behavior of PCDMs with various diameters to establish structural disparities on both sides of the Janus bio-gel, thereby resolving multiple predicaments including the tedious synthesis steps and poor bonding of multilayer hydrogels. Owing to the multiple dynamic interactions between polymers and PCDMs, the Janus supramolecular bio-gel demonstrates outstanding mechanical toughness (1.97 MJ/m³) and elongation rate (≈800 %). More attractively, the resulting Janus bio-gel exhibits remarkable adhesiveness (316.4 J/m² for interfacial toughness) and adhesive differences that are exceed 50 times between the two surfaces. Furthermore, the Janus supramolecular bio-gel also has excellent antibacterial properties, biocompatibility, environmental stability, and multiple monitoring functions, accelerating wound stably healing and monitoring physiologic parameters on the skin. This strategy provides a straightforward and promising approach to directly achieve multifunctional integration for smart health management.

尽管杰纳斯粘合水凝胶的发展十分迅速，但大多数水凝胶仍需要复杂的制造工艺，并存在脆性和不稳定性等固有缺陷，从而限制了其在生物医学领域的应用。本研究利用聚环糊精微球（PCDMs），通过重力驱动沉降策略，简便地制备了一种具有强大机械和智能粘附功能的新型 Janus 生物凝胶。这种策略利用不同直径的聚环糊精微球的沉降行为，在 Janus 生物凝胶的两侧建立结构差异，从而解决了包括繁琐的合成步骤和多层水凝胶粘合不良在内的多种难题。由于聚合物和 PCDM 之间的多重动态相互作用，Janus 超分子生物凝胶显示出卓越的机械韧性（1.97 MJ/m3）和伸长率（≈800%）。更吸引人的是，由此产生的 Janus 生物凝胶具有出色的粘合力（界面韧性为 316.4 J/m2），两个表面之间的粘合力差异超过 50 倍。此外，Janus 超分子生物凝胶还具有优异的抗菌性、生物相容性、环境稳定性和多种监测功能，可加速伤口稳定愈合并监测皮肤生理参数。这种策略为直接实现多功能集成的智能健康管理提供了一种直接而有前景的方法。

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引用次数: 0

Environmentally stable and multi-functional conductive gelatin/PVA/black wattle bark tannin based organogel as strain, temperature and bioelectric sensor for multi-mode sensing 环境稳定的多功能导电明胶/PVA/黑荆树皮单宁有机凝胶作为多模式传感的应变、温度和生物电传感器。

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science

Pub Date : 2024-11-10 DOI: 10.1016/j.jcis.2024.11.045

Li Zhao , Xinru Wang , Xianyao Feng , Wenhua Yang , Zhenye Wang , Jinwei Zhang , Liyuan Zhang , Yaohui You

Conductive hydrogels are regarded as ideal candidates for the application of flexible sensors owing to their excellent flexibility, portability and conductivity. However, it is still challenging and meaningful to prepare multifunctional (self-healing, adhesion, anti-freezing, biocompatibility, antibacterial and conductivity properties) and multi-mode sensing hydrogel-based sensors. Herein, we developed an environmentally stable and multi-functional conductive organogel via dynamic crosslinks based on biomass materials gelatin, black wattle bark tannin and PVA in the propylene glycol/water binary solvent system. Thanks to the dynamic interactions in the system, the good mechanical strength and self-healing performance of the obtained organogel are simultaneously realized. Meanwhile, the organogel integrates many crucial properties such as adhesion, environmental stability (anti-freezing and water retention), biocompatibility, antibacterial behavior and conductivity capacity. Significantly, the organogel can be assembled as three-mode sensors for strain, bioelectricity and temperature sensing. This three-mode sensor can effectively monitor human health data, resulting in providing supplement human health information and conditions. This work displays an interesting approach to construct an intelligent multi-functional conductive biomass organogel based multi-mode flexible sensors.

