Aqueous zinc-ion batteries (AZIBs) represent a forefront technology for grid-scale energy storage, distinguished by inherent safety, economic viability, and ecological compatibility. Nevertheless, prevailing AZIBs research remains tethered to conventional methods, thereby hindering both mechanism elucidation and real-world interdisciplinary application. In this review, we commence by critically examining recent advancements in methodological innovations pertaining to the optimization of cathode, anode, and electrolyte in AZIBs. Subsequently, we elucidate pioneering applications of AZIBs in emerging domains, with particular emphasis on their enormous potential in biomedical technologies. To conclude, we unveil contemporary challenges, propose evidence-based strategies, and delineate future directions to establish robust theoretical cornerstones and practical roadmaps for the commercial scalability of AZIBs. By integrating foundational science with cross-disciplinary research achievements, this review aims to substantially advance fundamental comprehension of AZIBs while accelerating their multidisciplinary progress across diverse technological frontiers.
{"title":"Novel approaches to aqueous zinc-ion batteries: Challenges, strategies, and prospects","authors":"Wei Lv, Junlin Liu, Zilei Shen, Xudong Li, Chao Xu","doi":"10.1016/j.esci.2025.100410","DOIUrl":"10.1016/j.esci.2025.100410","url":null,"abstract":"<div><div>Aqueous zinc-ion batteries (AZIBs) represent a forefront technology for grid-scale energy storage, distinguished by inherent safety, economic viability, and ecological compatibility. Nevertheless, prevailing AZIBs research remains tethered to conventional methods, thereby hindering both mechanism elucidation and real-world interdisciplinary application. In this review, we commence by critically examining recent advancements in methodological innovations pertaining to the optimization of cathode, anode, and electrolyte in AZIBs. Subsequently, we elucidate pioneering applications of AZIBs in emerging domains, with particular emphasis on their enormous potential in biomedical technologies. To conclude, we unveil contemporary challenges, propose evidence-based strategies, and delineate future directions to establish robust theoretical cornerstones and practical roadmaps for the commercial scalability of AZIBs. By integrating foundational science with cross-disciplinary research achievements, this review aims to substantially advance fundamental comprehension of AZIBs while accelerating their multidisciplinary progress across diverse technological frontiers.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100410"},"PeriodicalIF":36.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340507","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-01Epub Date: 2024-12-07DOI: 10.1016/j.esci.2024.100352
Xiu-Mei Lin , Yu-Lin Sun , Yan-Xin Chen , Shun-Xing Li , Jian-Feng Li
Electrocatalysis plays an essential role in sustainable energy conversion technologies such as fuel cells, water electrolysis, and the carbon dioxide reduction reaction that occurs at solid–liquid interfaces. However, due to the complexity of the respective electrochemical interfaces and trace amounts of interfacial species, researchers’ knowledge of these reaction mechanisms remains incomplete, limiting our ability to improve electrocatalytic performance. In situ electrochemical surface-enhanced Raman spectroscopy (EC-SERS) has proven to have appealing potential for the study of electrocatalytic reaction mechanisms because it can provide exceptionally sensitive fingerprint vibrational spectroscopic information about interfacial species and their interactions. This review offers insights into electrocatalysis through in situ EC-SERS. We begin with an introduction to the basic principles, substrate engineering, and the implementation of in situ EC-SERS for electrocatalysis, with an emphasis on capturing trace interfacial species and determining the capability of this technique. We then discuss fundamentals, still-debated mechanistic issues, as well as advanced applications of EC-SERS for mechanism studies of the fundamentally and practically important reactions in sustainable energy conversion technologies, to gain insights into electrocatalysis. Finally, we propose directions for the future development of in situ EC-SERS in catalysis. Through this review paper, we aim to attract greater attention to the use of in situ EC-SERS in catalysis studies and introduce versatile methodologies and techniques for catalytic studies that will result in superior performance.
