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Functional additives for proton exchange membrane fuel cells 质子交换膜燃料电池的功能性添加剂
IF 22.2 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-30 DOI: 10.1016/j.enchem.2025.100144
Weihao Liu , Dandan Liu , Xin Wan , Jianglan Shui
Proton exchange membrane fuel cell (PEMFC) is an electrochemical energy conversion system with remarkable efficiency and eco-friendly operation. It holds immense promise and application potential in facilitating the transition towards sustainable energy solutions. Nevertheless, the widespread commercial adoption of PEMFCs is hindered by the immaturity of individual components within the system. Chief among these obstacles are the high cost and inadequate activity of the cathode catalyst, limited proton conductivity of the PEM, and fuel starvation issues at the anode. Furthermore, concerns regarding the mass transport limitation and the degradation of the membrane electrode assembly (MEA) during practical operation collectively impede performance optimization and lifetime extension. Despite the advancements in delicate catalyst design, the complex synthesis processes coupled with trial-and-error methodologies complicate scalability for large-scale applications. In response to these multifaceted challenges, incorporating functional additives (FAs) has emerged as a promising and versatile strategy. These smart additives, with diverse and unique functions, have rapidly gained traction and are being applied across nearly all components of the MEA. However, research efforts to utilize FAs to achieve high-performance and durable PEMFCs are not comprehensively documented, particularly concerning the underlying operational mechanisms. This review aims to bridge this knowledge gap by consolidating current understanding, providing a detailed analysis of the diverse mechanisms at play, and highlighting both the merits and limitations associated with the FA strategy. We aspire to offer valuable insights into this emerging field and contribute to the innovation of next-generation functional additives tailored for advanced PEMFC systems.
质子交换膜燃料电池(PEMFC)是一种高效、环保的电化学能量转换系统。它在促进向可持续能源解决方案过渡方面具有巨大的前景和应用潜力。然而,pemfc的广泛商业应用受到系统内单个组件不成熟的阻碍。这些障碍主要是阴极催化剂的高成本和活性不足,PEM的质子导电性有限,以及阳极的燃料短缺问题。此外,在实际操作过程中,对质量传输限制和膜电极组件(MEA)退化的担忧共同阻碍了性能优化和寿命延长。尽管精致的催化剂设计取得了进步,但复杂的合成过程加上试错方法使大规模应用的可扩展性复杂化。为了应对这些多方面的挑战,加入功能性添加剂(FAs)已成为一种有前途的通用策略。这些智能添加剂具有多样化和独特的功能,已迅速获得牵引力,并被应用于MEA的几乎所有组成部分。然而,利用fa来实现高性能和耐用的pemfc的研究工作并没有全面的记录,特别是关于潜在的操作机制。这篇综述旨在通过巩固现有的理解来弥合这一知识差距,提供对不同机制的详细分析,并强调与FA策略相关的优点和局限性。我们渴望在这一新兴领域提供有价值的见解,并为先进PEMFC系统量身定制的下一代功能添加剂的创新做出贡献。
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引用次数: 0
Performance optimization by antioxidant strategies for proton exchange membrane fuel cells: Recent progress and future 利用抗氧化策略优化质子交换膜燃料电池的性能:最新进展与展望
IF 22.2 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-01 DOI: 10.1016/j.enchem.2024.100142
Xianghui Yu , Shuxing Bai , Qinzhu Li , Ziyan Zhao , Qi Sun , Shuang Cao , Hongzhi Cui , Mingxu Liu , Qiang Xu , Chun-Chao Hou
Although proton exchange membrane fuel cells (PEMFCs) have become a potential replacement for traditional energy sources because of their minimal environmental impact and superior efficiency, their vulnerability to degradation caused by in situ generated peroxide and oxygen radical species has seriously hindered their widespread application. To mitigate the negative effects of chemical attack on components of PEMFCs, especially on proton exchange membranes (PEMs), there has been significant efforts devoted in employing antioxidant strategies as the preferred solution, which can directly eliminate and remove harmful peroxide and oxygen radical species. However, due to the rigorous operating conditions, such as low pH, electric potential, water flow, and ion exchange/concentration gradient, undesirable degradation occurred for antioxidant additives. Moreover, the diminished activity and capability of antioxidants resulting from alterations in the physical state, such as migration, agglomeration, and dissolution, are also crucial factors to be taken into account. In this review, we mainly focus on the recent advancements in antioxidant therapy in enhancing the durability of PEMs, especially offering a comprehensive overview of advanced techniques for designing synthetic compounds and conducting thorough analyses of antioxidants to enhance activity-stability factors, aiming to inspire further advancements in this exciting field.