导电水凝胶具有出色的柔韧性、便携性和导电性，因此被视为柔性传感器应用的理想候选材料。然而，制备多功能（自愈性、粘附性、抗冻性、生物相容性、抗菌性和导电性）和多模式传感的水凝胶传感器仍然具有挑战性和意义。在此，我们以生物质材料明胶、黑荆树皮单宁和 PVA 为基础，在丙二醇/水二元溶剂体系中通过动态交联开发出了一种环境稳定的多功能导电有机凝胶。由于体系中的动态相互作用，所获得的有机凝胶同时具有良好的机械强度和自愈性能。同时，该有机凝胶还集成了许多关键特性，如粘附性、环境稳定性（抗冻性和保水性）、生物相容性、抗菌性和导电性。重要的是，这种有机凝胶可以组装成应变、生物电和温度三模传感器。这种三模式传感器可有效监测人体健康数据，从而提供补充的人体健康信息和状况。这项工作展示了一种构建基于生物质有机凝胶的智能多功能导电多模柔性传感器的有趣方法。

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引用次数: 0

Se–S bonded non-metal elementary substance heterojunction activating photoelectrochemical water splitting 激活光电化学水分离的 Se-S 键非金属基本物质异质结。

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science

Pub Date : 2024-11-10 DOI: 10.1016/j.jcis.2024.11.059

Qingxia Zhou, Chuanzhen Feng, Xiaodong Wang, Jialing He, Junyu Wang, Huijuan Zhang, Yu Wang

Non-metal elements are often merely regarded as electronic modulators, yet their intrinsic characteristics are frequently overlooked. Indeed, non-metal elements possess notable advantages in high-abundance, excellent hydrogen adsorption and the ability of active sites to be inversely activated, rendering them potential photoelectrochemical (PEC) materials. However, weak non-metal interbinding, susceptibility to photocorrosion, and high photogenerated carrier recombination rates hinder their practical applications. Herein, for the first time, we report a novel non-metal elementary substance heterojunction Se/S based on interfacial bonding engineering strategy. Atomic-level tight coupling of sulfonyl-rich sulfur quantum dots (SQDs) with selenium microtube arrays (Se-MTAs) enhances the structural stability of Se/S and introduces crucial Se–S heterointerfacial bonds, which not only endow Se/S with robust internal electronic interactions, but also provide high-speed channels for charge separation via unique bridging. Consequently, Se/S achieves optimal photocurrent density of 3.91 mA cm⁻² at 0 V_RHE, accompanied by long-term stability over 24 h. It is the highest value reported to date for Se-based photocathodes without co-catalyst and outperforms most metal-selenide-based photoelectrodes. Furthermore, the direct Z-scheme charge transport mechanism is exposed by in-depth spectroscopic analyses. Our work fills the gap in application of non-metal elementary substance heterojunction for PEC, poised for potential expansion into other new-energy devices.

非金属元素通常只被视为电子调制器，但其内在特性却经常被忽视。事实上，非金属元素具有高丰度、出色的氢吸附性和活性位点反向活化能力等显著优势，使其成为潜在的光电化学（PEC）材料。然而，非金属间结合力弱、易受光腐蚀以及光生载流子重组率高等问题阻碍了它们的实际应用。在此，我们首次报道了一种基于界面结合工程策略的新型非金属基本物质异质结 Se/S。富磺酰基硫量子点（SQDs）与硒微管阵列（Se-MTAs）的原子级紧密耦合增强了 Se/S 的结构稳定性，并引入了关键的 Se-S 异界面键，这不仅赋予了 Se/S 强大的内部电子相互作用，还通过独特的桥接为电荷分离提供了高速通道。因此，Se/S 在 0 VRHE 条件下可达到 3.91 mA cm-2 的最佳光电流密度，并可在 24 小时内保持长期稳定性。这是迄今为止所报道的不含助催化剂的硒基光电阴极的最高值，其性能优于大多数金属硒基光电电极。此外，深入的光谱分析揭示了直接 Z 型电荷传输机制。我们的研究填补了非金属基本物质异质结在 PEC 应用方面的空白，有望扩展到其他新能源设备。

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引用次数: 0

K-Mn3O4-NCs@PANI nanochains for high-rate and stable aqueous zinc-ion batteries: A doping and morphology-tailored synthesis strategy 用于高倍率和稳定水性锌离子电池的 K-Mn3O4-NCs@PANI 纳米链：掺杂和形态定制合成策略。