{"title":"Insights into electrocatalysis through in situ electrochemical surface-enhanced Raman spectroscopy","authors":"Xiu-Mei Lin , Yu-Lin Sun , Yan-Xin Chen , Shun-Xing Li , Jian-Feng Li","doi":"10.1016/j.esci.2024.100352","DOIUrl":"10.1016/j.esci.2024.100352","url":null,"abstract":"<div><div>Electrocatalysis plays an essential role in sustainable energy conversion technologies such as fuel cells, water electrolysis, and the carbon dioxide reduction reaction that occurs at solid–liquid interfaces. However, due to the complexity of the respective electrochemical interfaces and trace amounts of interfacial species, researchers’ knowledge of these reaction mechanisms remains incomplete, limiting our ability to improve electrocatalytic performance. <em>In situ</em> electrochemical surface-enhanced Raman spectroscopy (EC-SERS) has proven to have appealing potential for the study of electrocatalytic reaction mechanisms because it can provide exceptionally sensitive fingerprint vibrational spectroscopic information about interfacial species and their interactions. This review offers insights into electrocatalysis through <em>in situ</em> EC-SERS. We begin with an introduction to the basic principles, substrate engineering, and the implementation of <em>in situ</em> EC-SERS for electrocatalysis, with an emphasis on capturing trace interfacial species and determining the capability of this technique. We then discuss fundamentals, still-debated mechanistic issues, as well as advanced applications of EC-SERS for mechanism studies of the fundamentally and practically important reactions in sustainable energy conversion technologies, to gain insights into electrocatalysis. Finally, we propose directions for the future development of <em>in situ</em> EC-SERS in catalysis. Through this review paper, we aim to attract greater attention to the use of <em>in situ</em> EC-SERS in catalysis studies and introduce versatile methodologies and techniques for catalytic studies that will result in superior performance.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100352"},"PeriodicalIF":36.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-01Epub Date: 2025-02-12DOI: 10.1016/j.esci.2025.100378
Sixiao Liu , Jun Lu , Xu Yu , Huan Pang , Qiang Zhang , Ho Seok Park
A faster and more environmentally friendly nitrogen treatment solution is required to address the demand for nitrogen resources and the negative environmental impacts of human activities. Nitrogen electrochemistry thus has received major attention as an avenue for achieving sustainable nitrogen conversion. Here, we comprehensively review recent progress in the rational design of metal–organic framework nanoparticle composites (MOF–NP) for sustainable nitrogen electrochemistry. Three synthesis MOF–NPs strategies are addressed, focusing on the growth of MOFs on NPs, the loading of NPs onto/into MOFs, and the simultaneous formation of MOFs and NPs. We also discuss the unique features of MOF materials and their derivatives for use in nitrogen reduction, nitrate reduction, and ammonia oxidation reactions. The review closes by describing the prospects and challenges for MOF–NP-based electrocatalysts in nitrogen electrochemistry applications.
{"title":"Rational design of metal–organic framework-nanoparticle composite electrocatalysts for sustainable nitrogen electrochemistry","authors":"Sixiao Liu , Jun Lu , Xu Yu , Huan Pang , Qiang Zhang , Ho Seok Park","doi":"10.1016/j.esci.2025.100378","DOIUrl":"10.1016/j.esci.2025.100378","url":null,"abstract":"<div><div>A faster and more environmentally friendly nitrogen treatment solution is required to address the demand for nitrogen resources and the negative environmental impacts of human activities. Nitrogen electrochemistry thus has received major attention as an avenue for achieving sustainable nitrogen conversion. Here, we comprehensively review recent progress in the rational design of metal–organic framework nanoparticle composites (MOF–NP) for sustainable nitrogen electrochemistry. Three synthesis MOF–NPs strategies are addressed, focusing on the growth of MOFs on NPs, the loading of NPs onto/into MOFs, and the simultaneous formation of MOFs and NPs. We also discuss the unique features of MOF materials and their derivatives for use in nitrogen reduction, nitrate reduction, and ammonia oxidation reactions. The review closes by describing the prospects and challenges for MOF–NP-based electrocatalysts in nitrogen electrochemistry applications.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100378"},"PeriodicalIF":36.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340504","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-01Epub Date: 2025-03-19DOI: 10.1016/j.esci.2025.100402
Zhirong Zhang , Peiyu Ma , Chuanyi Jia , Wenting Gao , Mingkai Liu , Kwun Nam Hui , Ming Zuo , Shiming Zhou , Jie Zeng
Developing efficient and economical non-precious metal electrocatalysts for acidic oxygen evolution reaction (OER) is crucial for proton exchange membrane water electrolyzers (PEMWE). Spinel oxides are considered promising non-precious acidic OER catalysts due to their excellent activities. However, the structure dissolution of spinel oxides in acidic conditions severely limits their applications in PEMWE. Introducing acid-resistant heteroatoms into spinel oxides is an available strategy to enhance their stability. Herein, by anchoring Ir single atoms at different sites of spinel oxide Co3O4, we demonstrated that the stabilizing effect strongly depends on the single-atom anchoring site. Electrochemical measurements and in situ spectroscopic characterization revealed that the Ir single atoms anchored at lattice sites significantly enhanced the stability of Co3O4 during acidic OER in comparison with ones at three-fold hollow sites. The long-term durability test showed that the Ir single atoms at lattice sites stabilized Co3O4 during a 200 h continuous operation at a current density of 10 mA cm−2. Moreover, the resultant PEMWE device fabricated by the catalyst achieved a stability time of about 60 h at a current density of 1 A cm−2. Mechanistic studies revealed that Ir single atoms at lattice sites enhanced the covalency between Co and O atoms, thereby suppressing their migration and improving the stability of spinel oxides. The discovery of the site-specific stabilizing effect of single atoms provides essential guidance for the rational design of highly stable electrocatalysts for PEMWE.