尽管质子交换膜燃料电池(pemfc)因其对环境影响小、效率高而成为传统能源的潜在替代品,但其易被原位生成的过氧化氢和氧自由基降解,严重阻碍了其广泛应用。为了减轻化学攻击对质子交换膜(pemcs)组分的负面影响,特别是对质子交换膜(pemms)的负面影响,人们一直致力于采用抗氧化策略作为首选解决方案,它可以直接消除和去除有害的过氧化氢和氧自由基。然而,由于苛刻的操作条件,如低pH值、电位、水流量和离子交换/浓度梯度,抗氧化添加剂会发生不良降解。此外,由于物理状态的改变,如迁移、团聚和溶解,抗氧化剂的活性和能力下降也是需要考虑的关键因素。本文主要综述了近年来抗氧化治疗在提高PEMs耐久性方面的研究进展,重点介绍了设计合成化合物和深入分析抗氧化剂以提高活性稳定性因素的先进技术,旨在激发这一令人兴奋的领域的进一步发展。
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引用次数: 0
Recent advances in two-dimensional metal pnictogenide nanosheets and their nanohybrids with diverse energy applications 具有多种能源应用的二维金属烟族纳米片及其纳米杂化材料的研究进展
IF 22.2 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-16 DOI: 10.1016/j.enchem.2024.100139
Jihyeong Lee , Taehoon Kim , Dong Hoon Sun , Xiaoyan Jin , Seong-Ju Hwang
Two-dimensional inorganic nanosheets have received prime attention because of their intriguing physicochemical properties and diverse functionalities. The reactivity and properties of inorganic nanosheets are influenced by their bonding characteristics and electronic structures. Consequently, controlling their chemical compositions and crystal structures can enhance the electrochemical and catalytic functionalities of these two-dimensional nanosheets. As an emerging family of inorganic nanosheets, two-dimensional transition metal pnictogenide nanosheets, characterized by highly covalent bonding, have attracted emerging attention owing to their excellent catalyst and electrode performances resulting from their high electrical conductivity, high surface reactivity, and high stability. Additionally, transition metal pnictogenide nanosheets are promising hybridization matrices that enhance various functionalities of hybridized species via the effective formation of interfacial coordinative bonds. This review highlights the exceptional advantages of transition metal pnictogenide nanosheets in developing efficient energy-functional materials, with an in-depth discussion of dominant governing factors for improving their performances. Depending on the synthesis methods and application fields, this review surveys a wide range of two-dimensional transition metal pnictogenide nanosheets and their nanohybrids, along with various characterization tools. Future research directions for designing and synthesizing high-performance metal-pnictogenide-nanosheet-based materials are discussed, providing valuable insights for optimizing their functionalities crucial for many energy applications.
