Developing highly efficient and stable catalysts for electrochemical carbon dioxide reduction reaction (CO2RR) remains a significant challenge, particularly for transition metal-based systems that often suffer from excessive hydrogen evolution and catalyst degradation. In this work, we report a carbon-coated NiFe alloy (NiFe@NC) synthesized via a substrate-anchored pyrolysis strategy, in which the carbon shell serves as an electronic modulator and protective layer. DFT calculations and in situ spectroscopic analysis reveal that the carbon layer induces notable electronic reconstruction at the NiFe surface, weakening the back-donation to the anti-bonding orbitals of the *CO intermediate, thus facilitating *CO desorption and improving CO2RR kinetics. Meanwhile, the carbon layer also suppresses undesired *H adsorption while protecting the catalyst from deactivation under long-term operation. As a result, the NiFe@NC catalyst achieves stable operation at 500 mA cm-2 for 250 h in a membrane electrode assembly (MEA) system, outperforming most previously reported transition-metal-based catalysts. This work provides a practical strategy for tuning surface electronic structures to overcome the intrinsic limitations of conventional transition metal CO2RR catalysts.
开发高效稳定的电化学二氧化碳还原反应（CO2RR）催化剂仍然是一个重大挑战，特别是对于过渡金属基体系，它经常遭受过度的析氢和催化剂降解。在这项工作中，我们报告了一种碳涂层NiFe合金（NiFe@NC）通过基质锚定热解策略合成，其中碳壳作为电子调制器和保护层。DFT计算和原位光谱分析表明，碳层在NiFe表面诱导了显著的电子重构，削弱了*CO中间体反键轨道的反给能，从而促进了*CO的脱附，提高了CO2RR动力学。同时，碳层还抑制了不需要的*H吸附，同时保护催化剂在长期运行下不失活。结果，NiFe@NC催化剂在膜电极组件（MEA）系统中以500 mA cm-2的速度稳定运行250小时，优于大多数先前报道的过渡金属基催化剂。这项工作为调整表面电子结构提供了一种实用的策略，以克服传统过渡金属CO2RR催化剂的固有局限性。
{"title":"Carbon Shell-Mediated Electronic Modulation of NiFe Alloy Electrocatalysts for Efficient CO2 Electroreduction.","authors":"Xiya Guan,Wenwen Cai,Hongwei Pan,Yueqing Wang,Xueying Cao,Jizhen Ma,Jintao Zhang","doi":"10.1002/smll.202514530","DOIUrl":"https://doi.org/10.1002/smll.202514530","url":null,"abstract":"Developing highly efficient and stable catalysts for electrochemical carbon dioxide reduction reaction (CO2RR) remains a significant challenge, particularly for transition metal-based systems that often suffer from excessive hydrogen evolution and catalyst degradation. In this work, we report a carbon-coated NiFe alloy (NiFe@NC) synthesized via a substrate-anchored pyrolysis strategy, in which the carbon shell serves as an electronic modulator and protective layer. DFT calculations and in situ spectroscopic analysis reveal that the carbon layer induces notable electronic reconstruction at the NiFe surface, weakening the back-donation to the anti-bonding orbitals of the *CO intermediate, thus facilitating *CO desorption and improving CO2RR kinetics. Meanwhile, the carbon layer also suppresses undesired *H adsorption while protecting the catalyst from deactivation under long-term operation. As a result, the NiFe@NC catalyst achieves stable operation at 500 mA cm-2 for 250 h in a membrane electrode assembly (MEA) system, outperforming most previously reported transition-metal-based catalysts. This work provides a practical strategy for tuning surface electronic structures to overcome the intrinsic limitations of conventional transition metal CO2RR catalysts.","PeriodicalId":228,"journal":{"name":"Small","volume":"16 1","pages":"e14530"},"PeriodicalIF":13.3,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502205","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}
Shaoxing Li,Yining Chen,Tao Zhang,Jingkang Ma,Quan Zong,Ziyi Zhu,Shuang Zhou,Xinmei Li,Anqiang Pan
The water-dominated inner Helmholtz plane (IHP) at the electrode/electrolyte interface is a critical factor responsible for notorious parasitic reactions and Zn dendrite growth, which severely limit the development of aqueous zinc-metal batteries (AZMBs). In this work, we report a universal competitive adsorption strategy to reconstruct the interfacial molecular distribution and induce orderly Zn2+ deposition behavior by introducing DL-malic acid additive (denoted as DL). Specifically, the DL molecules preferentially adsorb on the Zn anode surface, forming a water-shielding IHP layer that effectively excludes water molecules. The zincophilic groups within DL provide abundant active sites and homogenize Zn2+ flux, achieving uniform Zn2+ deposition. Moreover, the original hydrogen-bond network is reset, thereby efficiently suppressing active water-induced parasitic reactions. As a result, symmetric cells with DL additive exhibit remarkable cycling stability over 8600 cycles at 5 mA cm-2 and 1 mAh cm-2, while Zn||Cu asymmetric cells achieve a coulombic efficiency of 99.9% over 3600 cycles. The advanced Zn||I2 full cell delivers stable operation for 4000 cycles with 82.7% capacity retention at 1 A g-1. Moreover, the Zn||I2 pouch cell with limited N/P (1.82) reserves 78.2% capacity after 860 cycles. Surprisingly, an Ah-level Zn||I2 pouch cell maintains marvel stability and reversibility over 220 cycles.