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science

Pub Date : 2024-11-10 DOI: 10.1016/j.jcis.2024.11.061

Haihong Yin , Yunfeng Wu , Zhipeng Chen , Zhirun Qian , Fuzhi Wang , Tingting Chen , Bocheng Su , Kangwei Wen , Lin Qin , Zhenguo Wang

Aqueous zinc ion batteries (AZIBs) are promising energy storage solutions due to their high energy density and safety. However, developing cathode materials that offer both high energy density and durability for Zn²⁺ ions storage remains challenging. Manganese (Mn) oxide-based cathodes have been developed for AZIBs due to their high discharge voltage and desirable capacity, but face challenges like poor conductivity, slow reaction kinetics, and dissolution during cycling. Doping, morphology/structure design, and protective layers are effective for enhancing the structure, conductivity, and electronic properties of Mn-based oxides. A synthetic strategy combining these methods for Mn₃O₄ cathodes is proposed for AZIBs. K⁺ ions doping in Mn₃O₄ (K-Mn₃O₄) can regulate local electronic structure, induce oxygen vacancies, improve conductivity, and provide more active sites for Zn²⁺ ions diffusion. Additionally, K-Mn₃O₄ nanochain (K-Mn₃O₄-NCs), with a unique chain-like nanostructure (NCs) and high aspect ratio, synthesized via Mn²⁺ ions chelation with nitrilotriacetic acid (NTA) and calcination, show reduced interparticle contact resistance, shorter Zn²⁺ ions diffusion length, and faster reaction kinetics. Meanwhile, the in-situ polymerized polyaniline (PANI) layer on K-Mn₃O₄-NCs shields against corrosion (K-Mn₃O₄-NCs@PANI), connects 1D K-Mn₃O₄-NCs into a continuous conductive network, suppresses volume expansion, and improves stability. Electrochemical analysis shows that K-Mn₃O₄-NCs@PANI exhibits higher stability and faster reaction kinetics due to a reduced bandgap, increased oxygen defects, and less coulombic repulsion between Zn²⁺ ions and Mn oxide hosts. The K-Mn₃O₄-NCs@PANI cathode achieved a high capacity of 510 mAh/g at 0.1 A/g and excellent rate capacity of 203.2 mAh/g at 5 A/g. After 20,000 cycles, it maintained a capacity of 90.3 mAh/g at 5 A/g, showing exceptional long-term stability with a minimal decay rate of 0.026 ‰ per cycle.

锌离子水电池（AZIBs）具有高能量密度和安全性，是一种前景广阔的储能解决方案。然而，开发既能提供高能量密度又能耐久储存 Zn2+ 离子的阴极材料仍具有挑战性。锰（Mn）氧化物基阴极具有高放电电压和理想的容量，因此已被开发用于 AZIB，但面临着导电性差、反应动力学缓慢以及在循环过程中溶解等挑战。掺杂、形态/结构设计和保护层可有效增强锰基氧化物的结构、导电性和电子特性。本文为 AZIBs 提出了一种结合这些方法的 Mn3O4 阴极合成策略。在 Mn3O4（K-Mn3O4）中掺入 K+ 离子可以调节局部电子结构，诱导氧空位，提高导电性，并为 Zn2+ 离子的扩散提供更多的活性位点。此外，通过硝基三乙酸（NTA）螯合 Mn2+ 离子并煅烧合成的 K-Mn3O4 纳米链（K-Mn3O4-NCs）具有独特的链状纳米结构（NCs）和高纵横比，可降低粒子间接触电阻、缩短 Zn2+ 离子扩散长度并加快反应动力学。同时，K-Mn3O4-NCs 上的原位聚合聚苯胺（PANI）层可防止腐蚀（K-Mn3O4-NCs@PANI），将一维 K-Mn3O4-NCs 连接成连续的导电网络，抑制体积膨胀，提高稳定性。电化学分析表明，K-Mn3O4-NCs@PANI 具有更高的稳定性和更快的反应动力学，这是由于带隙减小、氧缺陷增加以及 Zn2+ 离子与氧化锰宿主之间的库仑斥力减小。K-Mn3O4-NCs@PANI 阴极在 0.1 A/g 条件下实现了 510 mAh/g 的高容量，在 5 A/g 条件下实现了 203.2 mAh/g 的优异速率容量。经过 20,000 次循环后，它在 5 A/g 时的容量仍保持在 90.3 mAh/g，显示出卓越的长期稳定性，每次循环的衰减率仅为 0.026 ‰。

