Qi Zhou, Yan Shi, Rui Li, Xiang Luo, Guoqing Zhao, Mengxiao Li, Fei Wu, Junjie Wang, Yu Li, Mingjun Hu, Shuang Wei, Jun Yang
Aqueous proton batteries (APBs) have emerged as a promising candidate for next-generation energy storage systems due to their intrinsic low cost, exceptional safety, and competitive power/energy density. However, the widely used MnO2 cathode in acidic electrolytes typically operates relying on a dissolution-deposition chemistry, inherently plagued by low manganese utilization efficiency and subpar practical energy density. Herein, we report a novel Mn-based cathode material—Mn2O3—for a proton battery, which demonstrates high redox potential and superior specific capacity. Nevertheless, as an Mn-based cathode material, Mn2O3 still suffers from dissolution and capacity decay in the long-term cycling process. To address this challenge, an in situ polymer-metal complex interphase engineering strategy was proposed to regulate the proton transfer kinetics and inhibit the dissolution of the Mn2O3 electrode. In this strategy, polyacrylonitrile (PAN) was employed as both the coating matrix and the adhesive while acting as a metal ligand after cyclization. Manganese triflate (Mn(OTf)2) was introduced to catalyze the pyrolysis of cyano groups and coordinate with the generated pyridine nitrogen, driving crosslinking reactions to stabilize the polymer network and optimize ion transport pathways. Consequently, the functional PAN-Mn2+ complex interphase (C-PMn) inhibits the transport and dissolution of Mn2+ ions, enhances H+ permeability, and improves the capacity, cycling stability, and coulombic efficiency of the Mn2O3 cathode. For the first time, we reveal that the Mn2O3 cathode stores energy through a proton insertion/extraction mechanism in H2SO4 electrolyte, holding promise for high-energy-density rocking-chair proton batteries. As-assembled diquinoxalino [2,3-a:2′,3′-c] phenazine (HATN)//Mn2O3 proton full battery exhibits a specific capacity of 239 mA h g−1 at 0.2 A g−1 (based on the cathode), an average discharge voltage of about 1 V, a good cycling stability (82% capacity retention after 500 cycles) and an energy density of 115 Wh kg−1 (based on the total mass of cathode and anode). These findings offer a promising cathode material for proton batteries and a cost-effective approach to optimizing the cathode performance in acidic electrolytes, thereby paving the way for the development of a durable, high-energy proton battery.
水性质子电池（apb）由于其固有的低成本、卓越的安全性和具有竞争力的功率/能量密度，已成为下一代储能系统的有希望的候选者。然而，在酸性电解质中广泛使用的二氧化锰阴极通常依赖于溶解-沉积化学，固有地受到锰利用效率低和实际能量密度低于标准的困扰。在此，我们报道了一种新型的锰基质子电池正极材料——mn2o3，它具有高氧化还原电位和优越的比容量。然而，作为锰基正极材料，Mn2O3在长期循环过程中仍然存在溶解和容量衰减的问题。为了解决这一挑战，研究人员提出了一种原位聚合物-金属络合物界面工程策略，以调节质子转移动力学并抑制Mn2O3电极的溶解。在该策略中，聚丙烯腈（PAN）作为涂层基质和粘合剂，同时在环化后作为金属配体。引入三酸锰（Mn(OTf)2）催化氰基热解，并与生成的吡啶氮配合，驱动交联反应，稳定聚合物网络，优化离子传输途径。因此，功能化PAN-Mn2+复合物界面（C-PMn）抑制了Mn2+离子的迁移和溶解，提高了H+的渗透率，提高了Mn2O3阴极的容量、循环稳定性和库仑效率。我们首次揭示了Mn2O3阴极在H2SO4电解质中通过质子插入/提取机制储存能量，有望用于高能量密度摇椅质子电池。组装后的二喹啉[2,3-a:2 ',3 ' -c]吩嗪(HATN)//Mn2O3质子电池在0.2 ag - 1时的比容量为239 mA h g - 1（基于阴极），平均放电电压约为1 V，循环稳定性好（500次循环后容量保持82%），能量密度为115 Wh kg - 1（基于阴极和阳极的总质量）。这些发现为质子电池提供了一种很有前途的阴极材料，并为优化阴极在酸性电解质中的性能提供了一种经济有效的方法，从而为开发耐用、高能质子电池铺平了道路。
{"title":"Enabling Durable and High-Energy Aqueous Proton Batteries by Engineering a Robust Polymer-Metal Complex Interphase on Mn2O3 Cathode","authors":"Qi Zhou, Yan Shi, Rui Li, Xiang Luo, Guoqing Zhao, Mengxiao Li, Fei Wu, Junjie Wang, Yu Li, Mingjun Hu, Shuang Wei, Jun Yang","doi":"10.1002/smll.202513715","DOIUrl":"https://doi.org/10.1002/smll.202513715","url":null,"abstract":"Aqueous proton batteries (APBs) have emerged as a promising candidate for next-generation energy storage systems due to their intrinsic low cost, exceptional safety, and competitive power/energy density. However, the widely used MnO<sub>2</sub> cathode in acidic electrolytes typically operates relying on a dissolution-deposition chemistry, inherently plagued by low manganese utilization efficiency and subpar practical energy density. Herein, we report a novel Mn-based cathode material—Mn<sub>2</sub>O<sub>3</sub>—for a proton battery, which demonstrates high redox potential and superior specific capacity. Nevertheless, as an Mn-based cathode material, Mn<sub>2</sub>O<sub>3</sub> still suffers from dissolution and capacity decay in the long-term cycling process. To address this challenge, an in situ polymer-metal complex interphase engineering strategy was proposed to regulate the proton transfer kinetics and inhibit the dissolution of the Mn<sub>2</sub>O<sub>3</sub> electrode. In this strategy, polyacrylonitrile (PAN) was employed as both the coating matrix and the adhesive while acting as a metal ligand after cyclization. Manganese triflate (Mn(OTf)<sub>2</sub>) was introduced to catalyze the pyrolysis of cyano groups and coordinate with the generated pyridine nitrogen, driving crosslinking reactions to stabilize the polymer