开发高效、经济的非贵金属酸性析氧电催化剂是质子交换膜水电解槽（PEMWE）发展的关键。尖晶石氧化物因其优异的活性被认为是很有前途的非贵重酸性OER催化剂。然而，尖晶石氧化物在酸性条件下的结构溶解严重限制了其在PEMWE中的应用。在尖晶石氧化物中引入耐酸杂原子是提高其稳定性的一种有效策略。本文通过将Ir单原子锚定在尖晶石氧化物Co3O4的不同位点，证明了稳定效果强烈依赖于单原子锚定位点。电化学测量和原位光谱表征表明，在酸性OER中，固定在晶格位置的Ir单原子比固定在三层空心位置的Ir单原子显著提高了Co3O4的稳定性。长期耐久性测试表明，在10 mA cm−2的电流密度下，晶格位置的Ir单原子在200 h的连续工作中稳定了Co3O4。此外，该催化剂制备的PEMWE器件在电流密度为1 a cm−2时的稳定时间约为60 h。机制研究表明，晶格位置的Ir单原子增强了Co和O原子之间的共价，从而抑制了Co和O原子的迁移，提高了尖晶石氧化物的稳定性。单原子的定点稳定效应的发现，为合理设计高稳定性的PEMWE电催化剂提供了重要的指导。
{"title":"Site-specific stabilizing effect of single atoms on spinel oxides for acidic oxygen evolution","authors":"Zhirong Zhang , Peiyu Ma , Chuanyi Jia , Wenting Gao , Mingkai Liu , Kwun Nam Hui , Ming Zuo , Shiming Zhou , Jie Zeng","doi":"10.1016/j.esci.2025.100402","DOIUrl":"10.1016/j.esci.2025.100402","url":null,"abstract":"<div><div>Developing efficient and economical non-precious metal electrocatalysts for acidic oxygen evolution reaction (OER) is crucial for proton exchange membrane water electrolyzers (PEMWE). Spinel oxides are considered promising non-precious acidic OER catalysts due to their excellent activities. However, the structure dissolution of spinel oxides in acidic conditions severely limits their applications in PEMWE. Introducing acid-resistant heteroatoms into spinel oxides is an available strategy to enhance their stability. Herein, by anchoring Ir single atoms at different sites of spinel oxide Co<sub>3</sub>O<sub>4</sub>, we demonstrated that the stabilizing effect strongly depends on the single-atom anchoring site. Electrochemical measurements and <em>in situ</em> spectroscopic characterization revealed that the Ir single atoms anchored at lattice sites significantly enhanced the stability of Co<sub>3</sub>O<sub>4</sub> during acidic OER in comparison with ones at three-fold hollow sites. The long-term durability test showed that the Ir single atoms at lattice sites stabilized Co<sub>3</sub>O<sub>4</sub> during a 200 h continuous operation at a current density of 10 mA cm<sup>−</sup><sup>2</sup>. Moreover, the resultant PEMWE device fabricated by the catalyst achieved a stability time of about 60 h at a current density of 1 A cm<sup>−</sup><sup>2</sup>. Mechanistic studies revealed that Ir single atoms at lattice sites enhanced the covalency between Co and O atoms, thereby suppressing their migration and improving the stability of spinel oxides. The discovery of the site-specific stabilizing effect of single atoms provides essential guidance for the rational design of highly stable electrocatalysts for PEMWE.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100402"},"PeriodicalIF":36.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145528416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-01Epub Date: 2025-05-26DOI: 10.1016/j.esci.2025.100431
Xin Zhao , Zhonghan Zhang , Chenfei Li , Lizhen Liu , Yonghao Xiao , Zihao Wang , Shuzhou Li , Han Sen Soo
One solution to the intermittency of renewable energy sources is energy storage in fuels such as hydrogen produced by water electrolysis. However, current water electrolysis systems are plagued by high costs. Here, a co-electrolysis system for biomass-derived glucose and water is shown to achieve green hydrogen generation of over 500 μmol h−1 cm−2 using a membrane-free undivided cell with electrocatalysts comprising only earth-abundant elements, driven by a triple-junction photovoltaic. Glucose is selectively electrooxidized to formate with high yields of up to 80%, instead of water being oxidized into oxygen; the former circumvents the need for costly membranes to separate the hydrogen and oxygen gaseous products. High selectivity is achieved through cascade carbon–carbon bond oxidation by regulating the adsorption mode and moderating the oxidation state of cobalt with copper doping. The overall electrolysis potential is lowered by ∼400 mV compared to water splitting. The revenue from the formate co-product can lower the levelized cost of hydrogen from water electrolysis by $4.63/kg of hydrogen produced, making it competitive with grey hydrogen generation.