二维无机纳米片因其独特的物理化学性质和多种功能而受到广泛关注。无机纳米片的反应性和性能受其成键特性和电子结构的影响。因此,控制它们的化学组成和晶体结构可以增强这些二维纳米片的电化学和催化功能。二维过渡金属烟属化合物纳米片作为一类新兴的无机纳米片,因其具有高导电性、高表面反应性和高稳定性等优异的催化剂和电极性能而受到人们的广泛关注。此外,过渡金属烟属化合物纳米片是一种很有前途的杂交基质,它通过有效地形成界面配位键来增强杂交物种的各种功能。这篇综述强调了过渡金属烟族纳米片在开发高效能量功能材料方面的独特优势,并深入讨论了提高其性能的主要控制因素。根据合成方法和应用领域的不同,本文综述了各种二维过渡金属烟属化合物纳米片及其纳米杂化体,以及各种表征工具。讨论了未来设计和合成高性能金属-烟族化合物-纳米片材料的研究方向,为优化其在许多能源应用中至关重要的功能提供了有价值的见解。
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引用次数: 0
Hierarchically ordered meso-/macroporous MOF-based materials for catalysis and energy applications 用于催化和能源应用的分层有序介孔/大孔 MOF 基材料
IF 22.2 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-01 DOI: 10.1016/j.enchem.2024.100137
Anqian Hu , Qiongyi Xie , Liyu Chen, Yingwei Li
Metal–organic frameworks (MOFs) have attracted significant attention due to their tunable structures and ease of functionalization. However, the predominance of micropores in most MOFs limits their effectiveness in diffusion-controlled applications. Recent developments in the construction of hierarchically ordered macro-/mesoporous MOFs, as well as their composites and derivatives, have broadened the application scope of traditional MOF-based materials. These ordered meso-/macropore structures enhance the exposure of active sites and improve mass transfer efficiency, thereby boosting reaction performance. This review discusses recent advancements in the design, synthesis, and catalysis and energy applications of ordered macro-/mesoporous MOF-based materials. Compared to conventional microporous materials, ordered macro-/mesoporous MOF-based materials demonstrate superior performance in applications including photo-, electro-, and thermocatalysis and electrochemical energy storage. The review also explores current challenges and future direction in the development of ordered macro-/mesoporous MOF-based materials, providing valuable insights for creating new materials with greater efficiency and broader applicability.
金属有机框架(MOFs)因其结构可调、易于功能化而备受关注。然而,大多数 MOFs 中微孔占主导地位,这限制了它们在扩散控制应用中的有效性。最近在构建分层有序的大孔/介孔 MOFs 及其复合材料和衍生物方面取得的进展拓宽了传统 MOF 基材料的应用范围。这些有序的介孔/大孔结构可提高活性位点的暴露率,改善传质效率,从而提高反应性能。本综述讨论了有序大孔/介孔 MOF 基材料在设计、合成、催化和能源应用方面的最新进展。与传统微孔材料相比,有序大孔/介孔 MOF 基材料在光催化、电催化、热催化和电化学储能等应用中表现出卓越的性能。综述还探讨了有序宏观/多孔 MOF 基材料目前面临的挑战和未来的发展方向,为创造具有更高效率和更广泛应用的新材料提供了宝贵的见解。
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引用次数: 0
The relationship between electronic behavior of single atom catalysts and CO2 reduction to oxygenates 单原子催化剂的电子行为与二氧化碳还原成含氧化合物之间的关系
IF 22.2 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-01 DOI: 10.1016/j.enchem.2024.100141
Fenghai Cao , Guangbo Liu , Xianbiao Wang , Li Tan , Noritatsu Tsubaki
Single-atom catalysts (SACs), with 100% atomic efficiency and distinctive electronic properties, show excellent catalytic performance for CO2 reduction to oxygenates. However, the electronic structure of active sites and key intermediates undergo continuous changes during the reaction on SACs. It is challenging to explain these phenomena through structure-activity relationship. Herein, the “electronic behavior” elucidates the dynamic nature of electronic interactions between active sites and key intermediates. In this review, we invesitgate the transformation of the electronic structure within the CO2 molecule and the active site of SACs during CO2 activation, elucidating the complex interplay between these two entities. Then, we delve into the electronic change processes involved in thermal, electro-, and photo-catalytic CO2 conversion, providing in-depth discussions. Additionally, the influence of the catalyst's electronic behavior on the structure-activity relationship is delineated with precision. At last, the challenges and future perspectives of electronic behavior for SACs are outlined.