network and optimize ion transport pathways. Consequently, the functional PAN-Mn<sup>2+</sup> complex interphase (C-PMn) inhibits the transport and dissolution of Mn<sup>2+</sup> ions, enhances H<sup>+</sup> permeability, and improves the capacity, cycling stability, and coulombic efficiency of the Mn<sub>2</sub>O<sub>3</sub> cathode. For the first time, we reveal that the Mn<sub>2</sub>O<sub>3</sub> cathode stores energy through a proton insertion/extraction mechanism in H<sub>2</sub>SO<sub>4</sub> electrolyte, holding promise for high-energy-density rocking-chair proton batteries. As-assembled diquinoxalino [2,3-a:2′,3′-c] phenazine (HATN)//Mn<sub>2</sub>O<sub>3</sub> proton full battery exhibits a specific capacity of 239 mA h g<sup>−1</sup> at 0.2 A g<sup>−1</sup> (based on the cathode), an average discharge voltage of about 1 V, a good cycling stability (82% capacity retention after 500 cycles) and an energy density of 115 Wh kg<sup>−1</sup> (based on the total mass of cathode and anode). These findings offer a promising cathode material for proton batteries and a cost-effective approach to optimizing the cathode performance in acidic electrolytes, thereby paving the way for the development of a durable, high-energy proton battery.","PeriodicalId":228,"journal":{"name":"Small","volume":"100 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968862","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}
Interfacial water serves as the intrinsic proton source for CO2 hydrogenation, yet synchronizing its activation with on-demand active hydrogen (*H) supply without triggering the hydrogen evolution reaction (HER) remains challenging. Herein, we construct an oxophilic amorphous MnOx overlayer on Ag to regulate the interfacial water network. In situ characterization and theoretical calculations demonstrate that under over 45% of interfacial water reorganizes into an ordered four-coordinate hydrogen-bonded (4-HB-H2O) structure under operation, facilitating targeted proton transfer to CO2 reduction intermediates. The distorted Mn-O polyhedra lower the water dissociation barrier by 0.54 eV while raising the HER barrier by 0.61 eV. It achieves a CO production rate of 12.8 mol h−1 g−1 and 68.6% Faraday efficiency (FE) at −1000 mA cm−2 and maintains >95% FECO over 500 h at −200 mA cm−2. It also enables efficient nitrate-to-ammonia conversion with the FE of 88.5 %, and the maximum NH3 production rate is 831.4 mmol h−1 g−1, and a Zn–CO2 rechargeable battery with FECO of 98.5% and power density of 2.1 mW cm−2. This study underscores the amorphous metal oxide-mediated interfacial water activation as a versatile and scalable strategy for enhancing selectivity in water-involved electrocatalytic reactions.
界面水作为CO2氢化的内在质子源，但在不触发析氢反应（HER）的情况下，将其与按需活性氢（*H）供应同步激活仍然是一个挑战。在此，我们在Ag上构建了一个亲氧无定形MnOx覆盖层来调节界面水网络。原位表征和理论计算表明，超过45%的界面水在操作过程中重组成有序的四坐标氢键（4-HB-H2O）结构，有利于质子定向转移到CO2还原中间体。扭曲的Mn-O多面体使水解离势垒降低了0.54 eV，使HER势垒提高了0.61 eV。在−1000 mA cm−2条件下，CO产率为12.8 mol h−1 g−1，法拉第效率（FE）为68.6%，在−200 mA cm−2条件下，500 h内FECO维持在95%。该工艺还实现了高效的硝酸盐-氨转化，FE为88.5%，NH3最大产率为831.4 mmol h−1 g−1，锌- co2可充电电池FECO为98.5%，功率密度为2.1 mW cm−2。这项研究强调了非晶态金属氧化物介导的界面水活化作为一种通用的和可扩展的策略，用于提高水参与的电催化反应的选择性。
{"title":"Promoting Electrocatalytic CO2 Reduction via Oxophilic Amorphous Metal Oxide-Mediated Interfacial Water Activation and Structure Evolution","authors":"Wenbo Wang, Shanhe Gong, Junpeng Huang, Minghui Zhu, Xiaozhen Zhang, Guangtong Hai, Xiaomeng Lv, Guoxing Zhu","doi":"10.1002/smll.202514230","DOIUrl":"https://doi.org/10.1002/smll.202514230","url":null,"abstract":"Interfacial water serves as the intrinsic proton source for CO<sub>2</sub> hydrogenation, yet synchronizing its activation with on-demand active hydrogen (<sup>*</sup>H) supply without triggering the hydrogen evolution reaction (HER) remains challenging. Herein, we construct an oxophilic amorphous MnO<sub>x</sub> overlayer on Ag to regulate the interfacial water network. In situ characterization and theoretical calculations demonstrate that under over 45% of interfacial water reorganizes into an ordered four-coordinate hydrogen-bonded (4-HB-H<sub>2</sub>O) structure under operation, facilitating targeted proton transfer to CO<sub>2</sub> reduction intermediates. The distorted Mn-O polyhedra lower the water dissociation barrier by 0.54 eV while raising the HER barrier by 0.61 eV. It achieves a CO production rate of 12.8 mol h<sup>−1</sup> g<sup>−1</sup> and 68.6% Faraday efficiency (FE) at −1000 mA cm<sup>−2</sup> and maintains >95% FE<sub>CO</sub> over 500 h at −200 mA cm<sup>−2</sup>. It also enables efficient nitrate-to-ammonia conversion with the FE of 88.5 %, and the maximum NH<sub>3</sub> production rate is 831.4 mmol h<sup>−1</sup> g<sup>−1</sup>, and a Zn–CO<sub>2</sub> rechargeable battery with FE<sub>CO</sub> of 98.5% and power density of 2.1 mW cm<sup>−2</sup>. This study underscores the amorphous metal oxide-mediated interfacial water activation as a versatile and scalable strategy for enhancing selectivity in water-involved electrocatalytic reactions.","PeriodicalId":228,"journal":{"name":"Small","volume":"4 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972339","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}