{"title":"Steering the adsorption modes and oxidation state of Co oxyhydroxide active sites to unlock selective glucose oxidation to formate for efficient solar reforming of biomass to green hydrogen","authors":"Xin Zhao , Zhonghan Zhang , Chenfei Li , Lizhen Liu , Yonghao Xiao , Zihao Wang , Shuzhou Li , Han Sen Soo","doi":"10.1016/j.esci.2025.100431","DOIUrl":"10.1016/j.esci.2025.100431","url":null,"abstract":"<div><div>One solution to the intermittency of renewable energy sources is energy storage in fuels such as hydrogen produced by water electrolysis. However, current water electrolysis systems are plagued by high costs. Here, a co-electrolysis system for biomass-derived glucose and water is shown to achieve green hydrogen generation of over 500 μmol h<sup>−1</sup> cm<sup>−2</sup> using a membrane-free undivided cell with electrocatalysts comprising only earth-abundant elements, driven by a triple-junction photovoltaic. Glucose is selectively electrooxidized to formate with high yields of up to 80%, instead of water being oxidized into oxygen; the former circumvents the need for costly membranes to separate the hydrogen and oxygen gaseous products. High selectivity is achieved through cascade carbon–carbon bond oxidation by regulating the adsorption mode and moderating the oxidation state of cobalt with copper doping. The overall electrolysis potential is lowered by ∼400 mV compared to water splitting. The revenue from the formate co-product can lower the levelized cost of hydrogen from water electrolysis by $4.63/kg of hydrogen produced, making it competitive with grey hydrogen generation.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100431"},"PeriodicalIF":36.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145366117","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-01Epub Date: 2025-05-16DOI: 10.1016/j.esci.2025.100430
Yang Liu , Ruyan Wu , Yongzhen Jin , Jiaye Dong , Hongju Li , Jianhui Wang
The practical application of the electrocatalytic methanol oxidation reaction (EMOR) has long been hindered by the lack of active and stable catalysts. Herein, we report a unique dealloyed PtMn catalyst on carbon cloth (d-PtMn/CC) characterized by a compressively strained Pt surface and a Mn concentration-gradient core. This d-PtMn/CC catalyst demonstrates EMOR activity that is 7–14 times higher than that of conventional Pt/CC catalysts in all-pH electrolytes, while exhibiting exceptional resistance to catalytic poisoning over a broad potential range of 0.4–1.2 V vs. reversible hydrogen electrode (RHE). When employed in direct methanol fuel cells, it achieves 111.6 mW cm−2 for over 10 h at ultralow 0.59 mgPt cm−2, substantially outperforming commercial Pt/C catalysts. Comparative analyses of adsorbed reactants/intermediates revealed that imbalanced adsorption of reactants on the catalyst surface is the primary cause of EMOR poisoning. The d-PtMn/CC catalyst, benefiting from surface compressive strain and ligand effects, maintains balanced reactant adsorption over the wide potential range, thereby achieving ultra-stable EMOR performance. These findings not only resolve the longstanding controversy regarding EMOR poisoning mechanism but also identify the effectiveness of the “ligand + surface strain” strategy in DMFCs, facilitating its practical applications.