单原子催化剂(SAC)具有 100% 的原子效率和独特的电子特性,在将 CO2 还原成含氧化合物的过程中表现出卓越的催化性能。然而,在 SACs 上进行反应时,活性位点和关键中间产物的电子结构会发生持续变化。通过结构-活性关系来解释这些现象具有挑战性。在这里,"电子行为 "阐明了活性位点和关键中间产物之间电子相互作用的动态性质。在这篇综述中,我们探讨了二氧化碳活化过程中二氧化碳分子和 SAC 活性位点内电子结构的转变,阐明了这两个实体之间复杂的相互作用。然后,我们深入探讨了热催化、电催化和光催化二氧化碳转化过程中涉及的电子变化过程。此外,我们还精确阐述了催化剂的电子行为对结构-活性关系的影响。最后,概述了 SAC 电子行为的挑战和未来前景。
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引用次数: 0
Promotion effects in ammonia synthesis over ruthenium catalysts: A review 钌催化剂对氨合成的促进作用综述
IF 22.2 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-01 DOI: 10.1016/j.enchem.2024.100140
Hsin-Yu Chen , Shih-Yuan Chen , Yves Ira A. Reyes , Martin Keller , Takehisa Mochizuki , Chien-Neng Liao , Hsin-Yi Tiffany Chen
Haber-Bosch (HB) process for industrial NH3 synthesis operated at high temperature (500 °C) and pressure conditions (100–300 atm) with iron ore catalysts. Ru-based catalysts promoted by 1A and 2A elements, particularly Ba and Cs, show promise in electrolysis-driven HB operating under intermittent conditions. However, the roles of these promoters, traditionally classified as structural and electronic promoters based on trial-and-error study, remain controversial and lack a comprehensive literature review. This paper systematically examined these promotion effects, integrating conventional knowledge with recent experimental and computational advancements. It highlighted new insights into the composition and intrinsic roles of Ba, Cs, and other 1A/2A elements. The reaction mechanism of thermo-catalyzed NH3 synthesis, including recent theories on spin promotion effects at active sites, is extensively discussed. This review provides a thorough understanding of promotion effects and guides the rational design of advanced metal catalysts with promoters for industrial NH3 synthesis and various energy-related processes.
在高温(500°C)和压力条件(100-300 atm)下,以铁矿石为催化剂的工业氨合成Haber-Bosch (HB)工艺。由1A和2A元素促进的钌基催化剂,特别是Ba和Cs,在间歇条件下的电解驱动HB运行中显示出前景。然而,这些启动子的作用,传统上分为结构启动子和电子启动子,基于试错研究,仍然存在争议,缺乏全面的文献综述。本文系统地考察了这些促进效应,将传统知识与最近的实验和计算进展结合起来。它突出了Ba, Cs和其他1A/2A元素的组成和内在作用的新见解。广泛讨论了热催化NH3合成的反应机理,包括活性位点自旋促进效应的最新理论。本文综述了促进剂在工业氨合成和各种能源相关工艺中的作用,为促进剂金属催化剂的合理设计提供了理论依据。
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引用次数: 0
Recent progress in the development of self-assembled porphyrin derivatives for photocatalytic hydrogen evolution 光催化析氢用自组装卟啉衍生物的研究进展
IF 22.2 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-01 DOI: 10.1016/j.enchem.2024.100138
Govardhana Babu Bodedla , Xunjin Zhu , Wai-Yeung Wong
Photocatalytic hydrogen evolution (PHE) offers a promising solution to mitigate environmental pollution and address the global energy crisis. Porphyrin derivatives have been extensively explored as photocatalysts for PHE, owing to their efficient light-harvesting ability in the UV–Vis absorption region, stable photoexcited states, reversible redox properties, high photo and chemical stabilities, and tailorable optoelectronic properties via structural engineering. However, the monomeric porphyrin photocatalysts typically exhibit a narrow absorption range in the visible spectrum, susceptibility to light corrosion, and difficulty in loading cocatalysts such as Pt due to limited interface contact area. These issues lead to a low electron transfer efficiency between monomeric porphyrin photocatalyst and cocatalyst and thus inferior PHE performance. In addition, porphyrin photocatalysts in their bulk powder form usually possess uncontrolled morphologies and thus inefficient separation and migration of photoinduced charge carriers, which subsequently lowers the PHE performance. To address these challenges, the development of self-assembled porphyrin derivatives with well-defined sizes and shapes in the solid state presents a promising strategy. Over the past decade, significant advancements have been made in creating porphyrin-based self-assembled materials for efficient PHE. In this review, we summarize the progress in developing porphyrin-based self-assembled materials for PHE, highlighting how the morphology of self-assembled porphyrins affects their light-harvesting abilities, electronic properties, and separation and migration of photoinduced charge carriers, ultimately impacting their PHE performances. We are optimistic that this review will guide the future development of innovative self-assembled porphyrins, enhancing their efficacy for PHE and broadening their applications across various areas.