A major obstacle in the advancement of sodium-ion batteries (SIBs) is the development of cathode active materials (CAMs) that offer both high specific capacity and long-term cycling stability. Among the various candidates, layered CAMs have attracted significant attention. In this work, we synthesized a high-entropy layered CAM with composition (Na0.52Ti0.19Mn0.19Fe0.21Ni0.21Co0.20O2) using a spray pyrolysis technique, yielding large (0.75 µm on average) and separated grains. The resulting material comprises a P3–O3 layered oxide mixture, along with ∼20% rock-salt and spinel phases. This CAM demonstrates a high specific capacity (∼180 mAh g−1 at 0.08 C), excellent rate capability (69% retention after 300 cycles at 1C), and high coulombic efficiency (>99.5%). In comparison, a CAM of identical composition synthesized via a conventional sol–gel method, exhibiting an agglomerated microstructure, showed lower capacity and retention, consistent with literature reports. These findings highlight the advantages of combining high entropy design and cathode morphology in developing next-generation cathodes for SIBs.
钠离子电池（sib）发展的一个主要障碍是阴极活性材料（CAMs）的发展，这种材料既能提供高比容量，又能提供长期循环稳定性。在各种候选方案中，分层cam引起了极大的关注。本文采用喷雾热解技术合成了一种高熵层状CAM，其组成为Na0.52Ti0.19Mn0.19Fe0.21Ni0.21Co0.20O2，晶粒大小平均为0.75µm。所得材料包括P3-O3层状氧化物混合物，以及约20%的岩盐和尖晶石相。该CAM具有高比容量（0.08℃时约180 mAh g−1），优异的倍率能力（在1C下300次循环后保持69%）和高库仑效率（99.5%）。相比之下，通过传统的溶胶-凝胶方法合成的相同成分的CAM，具有团聚的微观结构，其容量和保留率较低，与文献报道一致。这些发现突出了高熵设计和阴极形貌相结合在开发下一代sib阴极中的优势。
{"title":"High Entropy Layered Cathode With Single Grain Morphology for High-Performance Sodium-Ion Batteries","authors":"Daniele Callegari, Giulia Maranini, Claudia Triolo, Mariam Maisuradze, Hemanth Kumar Beere, Abdelhaq Nassiri, Umberto Anselmi-Tamburini, Saveria Santangelo, Marco Giorgetti, Mauro Coduri","doi":"10.1002/smll.202511833","DOIUrl":"https://doi.org/10.1002/smll.202511833","url":null,"abstract":"A major obstacle in the advancement of sodium-ion batteries (SIBs) is the development of cathode active materials (CAMs) that offer both high specific capacity and long-term cycling stability. Among the various candidates, layered CAMs have attracted significant attention. In this work, we synthesized a high-entropy layered CAM with composition (Na<sub>0.52</sub>Ti<sub>0.19</sub>Mn<sub>0.19</sub>Fe<sub>0.21</sub>Ni<sub>0.21</sub>Co<sub>0.20</sub>O<sub>2</sub>) using a spray pyrolysis technique, yielding large (0.75 µm on average) and separated grains. The resulting material comprises a P3–O3 layered oxide mixture, along with ∼20% rock-salt and spinel phases. This CAM demonstrates a high specific capacity (∼180 mAh g<sup>−1</sup> at 0.08 C), excellent rate capability (69% retention after 300 cycles at 1C), and high coulombic efficiency (>99.5%). In comparison, a CAM of identical composition synthesized via a conventional sol–gel method, exhibiting an agglomerated microstructure, showed lower capacity and retention, consistent with literature reports. These findings highlight the advantages of combining high entropy design and cathode morphology in developing next-generation cathodes for SIBs.","PeriodicalId":228,"journal":{"name":"Small","volume":"49 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968860","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}
Xin Sheng, Yahui Li, Xiaohe Miao, Yanxin Han, Jie Meng, Baini Li, Ming Xia, Yiling Zhang, Yunfan Guo, Enzheng Shi
Ruddlesden-Popper (RP) perovskites offer exceptional optoelectronic properties but face persistent challenges in achieving simultaneous control over phase purity, processability, and scalable synthesis. Here, we overcome this limitation through iodide-mediated liquid-assisted grinding (LAG), enabling gram-scale synthesis of phase-pure quantum-well perovskites (n = 1–4) with >98% phase fidelity. By introducing hydroiodic acid (HI) during mechanochemical milling, we achieve kinetic acceleration via liquid-phase ionic incorporation, bypassing solid-state diffusion barriers to drive stoichiometry-directed assembly into monophase crystals (0.1–5 µm). The resulting powders resolve scalability-processability constraints by enabling spark plasma sintering consolidation into centimeter-scale bulk monoliths with improved crystallographic orientation, and facilitating conformal coatings on flexible/curved substrates via screen printing. Critically, these processable forms support heterogeneous integration with 3D perovskites to create functional heterostructures. This work establishes a platform for deterministic quantum-well design, unlocking scalable production and integration of 2D perovskites for advanced optoelectronics.