由于缺乏活性稳定的催化剂，电催化甲醇氧化反应（EMOR）的实际应用一直受到阻碍。在此，我们报道了一种独特的碳布合金PtMn催化剂（d-PtMn/CC），其特征是压缩应变的Pt表面和Mn浓度梯度的核心。这种d-PtMn/CC催化剂的EMOR活性比传统Pt/CC催化剂在全ph电解质中的EMOR活性高7-14倍，同时与可逆氢电极（RHE）相比，在0.4-1.2 V的宽电位范围内表现出优异的抗催化中毒能力。当用于直接甲醇燃料电池时，它在超低0.59 mgPt cm - 2下达到111.6 mW cm - 2超过10小时，大大优于商用Pt/C催化剂。吸附反应物/中间体的对比分析表明，反应物在催化剂表面的不平衡吸附是EMOR中毒的主要原因。d-PtMn/CC催化剂得益于表面压缩应变和配体效应，在较宽的电位范围内保持平衡的反应物吸附，从而实现超稳定的EMOR性能。这些发现不仅解决了长期以来关于EMOR中毒机制的争议，而且确定了“配体+表面应变”策略在dmfc中的有效性，为其实际应用提供了便利。
{"title":"Balancing reactant adsorption for ultra-stable electrocatalytic methanol oxidation reaction","authors":"Yang Liu , Ruyan Wu , Yongzhen Jin , Jiaye Dong , Hongju Li , Jianhui Wang","doi":"10.1016/j.esci.2025.100430","DOIUrl":"10.1016/j.esci.2025.100430","url":null,"abstract":"<div><div>The practical application of the electrocatalytic methanol oxidation reaction (EMOR) has long been hindered by the lack of active and stable catalysts. Herein, we report a unique dealloyed PtMn catalyst on carbon cloth (<em>d</em>-PtMn/CC) characterized by a compressively strained Pt surface and a Mn concentration-gradient core. This <em>d</em>-PtMn/CC catalyst demonstrates EMOR activity that is 7–14 times higher than that of conventional Pt/CC catalysts in all-pH electrolytes, while exhibiting exceptional resistance to catalytic poisoning over a broad potential range of 0.4–1.2 V vs. reversible hydrogen electrode (RHE). When employed in direct methanol fuel cells, it achieves 111.6 mW cm<sup>−2</sup> for over 10 h at ultralow 0.59 mg<sub>Pt</sub> cm<sup>−2</sup>, substantially outperforming commercial Pt/C catalysts. Comparative analyses of adsorbed reactants/intermediates revealed that imbalanced adsorption of reactants on the catalyst surface is the primary cause of EMOR poisoning. The <em>d</em>-PtMn/CC catalyst, benefiting from surface compressive strain and ligand effects, maintains balanced reactant adsorption over the wide potential range, thereby achieving ultra-stable EMOR performance. These findings not only resolve the longstanding controversy regarding EMOR poisoning mechanism but also identify the effectiveness of the “ligand + surface strain” strategy in DMFCs, facilitating its practical applications.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100430"},"PeriodicalIF":36.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145366119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-01Epub Date: 2025-04-03DOI: 10.1016/j.esci.2025.100406
Haoxiang Sun , Youxuan Ni , Xinyao Wu , Dongjie Shi , Zhenhua Yan , Kai Zhang , Fangyi Cheng , Weiwei Xie , Wei Zhang , Jun Chen
Migration of transition metal (TM) ions out of the TM layer is detrimental and unavoidable in lithium-rich layered oxides, which drives in-plane cation migration, O2 release and energy loss. Since out-of-plane migration generally occurs through tetrahedral interstices (TLi) in the Li layer, doping TLi sites has been believed as a promising way to block migration pathways at the dopant site. However, with only trace dopants (<1 at.%) sparsely distributed in bulk, the ability of isolated dopants to suppress cation disorder in undoped regions remains unknown—largely due to no suitable model materials. Here, combining atomic-scale imaging, X-ray diffraction measurements and first-principles calculations, we demonstrate that W6+ ions (0.75 at.%) can occupy TLi sites in Li1·2Mn0·6Ni0·2O2. TLi-site doping maximizes dopant efficiency, as each single W6+ ion exerts a long-range Coulomb repulsion on TM/Li+ ions in the TM layer, suppressing both in-plane and out-of-plane cation migration over a broad range (∼2 nm diameter), in contrast to local stabilization via other doping techniques. Remarkably, cation ordering is preserved for over 250 cycles, far exceeding the limited structural stability (∼50 cycles) typically achieved with conventional modification strategies. Consequently, O2 release and formation of low-voltage Mn3+/Mn4+ redox couple are inhibited, resulting in negligible voltage decay.