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引用次数: 0

Constructing artificial photosynthetic system based on graphdiyne double heterojunction to enhance REDOX capacity and hydrogen evolution efficiency 构建基于石墨二炔双异质结的人工光合作用系统，提高 REDOX 能力和氢进化效率。

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science

Pub Date : 2024-11-10 DOI: 10.1016/j.jcis.2024.11.054

Huijun Zhang , Minjun Lei , Fei Jin , Hai Liu , Zhiliang Jin

Although traditional type II heterojunction designs for artificial photosynthesis show promise for photocatalytic hydrogen production, their redox capacity is somewhat limited due to the spatial separation of hydrogen evolution and oxidation reactions at less favorable sites. To overcome this limitation, ohmic junctions based on type II heterojunctions have been designed to enhance hydrogen evolution by transferring electrons to the metal component. In this study, a copper powder graphdiyne (Cu-GDY) composite catalyst with ohmic angle contact was synthesized by coupling copper foil with hexa-hexylbenzene. Incorporating Cu-GDY into CoGdO₃ results in an interleaved band structure forming a type II heterojunction at the contact interface. This configuration overcomes the issue of the unfavorable conduction band position of CoGdO₃, thereby promoting charge transfer. The internal electric field created by the Fermi level difference between Cu-GDY and CoGdO₃, increase in REDOX capacity is the main reason for the increase of carrier separation rate. In addition, the plasmonic properties of copper expand the active reaction sites and promote the hydrogen evolution reaction. The composite catalyst exhibits b a hydrogen production rate that is 10.5 times higher than that of the individual catalysts. This work demonstrates that the formation of two distinct contact interfaces between Cu-GDY and CoGdO₃ significantly improves the electron transfer and hydrogen evolution performance.

虽然用于人工光合作用的传统 II 型异质结设计显示出光催化制氢的前景，但由于氢气进化和氧化反应在空间上分离于较不利的位置，其氧化还原能力受到一定限制。为了克服这一局限性，人们设计了基于 II 型异质结的欧姆结，通过将电子转移到金属成分来增强氢气进化。在本研究中，通过将铜箔与六己基苯偶联，合成了具有欧姆角接触的铜粉石墨二炔（Cu-GDY）复合催化剂。在 CoGdO3 中加入 Cu-GDY 会产生交错带结构，在接触界面形成 II 型异质结。这种结构克服了 CoGdO3 不利于传导带位置的问题，从而促进了电荷转移。Cu-GDY 和 CoGdO3 之间的费米级差所产生的内电场、REDOX 容量的增加是载流子分离率提高的主要原因。此外，铜的等离子特性扩大了活性反应位点，促进了氢进化反应。复合催化剂的产氢率是单个催化剂的 10.5 倍。这项研究表明，在 Cu-GDY 和 CoGdO3 之间形成两个不同的接触界面可显著提高电子转移和氢进化性能。

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引用次数: 0

Synergy strategy of multi-metals confined in heteroatom framework toward constructing high-performance water oxidation electrocatalysts 构建高性能水氧化电催化剂的多金属杂原子框架协同战略。

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science

Pub Date : 2024-11-10 DOI: 10.1016/j.jcis.2024.11.050

Hanzhong Ren, Hao Liu, Rentong Qin, Hucheng Fu, Weixiang Xu, Rong Jia, Jia Jiang, Yizhang Yang, Yiting Xu, Birong Zeng, Conghui Yuan, Lizong Dai