{"title":"Bulk Synthesis of Phase-Pure Ruddlesden-Popper Phase Perovskites via Iodide-Mediated Mechanochemistry","authors":"Xin Sheng, Yahui Li, Xiaohe Miao, Yanxin Han, Jie Meng, Baini Li, Ming Xia, Yiling Zhang, Yunfan Guo, Enzheng Shi","doi":"10.1002/smll.202514815","DOIUrl":"https://doi.org/10.1002/smll.202514815","url":null,"abstract":"Ruddlesden-Popper (RP) perovskites offer exceptional optoelectronic properties but face persistent challenges in achieving simultaneous control over phase purity, processability, and scalable synthesis. Here, we overcome this limitation through iodide-mediated liquid-assisted grinding (LAG), enabling gram-scale synthesis of phase-pure quantum-well perovskites (n = 1–4) with >98% phase fidelity. By introducing hydroiodic acid (HI) during mechanochemical milling, we achieve kinetic acceleration via liquid-phase ionic incorporation, bypassing solid-state diffusion barriers to drive stoichiometry-directed assembly into monophase crystals (0.1–5 µm). The resulting powders resolve scalability-processability constraints by enabling spark plasma sintering consolidation into centimeter-scale bulk monoliths with improved crystallographic orientation, and facilitating conformal coatings on flexible/curved substrates via screen printing. Critically, these processable forms support heterogeneous integration with 3D perovskites to create functional heterostructures. This work establishes a platform for deterministic quantum-well design, unlocking scalable production and integration of 2D perovskites for advanced optoelectronics.","PeriodicalId":228,"journal":{"name":"Small","volume":"81 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968867","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}
Sam Daly, Joseph E. Chambers, Caroline Jones, Bin Fu, James D. Manton, Joseph S. Beckwith, Stefan J. Marciniak, David C. Gershlick, Steven F. Lee
The non-covalent interactions that underpin major cellular functions depend on molecular motion within 3D environments. Large depth-of-field single-molecule localization microscopy (3D-SMLM) methods facilitate these measurements, but their increased optical complexity and bespoke post-processing pipelines often sacrifice important cellular context. Here, we combine single-molecule light-field microscopy (SMLFM) with widefield Fourier light-field microscopy for correlative volumetric organelle imaging. The instantaneous acquisition of subcellular volumes improves the sensitivity of molecular organization, chemical environment, and diffusion measurements through the use of volumetric sub-cellular segmentation. We first demonstrate our approach by measuring the molecular organization of a nuclear-localized HaloTag protein relative to cell nuclei. Next, we characterize the molecular diffusion of the soluble protein, calreticulin, in the context of -antitrypsin deficiency, which revealed an increase in heterogeneous motion within endoplasmic reticulum inclusions.
{"title":"Volumetric Single-Molecule Tracking Inside Subcellular Structures","authors":"Sam Daly, Joseph E. Chambers, Caroline Jones, Bin Fu, James D. Manton, Joseph S. Beckwith, Stefan J. Marciniak, David C. Gershlick, Steven F. Lee","doi":"10.1002/smll.202509162","DOIUrl":"https://doi.org/10.1002/smll.202509162","url":null,"abstract":"The non-covalent interactions that underpin major cellular functions depend on molecular motion within 3D environments. Large depth-of-field single-molecule localization microscopy (3D-SMLM) methods facilitate these measurements, but their increased optical complexity and bespoke post-processing pipelines often sacrifice important cellular context. Here, we combine single-molecule light-field microscopy (SMLFM) with widefield Fourier light-field microscopy for correlative volumetric organelle imaging. The instantaneous acquisition of subcellular volumes improves the sensitivity of molecular organization, chemical environment, and diffusion measurements through the use of volumetric sub-cellular segmentation. We first demonstrate our approach by measuring the molecular organization of a nuclear-localized HaloTag protein relative to cell nuclei. Next, we characterize the molecular diffusion of the soluble protein, calreticulin, in the context of <span data-altimg=\"/cms/asset/a205ec83-27f1-43d3-8df7-dc93d5bca193/smll71966-math-0001.png\"></span><mjx-container ctxtmenu_counter=\"97\" ctxtmenu_oldtabindex=\"1\" jax=\"CHTML\" role=\"application\" sre-explorer- style=\"font-size: 103%; position: relative;\" tabindex=\"0\"><mjx-math aria-hidden=\"true\" location=\"graphic/smll71966-math-0001.png\"><mjx-semantics><mjx-msub data-semantic-children=\"0,1\" data-semantic- data-semantic-role=\"greekletter\" data-semantic-speech=\"alpha 1\" data-semantic-type=\"subscript\"><mjx-mi data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"italic\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"greekletter\" data-semantic-type=\"identifier\"><mjx-c></mjx-c></mjx-mi><mjx-script style=\"vertical-align: -0.15em;\"><mjx-mn data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\" size=\"s\"><mjx-c></mjx-c></mjx-mn></mjx-script></mjx-msub></mjx-semantics></mjx-math><mjx-assistive-mml display=\"inline\" unselectable=\"on\"><math altimg=\"urn:x-wiley:16136810:media:smll71966:smll71966-math-0001\" display=\"inline\" location=\"graphic/smll71966-math-0001.png\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><semantics><msub data-semantic-=\"\" data-semantic-children=\"0,1\" data-semantic-role=\"greekletter\" data-semantic-speech=\"alpha 1\" data-semantic-type=\"subscript\"><mi data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"italic\" data-semantic-parent=\"2\" data-semantic-role=\"greekletter\" data-semantic-type=\"identifier\">α</mi><mn data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\">1</mn></msub>$ualpha_1$</annotation></semantics></math></mjx-assistive-mml></mjx-container>-antitrypsin deficiency, which revealed an increase in heterogeneous motion within endoplasmic reticulum inclusions.","PeriodicalId":228,"journal":{"name":"Small","volume":"45 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968868","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}