{"title":"Single-dopant long-range stabilization in long-cycled Li-rich layered cathodes via trace tetrahedral-site doping","authors":"Haoxiang Sun , Youxuan Ni , Xinyao Wu , Dongjie Shi , Zhenhua Yan , Kai Zhang , Fangyi Cheng , Weiwei Xie , Wei Zhang , Jun Chen","doi":"10.1016/j.esci.2025.100406","DOIUrl":"10.1016/j.esci.2025.100406","url":null,"abstract":"<div><div>Migration of transition metal (TM) ions out of the TM layer is detrimental and unavoidable in lithium-rich layered oxides, which drives in-plane cation migration, O<sub>2</sub> release and energy loss. Since out-of-plane migration generally occurs through tetrahedral interstices (T<sub>Li</sub>) in the Li layer, doping T<sub>Li</sub> sites has been believed as a promising way to block migration pathways at the dopant site. However, with only trace dopants (<1 at.%) sparsely distributed in bulk, the ability of isolated dopants to suppress cation disorder in undoped regions remains unknown—largely due to no suitable model materials. Here, combining atomic-scale imaging, X-ray diffraction measurements and first-principles calculations, we demonstrate that W<sup>6+</sup> ions (0.75 at.%) can occupy T<sub>Li</sub> sites in Li<sub>1</sub><sub>·</sub><sub>2</sub>Mn<sub>0·6</sub>Ni<sub>0·2</sub>O<sub>2</sub>. T<sub>Li</sub>-site doping maximizes dopant efficiency, as each single W<sup>6+</sup> ion exerts a long-range Coulomb repulsion on TM/Li<sup>+</sup> ions in the TM layer, suppressing both in-plane and out-of-plane cation migration over a broad range (∼2 nm diameter), in contrast to local stabilization via other doping techniques. Remarkably, cation ordering is preserved for over 250 cycles, far exceeding the limited structural stability (∼50 cycles) typically achieved with conventional modification strategies. Consequently, O<sub>2</sub> release and formation of low-voltage Mn<sup>3+</sup>/Mn<sup>4+</sup> redox couple are inhibited, resulting in negligible voltage decay.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100406"},"PeriodicalIF":36.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145366120","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two-dimensional (2D) reticular framework films featuring highly accessible surface areas, tunable active sites, and well-defined channels are promising candidates for flexible in-plane micro-supercapacitor (MSC) electrodes. However, the interlayer Van der Waals forces in 2D heterojunctions can limit mass/charge transport. Herein, we design a non-Van der Waals force bonded heterojunction of covalent organic frameworks (COFs) and metal–organic frameworks (MOFs) linked by metal-ion coordination. A COF@MOF monolithic nanofilm is constructed by growing MOF (M3(HHTP)2) in situ on the COF (COFTD) surface, using nickel (Ni) as the optimal metal to connect the two layers and form a sandwich electrode. We further explore various transition metals in M3(HHTP)2, from manganese (Mn) to zinc (Zn), to adjust the electronic structure and charge redistribution. The optimal MSC-Ni-COFTD@Co3(HHTP)2 device exhibits an impressive specific capacitance (1645.3 F cm−3 at 10 mV s−1), a high energy density (146.3 mWh cm−3), as well as superior cycling and bending stability. This work offers an innovative perspective on overcoming the mass transfer and electron migration limitations of 2D reticular frameworks for miniaturization and wearable energy storage electronics.
二维（2D）网状框架薄膜具有高度可接近的表面积、可调的活性位点和明确的通道，是柔性面内微超级电容器（MSC）电极的有希望的候选者。然而，二维异质结中的层间范德华力会限制质量/电荷输运。本文设计了共价有机骨架（COFs）和金属-有机骨架（MOFs）通过金属离子配位连接的非范德华力键异质结。通过在COF （COFTD）表面原位生长MOF (M3(HHTP)2)，以镍（Ni）作为连接两层的最佳金属，形成夹层电极，构建了COF@MOF单片纳米膜。我们进一步探索了M3(HHTP)2中的各种过渡金属，从锰（Mn）到锌（Zn），以调节电子结构和电荷再分配。最佳的MSC-Ni-COFTD@Co3(HHTP)2器件具有令人印象深刻的比电容（10mv s - 1时1645.3 F cm - 3），高能量密度（146.3 mWh cm - 3），以及优越的循环和弯曲稳定性。这项工作为克服小型化和可穿戴储能电子设备的二维网状框架的传质和电子迁移限制提供了一个创新的视角。