光催化析氢(PHE)为减轻环境污染和解决全球能源危机提供了一个有前途的解决方案。由于卟啉衍生物在UV-Vis吸收区具有高效的光捕获能力、稳定的光激发态、可逆的氧化还原性能、高的光和化学稳定性以及通过结构工程可定制的光电性能,卟啉衍生物已被广泛探索作为PHE的光催化剂。然而,单体卟啉光催化剂通常表现出可见光吸收范围窄,易受光腐蚀,并且由于界面接触面积有限而难以加载Pt等助催化剂。这些问题导致单体卟啉光催化剂与助催化剂之间的电子传递效率较低,从而导致PHE性能较差。此外,散装粉末形式的卟啉光催化剂通常具有不受控制的形态,因此光诱导载流子的分离和迁移效率低下,从而降低了PHE性能。为了解决这些挑战,在固态中开发具有明确尺寸和形状的自组装卟啉衍生物是一种很有前途的策略。在过去的十年中,基于卟啉的高效PHE自组装材料的制造取得了重大进展。本文综述了卟啉自组装材料的研究进展,重点介绍了卟啉自组装材料的形态如何影响其光收集能力、电子性能和光诱导载流子的分离和迁移,最终影响其PHE性能。我们乐观地认为,这一综述将指导未来创新自组装卟啉的发展,提高其对PHE的功效,扩大其在各个领域的应用。
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引用次数: 0
Hydrothermal treatment of lignocellulosic biomass towards low-carbon development: Production of high-value-added bioproducts 水热处理木质纤维素生物质,实现低碳发展:生产高附加值生物产品
IF 22.2 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-12 DOI: 10.1016/j.enchem.2024.100133
Caiwei Wang , Wenli Zhang , Xueqing Qiu , Chunbao Xu

The comprehensive and efficient utilization of lignocellulosic biomass is of great significance to humanity due to its low-carbon and sustainable characteristics. Hydrothermal treatment is a low-carbon technology for the valorization of lignocellulosic biomass toward diverse value-added bioproducts through the disintegration and conversion of lignocellulosic biomasses. This review first introduces the chemical compositions of lignocellulosic biomasses and the operating principles of hydrothermal treatment. Then, the transformation of the chemical compositions during hydrothermal treatment (<300 °C) is elucidated comprehensively. In addition, the recent advances in the hydrothermal valorization of lignocellulosic biomass into bio-oil, wood vinegar, briquette fuels, absorbents, carbonaceous electrode materials, and catalysts are introduced and discussed emphatically. The bridge between the hydrothermal treatment and the physicochemical properties and performances of the obtained value-added bioproducts is further built. The precise removal of chemical compositions and the followed directional conversion are the keys affecting the structure and physiochemical properties of the bioproducts. It is difficult to regulate the extraction and decomposition of chemical compositions in one step because of the heterogeneous structure and recalcitrant cross-linking barrier of lignocellulosic biomass. In this regard, a multi-step process is promising undoubtedly, while tailoring the specific application is necessary for industrialization due to the diversity of bioproducts. The future direction of fully efficient utilization of lignocellulosic biomass is proposed for the researches on the multipurpose valorization of high-value-added bioproducts. We believe this review would provide valuable guidance for the exploitation of biomass-derived high-value-added bioproducts through multipurpose production processes, ideally towards the achievement of a low-carbon blueprint.