Although the electron correlation (U) within d-orbital perovskite Mott-systems is the root-cause for their unconventional functionalities, such as metal-to-insulator transitions (MIT), high-TC superconductivity, and multiferroics, it yet lacks strategy to modulate their U. Herein, we enable the tunability in U for correlated perovskite nickelates (RENiO3) by manipulating their RE-site covalency via introducing partial Bi-substitutions, based on which huge improvement in their electronic MIT abruptions beyond one order was achieved. The more covalent bonding between Bi-6s and O-2p enlarges the Ni-3d occupancy that enlarges U by 2–3 times, as indicated by synchrotron-based X-ray absorption spectroscopies and first principal calculations. Consequently, the ground-state band gap (Eg) and resistivity are effectively increased, giving rise to significant enhancement in their resistive switches across adjustable critical temperatures (TMIT) within 75–400 K, by up to 40 times. Simultaneously, the Bi-substitutions concurrently descend TMIT owing to their larger sizes than RE3+, indicating the prevailing dominance in the relative phase stability by the O-2p to Ni-3d charge transfer gap. This unravels the mystery in U that only electronically enlarges the ground-state Eg and resistivity rather than determines the relative phase stability across MIT (or TMIT). Tuning U via A-site covalency provides new freedom for optimizing functionalities of correlated perovskites.
{"title":"Realizing Modulations in Electron Correlations for Perovskite Mott-System via Tunning A-Site Covalency","authors":"Jingxin Gao, Yusong Zhao, Hao Zhang, Peiheng Jiang, Jiaou Wang, Binghui Ge, Zhicheng Zhong, Jiacai Nie, Jikun Chen","doi":"10.1002/smll.202509859","DOIUrl":"https://doi.org/10.1002/smll.202509859","url":null,"abstract":"Although the electron correlation (<i>U</i>) within <i>d-</i>orbital perovskite Mott-systems is the root-cause for their unconventional functionalities, such as metal-to-insulator transitions (MIT), high-<i>T</i><sub>C</sub> superconductivity, and multiferroics, it yet lacks strategy to modulate their <i>U</i>. Herein, we enable the tunability in <i>U</i> for correlated perovskite nickelates (<i>RE</i>NiO<sub>3</sub>) by manipulating their <i>RE</i>-site covalency via introducing partial Bi-substitutions, based on which huge improvement in their electronic MIT abruptions beyond one order was achieved. The more covalent bonding between Bi-6<i>s</i> and O-2<i>p</i> enlarges the Ni-3<i>d</i> occupancy that enlarges <i>U</i> by 2–3 times, as indicated by synchrotron-based X-ray absorption spectroscopies and first principal calculations. Consequently, the ground-state band gap (<i>E</i><sub>g</sub>) and resistivity are effectively increased, giving rise to significant enhancement in their resistive switches across adjustable critical temperatures (<i>T</i><sub>MIT</sub>) within 75–400 K, by up to 40 times. Simultaneously, the Bi-substitutions concurrently descend <i>T</i><sub>MIT</sub> owing to their larger sizes than <i>RE</i><sup>3+</sup>, indicating the prevailing dominance in the relative phase stability by the O-2<i>p</i> to Ni-3<i>d</i> charge transfer gap. This unravels the mystery in <i>U</i> that only electronically enlarges the ground-state <i>E</i><sub>g</sub> and resistivity rather than determines the relative phase stability across MIT (or <i>T</i><sub>MIT</sub>). Tuning <i>U</i> via A-site covalency provides new freedom for optimizing functionalities of correlated perovskites.","PeriodicalId":228,"journal":{"name":"Small","volume":"81 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968937","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}
Aqueous zinc-iodine (Zn-I2) batteries, despite their cost-effectiveness and safety, are plagued by zinc anode corrosion and the polyiodide shuttle effect. Herein, trace tetraethylenepentamine (TEP), with a high-density N-H proton array, is employed to regulate the running environment of Zn-I2 batteries, which suppresses anode corrosion and polyiodide formation, enabling long-term cycling under high-loading conditions. For the zinc anode, TEP's high-density N-H array facilitates preferential surface adsorption, optimizing the interfacial Helmholtz layer. Rich in lone-pair electrons, its -NH2 and -NH- groups as Lewis bases coordinate with Zn2+ ions to regulate interfacial ion dynamics, enabling dendrite-free Zn deposition. For the iodine cathode, TEP coordinates with I2 via the lone pair electrons of N atoms and forms strong electrostatic hydrogen bonds between H protons and I−, synergistically suppressing polyiodides formation, thereby enhancing the utilization of the iodine cathode. Consequently, TEP enables the Zn||Zn battery to achieve a stable cycling for over 2333 h (1 mA cm−2, 1 mAh cm−2). The Zn-I2 battery with a high iodine loading (15.9 mg cm−2) retains 91.3% capacity after 8900 cycles. This study demonstrates that incorporating a trace amount of TEP provides a new insight into the development of sustainable, long-life Zn-I2 batteries.