The development of a low-cost, highly active, and non-precious metal catalyst for oxygen evolution reaction (OER) is of great significance. Multi-metallic catalysts containing Fe, Co, and Ni exhibit remarkable OER activity, while the specific contributions of each component and the synergistic effects in the ternary metal catalyst has remained elusive. In this work, we synthesized a series of S and N-doped mono-metallic, bi-metallic, and tri-metallic hollow carbon sphere electrocatalysts (M−SNC) with the goal of enhancing the catalysts OER activity and shedding light on the unique roles and synergistic effects of the various metals in the FeCoNi ternary metal catalyst. Our systematic analyses demonstrated the introduction of Fe effectively reduces the overpotential, Co accelerates the kinetics of OER, and the addition of Ni further improves the OER performance. Benefiting from the synergistic effects, the FeCoNi-SNC exhibits a low overpotential of 270 mV, with no morphological or structural changes after reaction, maintaining high activity for 72 h at 10 mA cm⁻². Moreover, the assembled FeCoNi-SNC || Pt/C water electrolysis device operates for 65,000 s with minimal degradation, demonstrating its potential for practical application. This work presents a synergy strategy for the preparation of low-cost and highly efficient OER catalysts and further provides insights into the rational design and preparation of multicomponent catalysts.

开发用于氧进化反应（OER）的低成本、高活性和非贵金属催化剂意义重大。含有铁、钴和镍的多金属催化剂具有显著的氧进化反应活性，而三元金属催化剂中每种组分的具体贡献和协同效应却一直难以确定。在这项工作中，我们合成了一系列 S 和 N 掺杂的单金属、双金属和三金属空心碳球电催化剂 (M-SNC)，目的是提高催化剂的 OER 活性，并阐明各种金属在铁钴镍三元金属催化剂中的独特作用和协同效应。我们的系统分析表明，铁的加入有效降低了过电位，钴加速了 OER 的动力学过程，而镍的加入则进一步提高了 OER 的性能。得益于这些协同效应，FeCoNi-SNC 的过电位低至 270 mV，反应后无形态或结构变化，在 10 mA cm-2 的条件下可维持 72 小时的高活性。此外，组装好的 FeCoNi-SNC ||Pt/C 水电解装置可持续运行 65,000 秒，降解极小，证明了其实际应用的潜力。这项工作提出了一种制备低成本、高效率 OER 催化剂的协同策略，并进一步为合理设计和制备多组分催化剂提供了启示。

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引用次数: 0

pH-activated metal–organic layer nanozyme for ferroptosis tumor therapy 用于治疗肿瘤的 pH 活化金属有机层纳米酶。

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science

Pub Date : 2024-11-10 DOI: 10.1016/j.jcis.2024.11.057

Deyan Gong , Lu Liu , Ziwen Xiao , Zhuonan Yang , Yaoyu Hu , Taikui Sheng , Yajing Liu , Zhaohua Miao , Zhengbao Zha

Nanozymes have made great achievements in the research of tumor therapy. However, due to the complex tumor microenvironment, the catalytic activity and biosafety of nanozymes are limited. High catalytic efficiency is a relentless pursuit for the preparation of high-performance nanozymes. Dimensional reduction from 3D nanoscale metal–organic frameworks (nMOFs) to 2D nanoscale metal–organic layers (nMOLs) increases the encounters frequency of nanozymes and substrate, which facilitates the diffusion of reactive oxygen species (ROS) from nMOLs, thus significantly improving the effectiveness of chemodynamic therapy. In this study, He@Ce-BTC nMOF and He@Ce-BTB nMOL based on Ce₆ SBUs were synthesized by solvothermal reaction. Compared with the 3D nMOFs, the 2D nanozymes He@Ce-BTB nMOL possessed enhanced ROS catalytic efficiency, were able to be activated by the tumor acidic microenvironment with the polymerase mimetic activities (CAT, POD, GSH-OXD) that enhances the lipid peroxidation process and accelerates the process of ferroptosis thereby killing tumor cells. In addition, He@Ce-BTB does not affect normal tissue cells, thus avoiding diffusion-induced side effects. He@Ce-BTB has shown excellent therapeutic effects in vitro and in vivo, which indicates its potential for clinical application, and is expected to become a new generation of drugs for the treatment of tumors.