木质纤维素生物质因其低碳、可持续的特点,综合高效利用对人类意义重大。水热处理是一种低碳技术,通过分解和转化木质纤维素生物质,实现木质纤维素生物质的价值化,生产出多种高附加值的生物产品。本综述首先介绍了木质纤维素生物质的化学成分和水热处理的工作原理。然后,全面阐述了水热处理(300 °C)过程中化学成分的转变。此外,还重点介绍和讨论了将木质纤维素生物质水热处理成生物油、木醋、压块燃料、吸收剂、碳质电极材料和催化剂的最新进展。进一步建立了水热处理与所获得的增值生物产品的物理化学特性和性能之间的桥梁。化学成分的精确去除和后续定向转化是影响生物产品结构和理化性质的关键。由于木质纤维素生物质具有异质结构和难降解的交联障碍,因此很难一步完成化学成分的提取和分解。在这方面,多步骤工艺无疑是大有可为的,而由于生物产品的多样性,量身定制具体应用是工业化的必要条件。为高附加值生物产品的多用途价值化研究提出了充分有效利用木质纤维素生物质的未来方向。我们相信,本综述将为通过多用途生产工艺开发生物质衍生的高附加值生物产品提供有价值的指导,从而理想地实现低碳蓝图。
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引用次数: 0
Hole transport materials for scalable p-i-n perovskite solar modules 用于可扩展 pi-n 型过氧化物太阳能模块的空穴传输材料
IF 22.2 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.enchem.2024.100135
Sibo Li , Xin Wang , Nuanshan Huang , Sisi He , Longbin Qiu , Yabing Qi
Perovskite solar cells (PSCs) have emerged as a promising avenue for sustainable energy production, offering high efficiency at a low cost. However, the commercialization of PSCs is significantly influenced by the characteristics and properties of the perovskite bottom layers. In this review, we explore the implications of the perovskite bottom layers of inverted p-i-n PSCs, specifically the hole transport layer (HTL) and the HTL/perovskite interface, which plays an important role in the commercial viability of PSCs, including the key factors such as scalability, stability, and environmental safety. We examine the scalability challenge, which is essential for moving from lab-scale prototypes to mass production, through layer uniformity and compatibility with broad-scale manufacturing techniques. Stability issues include both the operational lifespan and environmental durability of PSCs, highlighting the significance of the bottom layers in safeguarding against degradation. Furthermore, we venture into environmental safety measures, emphasizing the approaches to curtailing lead leakage via sophisticated HTL and HTL/perovskite interface engineering. Through a holistic evaluation of these pivotal aspects, this review aims to establish a blueprint for forthcoming enhancements in PSC technology, highlighting the imperative of optimizing the HTL and HTL/perovskite interface to navigate commercialization obstacles and fully explore the potential of PSCs in sustainable energy production.
过氧化物太阳能电池(PSCs)具有高效率、低成本的特点,已成为可持续能源生产的一条大有可为的途径。然而,包晶石底层的特性和属性对 PSC 的商业化有很大影响。在这篇综述中,我们探讨了倒置 pi-i-n PSC 的包晶底层,特别是空穴传输层(HTL)和 HTL/ 包晶界面的影响,它们对 PSC 的商业可行性起着重要作用,包括可扩展性、稳定性和环境安全性等关键因素。我们通过层均匀性和与大规模制造技术的兼容性研究了可扩展性挑战,这对于从实验室规模的原型转向大规模生产至关重要。稳定性问题包括 PSC 的运行寿命和环境耐久性,强调了底层在防止降解方面的重要性。此外,我们还探讨了环境安全措施,强调了通过复杂的 HTL 和 HTL/过氧化物界面工程来减少铅泄漏的方法。通过对这些关键方面的整体评估,本综述旨在为即将到来的 PSC 技术改进绘制蓝图,强调优化 HTL 和 HTL/过氧化物界面的必要性,以克服商业化障碍,充分挖掘 PSC 在可持续能源生产方面的潜力。
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引用次数: 0
Highly asymmetrically configured single atoms anchored on flame-roasting deposited carbon black as cathode catalysts for ultrahigh power density Zn-air batteries 锚定在火焰焙烧沉积炭黑上的高度不对称配置单原子作为超高功率密度锌-空气电池的阴极催化剂
IF 22.2 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-01 DOI: 10.1016/j.enchem.2024.100134