水基锌碘（Zn-I2）电池，尽管具有成本效益和安全性，但受到锌阳极腐蚀和多碘化物穿梭效应的困扰。本文采用痕量四乙基戊二胺（TEP），通过高密度N-H质子阵列调节Zn-I2电池的运行环境，抑制阳极腐蚀和多碘化物的形成，实现高负载条件下的长期循环。对于锌阳极，TEP的高密度N-H阵列促进了优先表面吸附，优化了界面亥姆霍兹层。富含孤对电子，其- nh2和- nhh -基团作为路易斯碱与Zn2+离子配合调节界面离子动力学，实现无枝晶Zn沉积。对于碘阴极，TEP通过N原子的孤对电子与I2配位，并在H质子与I−之间形成强的静电氢键，协同抑制多碘化物的形成，从而提高碘阴极的利用率。因此，TEP使Zn||锌电池能够实现超过2333小时的稳定循环（1ma cm - 2, 1mah cm - 2）。高碘负载（15.9 mg cm−2）的锌- i2电池在8900次循环后仍保持91.3%的容量。这项研究表明，加入微量的TEP为开发可持续的、长寿命的Zn-I2电池提供了新的见解。
{"title":"Polyamine Compound with High-Density N-H Proton Arrays Enables High-Loading and Long Lifespan Zinc-Iodine Batteries","authors":"Yanzi Deng, Tiancheng You, Qiwen Zhao, Bo Xiao, Risheng Cheng, Bingang Xu, Yuejiao Chen, Libao Chen","doi":"10.1002/smll.202514273","DOIUrl":"https://doi.org/10.1002/smll.202514273","url":null,"abstract":"Aqueous zinc-iodine (Zn-I<sub>2</sub>) batteries, despite their cost-effectiveness and safety, are plagued by zinc anode corrosion and the polyiodide shuttle effect. Herein, trace tetraethylenepentamine (TEP), with a high-density N-H proton array, is employed to regulate the running environment of Zn-I<sub>2</sub> batteries, which suppresses anode corrosion and polyiodide formation, enabling long-term cycling under high-loading conditions. For the zinc anode, TEP's high-density N-H array facilitates preferential surface adsorption, optimizing the interfacial Helmholtz layer. Rich in lone-pair electrons, its -NH<sub>2</sub> and -NH- groups as Lewis bases coordinate with Zn<sup>2+</sup> ions to regulate interfacial ion dynamics, enabling dendrite-free Zn deposition. For the iodine cathode, TEP coordinates with I<sub>2</sub> via the lone pair electrons of N atoms and forms strong electrostatic hydrogen bonds between H protons and I<sup>−</sup>, synergistically suppressing polyiodides formation, thereby enhancing the utilization of the iodine cathode. Consequently, TEP enables the Zn||Zn battery to achieve a stable cycling for over 2333 h (1 mA cm<sup>−2</sup>, 1 mAh cm<sup>−2</sup>). The Zn-I<sub>2</sub> battery with a high iodine loading (15.9 mg cm<sup>−2</sup>) retains 91.3% capacity after 8900 cycles. This study demonstrates that incorporating a trace amount of TEP provides a new insight into the development of sustainable, long-life Zn-I<sub>2</sub> batteries.","PeriodicalId":228,"journal":{"name":"Small","volume":"126 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972305","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}
Yu Pan, Hui-Min Xu, Hong-Rui Zhu, Xue-Shan Lin, Lian-Jie Song, Wan-Qing Lu, Jun Mao, Vyacheslav Yu. Fominski, Mikhail M. Maslov, Gao-Ren Li
Electrocatalytic nitrate reduction reaction (NO3−RR) for ammonia synthesis is extremely compatible with the concept of green development as it enables both low carbon emission and low energy consumption ammonia (NH3) production, as well as the treatment of pollution in wastewater. However, the unavoidable competing reactions present in the NO3−RR process and adsorption limitations of the reactants on the surface hinder the effective activation of nitrate and affect the efficient NH3 synthesis. Herein, the high-performance VP- CoP/Co(OH)2 heterojunction catalysts for enhancing NO3−RR competition in the NO3− to NH3 conversion process was skillfully constructed by successfully growing Co(OH)2 nanosheets on P vacancy-rich CoP via an electrochemical in situ reconfiguration strategy. The optimized VP-CoP/Co(OH)2 exhibits excellent electrocatalytic performance of NO3−RR at −0.1 V vs. RHE, corresponding to an NH3 Faraday efficiency of 96.60% and an NH3 yield of 0.091 mmol h−1 cm−2, with a favorable stability. Combination of experimental studies and theoretical calculations demonstrates that P vacancies modify the coordination environment of the Co sites, which in turn modulates the electronic structure and accelerates the charge transfer rate. Heterojunctions, on the other hand, lead to a reconfiguration of the electronic structure at the interface, inducing a further accumulation of charge at the Co active sites. The synergy of both further activates the electronic states around the Co sites, which causes the d-band center moving toward the Fermi energy level, further enhancing the adsorption of NO3− and promoting the reduction of NO3−. This work focuses on modulating the electronic structure of the Co active sites to enhance its NO3−RR electrocatalytic performance, thus delivering a viable pathway for NO3− to NH3 high-efficiency conversion.