纳米酶在肿瘤治疗研究中取得了巨大成就。然而，由于肿瘤微环境复杂，纳米酶的催化活性和生物安全性受到限制。高催化效率是制备高性能纳米酶的不懈追求。从三维纳米级金属有机框架（nMOFs）降维到二维纳米级金属有机层（nMOLs），增加了纳米酶与底物的相遇频率，有利于活性氧（ROS）从nMOLs中扩散，从而显著提高化学动力学治疗的效果。本研究通过溶热反应合成了基于 Ce6 SBUs 的 He@Ce-BTC nMOF 和 He@Ce-BTB nMOL。与三维 nMOFs 相比，二维纳米分子 He@Ce-BTB nMOL 具有更高的 ROS 催化效率，能被肿瘤酸性微环境激活，具有模拟聚合酶（CAT、POD、GSH-OXD）的活性，能增强脂质过氧化过程，加速铁氧化过程，从而杀死肿瘤细胞。此外，He@Ce-BTB 不会影响正常组织细胞，从而避免了扩散引起的副作用。He@Ce-BTB 在体外和体内均显示出良好的治疗效果，表明其具有临床应用潜力，有望成为治疗肿瘤的新一代药物。

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引用次数: 0

Self-assembled hole transport engineering and bio-inspired coordination/incoordination ligands synergizing strategy for productive photoelectrochemical water splitting 自组装空穴传输工程和生物启发配位/不配位配体协同战略，实现高效光电化学水分离。

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science

Pub Date : 2024-11-10 DOI: 10.1016/j.jcis.2024.11.051

Kehui Xue , Lianqing Yu , Chong Liu , Huihua Luo , Zhe Li , Yaping Zhang , Haifeng Zhu

Charge transport and metal site stability play a critical role on realizing efficient solar water splitting in photoelectrochemical devices. Here, we investigated BiVO₄-based composite photoanodes (labelled as NF@PTA/2PACz/BVO) in which BiVO₄, [2-(9H-carbazol-9-yl) ethyl] phosphonic acid (2PACz) hole transport layers based on self-assembled monolayers (SAMs), and terephthalic acid (PTA)-functionalized NiFeOOH (NF@PTA) oxygen evolution cocatalysts (OECs) structurally similar to the OECs in natural photosystem II, were assembled sequentially. Alignment of energy levels and stabilization of metal sites can be achieved by this layer-designed structure. And the uncoordinated (COOH) carboxylate groups can accelerate the proton transfer. Fundamental investigations reveal that the NF@PTA/2PACz/BVO photoanode exhibits unique properties including passivated surface traps, excellent carrier density and lifetime, enlarged photovoltage, and smoother hole transport band structure. Consequently, the optimum NF@PTA/2PACz/BVO photoanode shows the photoelectrochemical (PEC) performance of 5.43 mA cm⁻² at 1.23 V vs reversible hydrogen electrode with an applied bias photon-to-current efficiency of 1.45 %. The coupled COFe bond between the coordinating carboxylate and the metals not only inhibits the leaching of the metal species but also maintains a steady photocurrent density over 20 h of stability test. Our work paves the way for the development of more efficient PEC cells with superior charge separation and breakthroughs in the stability of metal active sites, thus broadening their potential applications.

在光电化学器件中，电荷传输和金属位点稳定性对实现高效太阳能水分离起着至关重要的作用。在这里，我们研究了基于 BiVO4 的复合光阳极（NF@PTA/2PACz/BVO），其中 BiVO4、[2-（9H-咔唑-9-基）乙基]膦酸（2PACz）空穴传输层基于自组装单层（SAM）、和对苯二甲酸（PTA）功能化的 NiFeOOH（NF@PTA）氧进化协同催化剂（OEC），其结构与天然光系统 II 中的 OEC 相似。这种层设计结构可实现能级对齐和金属位点稳定。非配位（COOH）羧酸基团可以加速质子转移。基础研究表明，NF@PTA/2PACz/BVO 光阳极具有独特的性能，包括钝化的表面陷阱、优异的载流子密度和寿命、更高的光电压和更平滑的空穴传输带结构。因此，最佳 NF@PTA/2PACz/BVO 光阳极在 1.23 V 电压下对可逆氢电极的光电化学（PEC）性能为 5.43 mA cm-2，外加偏压光子对电流效率为 1.45%。配位羧酸盐和金属之间的耦合 COFe 键不仅抑制了金属物种的浸出，而且在 20 小时的稳定性测试中保持了稳定的光电流密度。我们的研究工作为开发更高效的 PEC 电池铺平了道路，这种电池具有卓越的电荷分离性能，并在金属活性位点的稳定性方面取得了突破，从而拓宽了其潜在的应用领域。

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引用次数: 0