{"title":"Metal ion-bonded two-dimensional framework non-Van der Waals sandwich heterojunctions for fast mass transfer in flexible in-plane micro-supercapacitors","authors":"Xiaoyang Xu , Zhenni Zhang , Zihao Zhang , Xiaomi Tang , Hong Chen , Tian Li , Jia Zhang , Qingliang Feng , Shanlin Qiao","doi":"10.1016/j.esci.2025.100404","DOIUrl":"10.1016/j.esci.2025.100404","url":null,"abstract":"<div><div>Two-dimensional (2D) reticular framework films featuring highly accessible surface areas, tunable active sites, and well-defined channels are promising candidates for flexible in-plane micro-supercapacitor (MSC) electrodes. However, the interlayer Van der Waals forces in 2D heterojunctions can limit mass/charge transport. Herein, we design a non-Van der Waals force bonded heterojunction of covalent organic frameworks (COFs) and metal–organic frameworks (MOFs) linked by metal-ion coordination. A COF@MOF monolithic nanofilm is constructed by growing MOF (M<sub>3</sub>(HHTP)<sub>2</sub>) <em>in situ</em> on the COF (COF<sub>TD</sub>) surface, using nickel (Ni) as the optimal metal to connect the two layers and form a sandwich electrode. We further explore various transition metals in M<sub>3</sub>(HHTP)<sub>2</sub>, from manganese (Mn) to zinc (Zn), to adjust the electronic structure and charge redistribution. The optimal MSC-Ni-COF<sub>TD</sub>@Co<sub>3</sub>(HHTP)<sub>2</sub> device exhibits an impressive specific capacitance (1645.3 F cm<sup>−3</sup> at 10 mV s<sup>−1</sup>), a high energy density (146.3 mWh cm<sup>−3</sup>), as well as superior cycling and bending stability. This work offers an innovative perspective on overcoming the mass transfer and electron migration limitations of 2D reticular frameworks for miniaturization and wearable energy storage electronics.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100404"},"PeriodicalIF":36.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145366121","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-01Epub Date: 2025-07-23DOI: 10.1016/j.esci.2025.100455
Xueting Hu , Guojun Lai , Yangyang Liu , Peng Zhou , Bingan Lu , Zeinhom M. El-Bahy , Manal S. Ebaid , Lina Chen , Jiang Zhou
Zinc-iodine (Zn–I2) batteries hold great promise for large-scale applications, yet their practical deployment is constrained by uncontrollable iodine conversion, polyiodide shuttling, and unpredictable zinc (Zn) depositional morphology. Furthermore, the mismatched kinetics of its interfacial reactions demand significant attention. Herein, we introduce a betaine (Bet) additive as a dual-electrode interfacial regulator to synergistically address the challenges faced at both the anode and cathode interface. Specifically, the hydrophilic group (–COO) of Bet preferentially adsorbs on the Zn anode surface, modulating Zn2+ solvation and electrodeposition dynamics to enable highly uniform Zn plating, extending the Zn–Zn symmetric cell lifespan beyond 7000 h at 1 mA cm−2. Moreover, Bet's lipophilic group (–N–R3) interacts with polyiodides, suppressing their migration and accelerating iodine redox kinetics, thereby mitigating cathodic side reactions. Consequently, Zn–I2 full-cell demonstrates exceptional cycle life, maintaining capacity with an ultralow decay rate of 0.007‰ per cycle over 15,500 cycles at 10 mA cm−2. Furthermore, an Ah-level pouch cell of ∼1.15 Ah can deliver a competitive capacity retention of 92.1% after 600 cycles, highlighting the scalability of this approach. This cost-effective and efficient interfacial modulation strategy offers a new perspective for realizing long-cycle Zn–I2 batteries and advancing their practical applications.
锌-碘（Zn - i2）电池具有大规模应用的巨大前景，但其实际部署受到不可控的碘转化、多碘化物穿梭和不可预测的锌（Zn）沉积形态的限制。此外，其界面反应的不匹配动力学值得重视。在此，我们引入甜菜碱（Bet）添加剂作为双电极界面调节剂，以协同解决阳极和阴极界面面临的挑战。具体来说，Bet的亲水性基团（-COO）优先吸附在Zn阳极表面，调节Zn2+的溶剂化和电沉积动力学，实现高度均匀的Zn电镀，延长Zn - Zn对称电池在1 mA cm - 2下的寿命超过7000小时。此外，Bet的亲脂基团（-N-R3）与多碘化物相互作用，抑制它们的迁移并加速碘氧化还原动力学，从而减轻阴极副反应。因此，锌- i2全电池表现出优异的循环寿命，在10 mA cm - 2下，在15,500次循环中，每循环保持0.007‰的超低衰减率。此外，约1.15 Ah的Ah级袋状电池在600次循环后可提供92.1%的竞争容量保留，突出了该方法的可扩展性。这种经济高效的界面调制策略为实现长周期锌- i2电池和推进其实际应用提供了新的前景。
{"title":"Design of dual-electrode interfacial kinetics regulator for long-lasting Ah-level zinc-iodine batteries","authors":"Xueting Hu , Guojun Lai , Yangyang Liu , Peng Zhou , Bingan Lu , Zeinhom M. El-Bahy , Manal S. Ebaid , Lina Chen , Jiang Zhou","doi":"10.1016/j.esci.2025.100455","DOIUrl":"10.1016/j.esci.2025.100455","url":null,"abstract":"<div><div>Zinc-iodine (Zn–I<sub>2</sub>) batteries hold great promise for large-scale applications, yet their practical deployment is constrained by uncontrollable iodine conversion, polyiodide shuttling, and unpredictable zinc (Zn) depositional morphology. Furthermore, the mismatched kinetics of its interfacial reactions demand significant attention. Herein, we introduce a betaine (Bet) additive as a dual-electrode interfacial regulator to synergistically address the challenges