Yu-Chieh Ting , Chih-Chieh Cheng , Fan-Yu Yen , Guan-Ru Li , Shao-I Chang , Chih-Heng Lee , Hsin-Yi Tiffany Chen , Shih-Yuan Lu
Iron group element-based single atom (SA) catalysts are highly regarded as promising alternatives to commercial Pt/C for catalysis of oxygen reduction reaction (ORR). For applications in rechargeable zinc-air batteries (ZABs), achieving the necessary high catalytic efficiency of the SAs toward oxygen evolution reaction (OER) however remains a significant challenge. Here, highly asymmetrically configured Fe SAs created with N,S co-coordination and anchored on flame-roasting deposited carbon black (CB), Fe-N3S1/CB, are developed, achieving outstanding bifunctional oxygen catalytic efficiency, with an ultra-small potential gap of 0.661 V at 10 mA cm-2 (ΔE10), outperforming the (Pt/C+RuO2) composite catalyst (0.697 V). With a newly proposed binder-free composite air cathode design, the Fe-N3S1/CB based ZAB achieves an ultrahigh power density of 365.7 mW cm-2 at a current density of 511.3 mA cm-2, largely outperforming the (Pt/C+RuO2) based ZAB (225.9 mW cm-2 at 344.7 mA cm-2). Furthermore, the Fe-N3S1/CB based ZAB demonstrates excellent long-term stability, with only 8.2 % decay in round-trip efficiency over 1000 (333.3 h) charge-discharge cycles at 10 mA cm-2. Density functional theory calculations elucidate that incorporation of sulfur into the coordination sphere of Fe facilitates the electrochemical dehydroxylation step for ORR and accelerates the electrochemical O2 desorption step for OER, thereby reducing the corresponding free energy differences on Fe SAs for largely enhanced catalytic efficiency.
1. A large size hetero-atom element, sulfur, is introduced to create highly asymmetrically configured Fe single atoms for enhancements in catalytic efficiency toward both oxygen reduction reaction and oxygen evolution reaction, and a binder-free composite air cathode design is proposed to improve electrochemical performances of zinc-air batteries.
2. An ultra-small potential gap of 0.661 V at 10 mA cm-2 (ΔE10) is achieved for the air cathode, and an ultrahigh discharge power density of 365.7 mW cm-2 at a current density of 511.3 mA cm-2 is acquired for the zinc-air battery.
以铁族元素为基础的单原子(SA)催化剂在催化氧还原反应(ORR)方面被认为是商用铂/钯(Pt/C)的理想替代品。然而,要在可充电锌-空气电池(ZABs)中实现单原子催化剂对氧进化反应(OER)所需的高催化效率,仍然是一项重大挑战。本文开发了高度不对称配置的铁质 SAs(Fe-N3S1/CB),这种 SAs 具有 N、S 共配位,并锚定在火焰焙烧沉积的炭黑(CB)上,实现了出色的双功能氧催化效率,在 10 mA cm-2 时具有 0.661 V 的超小电位差(ΔE10),优于(Pt/C+RuO2)复合催化剂(0.697 V)。通过新提出的无粘结剂复合空气阴极设计,基于 Fe-N3S1/CB 的 ZAB 在 511.3 mA cm-2 的电流密度下实现了 365.7 mW cm-2 的超高功率密度,大大超过了基于(Pt/C+RuO2)的 ZAB(在 344.7 mA cm-2 下为 225.9 mW cm-2)。此外,基于 Fe-N3S1/CB 的 ZAB 还具有出色的长期稳定性,在 10 mA cm-2 的条件下,经过 1000 次(333.3 h)充放电循环后,往返效率仅下降 8.2%。密度泛函理论计算阐明,在铁的配位层中加入硫元素可促进 ORR 的电化学脱羟步骤,并加速 OER 的电化学 O2 解吸步骤,从而减少铁 SA 上的相应自由能差,在很大程度上提高催化效率。引入大尺寸异质原子元素硫,创造出高度不对称配置的铁单质原子,从而提高氧还原反应和氧进化反应的催化效率,并提出一种无粘结剂的复合空气阴极设计,以改善锌-空气电池的电化学性能。空气阴极在 10 mA cm-2 条件下实现了 0.661 V 的超小电位差(ΔE10),锌空气电池在 511.3 mA cm-2 电流密度条件下获得了 365.7 mW cm-2 的超高放电功率密度。
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EnergyChem
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