{"title":"Enhancing the Catalytic Activity of Co Sites by the Synergistic Effect of Vacancy and Heterojunction Engineering for Efficient Electroreduction Nitrate to Ammonia","authors":"Yu Pan, Hui-Min Xu, Hong-Rui Zhu, Xue-Shan Lin, Lian-Jie Song, Wan-Qing Lu, Jun Mao, Vyacheslav Yu. Fominski, Mikhail M. Maslov, Gao-Ren Li","doi":"10.1002/smll.202512893","DOIUrl":"https://doi.org/10.1002/smll.202512893","url":null,"abstract":"Electrocatalytic nitrate reduction reaction (NO<sub>3</sub><sup>−</sup>RR) for ammonia synthesis is extremely compatible with the concept of green development as it enables both low carbon emission and low energy consumption ammonia (NH<sub>3</sub>) production, as well as the treatment of pollution in wastewater. However, the unavoidable competing reactions present in the NO<sub>3</sub><sup>−</sup>RR process and adsorption limitations of the reactants on the surface hinder the effective activation of nitrate and affect the efficient NH<sub>3</sub> synthesis. Herein, the high-performance V<sub>P</sub>- CoP/Co(OH)<sub>2</sub> heterojunction catalysts for enhancing NO<sub>3</sub><sup>−</sup>RR competition in the NO<sub>3</sub><sup>−</sup> to NH<sub>3</sub> conversion process was skillfully constructed by successfully growing Co(OH)<sub>2</sub> nanosheets on P vacancy-rich CoP via an electrochemical in situ reconfiguration strategy. The optimized V<sub>P</sub>-CoP/Co(OH)<sub>2</sub> exhibits excellent electrocatalytic performance of NO<sub>3</sub><sup>−</sup>RR at −0.1 V vs. RHE, corresponding to an NH<sub>3</sub> Faraday efficiency of 96.60% and an NH<sub>3</sub> yield of 0.091 mmol h<sup>−1</sup> cm<sup>−2</sup>, with a favorable stability. Combination of experimental studies and theoretical calculations demonstrates that P vacancies modify the coordination environment of the Co sites, which in turn modulates the electronic structure and accelerates the charge transfer rate. Heterojunctions, on the other hand, lead to a reconfiguration of the electronic structure at the interface, inducing a further accumulation of charge at the Co active sites. The synergy of both further activates the electronic states around the Co sites, which causes the d-band center moving toward the Fermi energy level, further enhancing the adsorption of NO<sub>3</sub><sup>−</sup> and promoting the reduction of NO<sub>3</sub><sup>−</sup>. This work focuses on modulating the electronic structure of the Co active sites to enhance its NO<sub>3</sub><sup>−</sup>RR electrocatalytic performance, thus delivering a viable pathway for NO<sub>3</sub><sup>−</sup> to NH<sub>3</sub> high-efficiency conversion.","PeriodicalId":228,"journal":{"name":"Small","volume":"50 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972306","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}
Developing direct-current triboelectric nanogenerators (DC-TENGs) with high output performance and reliable operation in humid environments remains a significant challenge. In this study, we introduce a high-performance DC-TENG fabricated by integrating electrospinning, vapor-phase infiltration (VPI), and atomic layer deposition (ALD) to construct a TiO2-modified polyvinylidene fluoride (PVDF) porous fiber (PTPF) membrane. The resulting PTPF10-TENG demonstrates superior electrical performance, generating a peak current of 0.72 mA, an output voltage of 1.79 V, and a maximum power density of 27.3 µW/cm2, representing a 5.4-fold improvement over the porous PVDF membrane. Owing to its strong humidity-responsive behavior, the PTPF10-TENG also functions as a self-powered humidity sensor with a linear sensitivity of 0.0134 mA/%RH (R2 = 0.981) in the 40–100% RH range. These findings underscore the versatility of the PTPF membrane as a multifunctional platform that bridges efficient energy conversion and environmental sensing. This strategy offers a promising route toward scalable fabrication of DC-TENGs tailored for next-generation wearable electronics and intelligent monitoring systems.