faced at both the anode and cathode interface. Specifically, the hydrophilic group (–COO) of Bet preferentially adsorbs on the Zn anode surface, modulating Zn<sup>2+</sup> solvation and electrodeposition dynamics to enable highly uniform Zn plating, extending the Zn–Zn symmetric cell lifespan beyond 7000 h at 1 mA cm<sup>−2</sup>. Moreover, Bet's lipophilic group (–N–R<sub>3</sub>) interacts with polyiodides, suppressing their migration and accelerating iodine redox kinetics, thereby mitigating cathodic side reactions. Consequently, Zn–I<sub>2</sub> full-cell demonstrates exceptional cycle life, maintaining capacity with an ultralow decay rate of 0.007‰ per cycle over 15,500 cycles at 10 mA cm<sup>−2</sup>. Furthermore, an Ah-level pouch cell of ∼1.15 Ah can deliver a competitive capacity retention of 92.1% after 600 cycles, highlighting the scalability of this approach. This cost-effective and efficient interfacial modulation strategy offers a new perspective for realizing long-cycle Zn–I<sub>2</sub> batteries and advancing their practical applications.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100455"},"PeriodicalIF":36.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425511","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-01Epub Date: 2025-03-25DOI: 10.1016/j.esci.2025.100403
Zhiang Hu , Han Wu , Xue Yong , Geoffrey I.N. Waterhouse , Zhiyong Tang , Junbiao Chang , Jiangwei Chang , Siyu Lu
The oxygen evolution reaction (OER), owing to its low kinetics, is a major obstacle to electrochemical water-splitting, which is essential for converting sustainable energy into clean and stable hydrogen energy carriers. The growing need for high-performance electrocatalysts to meet industrial demands, along with a deepening exploration of the OER catalytic process, has led to advancements in OER catalyst design—from conventional single-site mechanisms (SSMs) to more sophisticated dual-site mechanisms (DSMs). However, DSMs, with their complex reaction pathways, still face multiple challenges in progressing towards industrial application, making a deeper understanding of these mechanisms essential. This review first examines the latest DSMs associated with the OER and compares them with conventional SSMs. On this basis, we highlight the structure–activity relationships and design principles of catalysts that align with DSMs by integrating experimental evidence with theoretical analysis. In addition, quasi in situ and in situ spectral detection techniques for DSM analysis are introduced, and the challenges and prospects for these new detection techniques are discussed.
{"title":"Advances in dual-site mechanisms for designing high-performance oxygen evolution electrocatalysts","authors":"Zhiang Hu , Han Wu , Xue Yong , Geoffrey I.N. Waterhouse , Zhiyong Tang , Junbiao Chang , Jiangwei Chang , Siyu Lu","doi":"10.1016/j.esci.2025.100403","DOIUrl":"10.1016/j.esci.2025.100403","url":null,"abstract":"<div><div>The oxygen evolution reaction (OER), owing to its low kinetics, is a major obstacle to electrochemical water-splitting, which is essential for converting sustainable energy into clean and stable hydrogen energy carriers. The growing need for high-performance electrocatalysts to meet industrial demands, along with a deepening exploration of the OER catalytic process, has led to advancements in OER catalyst design—from conventional single-site mechanisms (SSMs) to more sophisticated dual-site mechanisms (DSMs). However, DSMs, with their complex reaction pathways, still face multiple challenges in progressing towards industrial application, making a deeper understanding of these mechanisms essential. This review first examines the latest DSMs associated with the OER and compares them with conventional SSMs. On this basis, we highlight the structure–activity relationships and design principles of catalysts that align with DSMs by integrating experimental evidence with theoretical analysis. In addition, quasi in situ and in situ spectral detection techniques for DSM analysis are introduced, and the challenges and prospects for these new detection techniques are discussed.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100403"},"PeriodicalIF":36.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340506","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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