{"title":"High-Current Triboelectric Nanogenerator Based on TiO2-Decorated PVDF Membrane via Atomic Layer Deposition for Self-Powered Humidity Sensing","authors":"Duy Linh Vu, Pham Thi Lanh, Thi Thuong Nguyen, Hung-Anh Tran Vu, Quang Tan Nguyen, Viet Huong Nguyen, Soon-Gil Yoon, Nguyen Van Hieu","doi":"10.1002/smll.202512870","DOIUrl":"https://doi.org/10.1002/smll.202512870","url":null,"abstract":"Developing direct-current triboelectric nanogenerators (DC-TENGs) with high output performance and reliable operation in humid environments remains a significant challenge. In this study, we introduce a high-performance DC-TENG fabricated by integrating electrospinning, vapor-phase infiltration (VPI), and atomic layer deposition (ALD) to construct a TiO<sub>2</sub>-modified polyvinylidene fluoride (PVDF) porous fiber (PTPF) membrane. The resulting PTPF10-TENG demonstrates superior electrical performance, generating a peak current of 0.72 mA, an output voltage of 1.79 V, and a maximum power density of 27.3 µW/cm<sup>2</sup>, representing a 5.4-fold improvement over the porous PVDF membrane. Owing to its strong humidity-responsive behavior, the PTPF10-TENG also functions as a self-powered humidity sensor with a linear sensitivity of 0.0134 mA/%RH (R<sup>2</sup> = 0.981) in the 40–100% RH range. These findings underscore the versatility of the PTPF membrane as a multifunctional platform that bridges efficient energy conversion and environmental sensing. This strategy offers a promising route toward scalable fabrication of DC-TENGs tailored for next-generation wearable electronics and intelligent monitoring systems.","PeriodicalId":228,"journal":{"name":"Small","volume":"266 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968861","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}
Qionghua Su, Dongqi Wu, Huanyi Zhou, Ye Yang, Xing Lu, Jinglin Wang, Zhihui Liu, Zhensang Tong, Qianxia Zhang, Chunxiao Guo, Jiangxuan Xu, Qi Pang, Anxiang Guan, Liya Zhou, Peican Chen
Ultraviolet (UV) radiation greatly affects the stability of perovskite solar cells (PSCs), limiting their application in extreme environments such as plateaus and deserts. Herein, the antioxidant [triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (AO-245) is introduced into the perovskite layer by anti-solvent method to improve the UV stability. AO-245 not only demonstrates UV absorption properties but also neutralizes harmful superoxide radicals () through a hydrogen atom transfer mechanism (HAT), thereby mitigating the photodegradation damage of perovskite. Additionally, the −OH group in AO-245 can form hydrogen bonds with I−, inhibit the migration of iodide ions due to photoaging, and synergistically enhance the UV stability of the device. As a result, even after 120 h of exposure to UV light at 275 and 365 nm, the AO-245-modified PSCs retain more than 88% and 83% of their initial power conversion efficiency (PCE), respectively. AO-245 additive passivates the uncoordinated Pb2+ through C═O and C─O bonds, thereby enhancing the film's quality and the device's stability. Consequently, the device achieves a PCE of 19.76%, which is among the highest efficiencies observed hole transport material (HTM)-free carbon-based PSCs (C-PSCs). This study provides a simple solution to improve the durability of PSCs under UV radiation, facilitating their application in extreme environments.
{"title":"Multifunctional AO-245 Antioxidant Enables UV-Resistant and High-Efficient Perovskite Solar Cells","authors":"Qionghua Su, Dongqi Wu, Huanyi Zhou, Ye Yang, Xing Lu, Jinglin Wang, Zhihui Liu, Zhensang Tong, Qianxia Zhang, Chunxiao Guo, Jiangxuan Xu, Qi Pang, Anxiang Guan, Liya Zhou, Peican Chen","doi":"10.1002/smll.202514080","DOIUrl":"https://doi.org/10.1002/smll.202514080","url":null,"abstract":"Ultraviolet (UV) radiation greatly affects the stability of perovskite solar cells (PSCs), limiting their application in extreme environments such as plateaus and deserts. Herein, the antioxidant [triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (AO-245) is introduced into the perovskite layer by anti-solvent method to improve the UV stability. AO-245 not only demonstrates UV absorption properties but also neutralizes harmful superoxide radicals (<span data-altimg=\"/cms/asset/9c276499-f20d-46c6-a075-c3bd62590fa3/smll72391-math-0001.png\"></span><math altimg=\"urn:x-wiley:16136810:media:smll72391:smll72391-math-0001\" display=\"inline\" location=\"graphic/smll72391-math-0001.png\">\u0000<semantics>\u0000<msubsup>\u0000<mi mathvariant=\"normal\">O</mi>\u0000<mn>2</mn>\u0000<mrow>\u0000<mo>•</mo>\u0000<mo>−</mo>\u0000</mrow>\u0000</msubsup>\u0000${mathrm{O}}_2^{ bullet - }$</annotation>\u0000</semantics></math>) through a hydrogen atom transfer mechanism (HAT), thereby mitigating the photodegradation damage of perovskite. Additionally, the −OH group in AO-245 can form hydrogen bonds with I<sup>−</sup>, inhibit the migration of iodide ions due to photoaging, and synergistically enhance the UV stability of the device. As a result, even after 120 h of exposure to UV light at 275 and 365 nm, the AO-245-modified PSCs retain more than 88% and 83% of their initial power conversion efficiency (PCE), respectively. AO-245 additive passivates the uncoordinated Pb<sup>2+</sup> through C═O and C─O bonds, thereby enhancing the film's quality and the device's stability. Consequently, the device achieves a PCE of 19.76%, which is among the highest efficiencies observed hole transport material (HTM)-free carbon-based PSCs (C-PSCs). This study provides a simple solution to improve the durability of PSCs under UV radiation, facilitating their application in extreme environments.","PeriodicalId":228,"journal":{"name":"Small","volume":"56 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968863","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}
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