电极/电解质界面处以水为主导的内亥姆霍兹平面（IHP）是导致不良寄生反应和Zn枝晶生长的关键因素，严重限制了水锌金属电池（azmb）的发展。在这项工作中，我们报道了一种通用的竞争吸附策略，通过引入DL-苹果酸添加剂（表示为DL）来重建界面分子分布并诱导有序的Zn2+沉积行为。具体来说，DL分子优先吸附在Zn阳极表面，形成水屏蔽IHP层，有效地排除了水分子。DL中的亲锌基团提供了丰富的活性位点，并使Zn2+通量均匀，实现了均匀的Zn2+沉积。此外，原始的氢键网络被重置，从而有效地抑制活跃的水诱导的寄生反应。结果表明，添加DL的对称电池在5ma cm-2和1mah cm-2下的8600次循环中表现出显著的循环稳定性，而Zn||Cu不对称电池在3600次循环中达到99.9%的库仑效率。先进的Zn||I2全电池在1 A g-1下可稳定运行4000次，容量保持率为82.7%。此外，在限定N/P（1.82）的情况下，Zn||I2袋状电池在860次循环后仍保留78.2%的容量。令人惊讶的是，一个ah级的锌b|i2袋电池在220次循环中保持了惊人的稳定性和可逆性。
{"title":"Tailoring Molecular Competitive Adsorption for Stable Ah-Level Aqueous Zinc Metal Batteries.","authors":"Shaoxing Li,Yining Chen,Tao Zhang,Jingkang Ma,Quan Zong,Ziyi Zhu,Shuang Zhou,Xinmei Li,Anqiang Pan","doi":"10.1002/smll.73197","DOIUrl":"https://doi.org/10.1002/smll.73197","url":null,"abstract":"The water-dominated inner Helmholtz plane (IHP) at the electrode/electrolyte interface is a critical factor responsible for notorious parasitic reactions and Zn dendrite growth, which severely limit the development of aqueous zinc-metal batteries (AZMBs). In this work, we report a universal competitive adsorption strategy to reconstruct the interfacial molecular distribution and induce orderly Zn2+ deposition behavior by introducing DL-malic acid additive (denoted as DL). Specifically, the DL molecules preferentially adsorb on the Zn anode surface, forming a water-shielding IHP layer that effectively excludes water molecules. The zincophilic groups within DL provide abundant active sites and homogenize Zn2+ flux, achieving uniform Zn2+ deposition. Moreover, the original hydrogen-bond network is reset, thereby efficiently suppressing active water-induced parasitic reactions. As a result, symmetric cells with DL additive exhibit remarkable cycling stability over 8600 cycles at 5 mA cm-2 and 1 mAh cm-2, while Zn||Cu asymmetric cells achieve a coulombic efficiency of 99.9% over 3600 cycles. The advanced Zn||I2 full cell delivers stable operation for 4000 cycles with 82.7% capacity retention at 1 A g-1. Moreover, the Zn||I2 pouch cell with limited N/P (1.82) reserves 78.2% capacity after 860 cycles. Surprisingly, an Ah-level Zn||I2 pouch cell maintains marvel stability and reversibility over 220 cycles.","PeriodicalId":228,"journal":{"name":"Small","volume":"6 1","pages":"e73197"},"PeriodicalIF":13.3,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502207","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}
Mi Gan,Wenbo Dong,Xiaofei Zhao,Maria Manzoor,Yingxue Xia,Jinzhang Liu
Aqueous rechargeable Zn-organic batteries at discharged state can self-charge through the spontaneous O2-oxidation of organic cathode, and the self-charged energy originates from the consumption of Zn anode, as the stripped Zn is converted into complex compounds on cathode surface. These byproducts block ion diffusion and shorten cycle life. Additional drawbacks include the semi-open battery case for air uptake, which leads to electrolyte evaporation, and the low discharge voltage plateau. To address these challenges, herein a triple strategy is presented: (i) The fabrication of a bicomponent organic cathode comprising a polymer and small molecules, achieving a synergistic effect by the regulation of molecular orbital levels; (ii) The incorporation of Pt nanoparticles into the organic blend to modulate redox reactions, thereby enhancing capacity and enabling self-charging capability based on proton chemistry, without the O2-oxidation mechanism; (iii) The implementation of an electrolyte decoupling strategy, which not only elevates the self-charged voltage to 2.1 V but also prevents byproduct formation on cathode surface. The hermetically sealed cell can self-charge to generate power by consuming the Zn anode. The role of Pt nanocatalyst in augmenting capacity and self-charging performance is investigated both experimentally and theoretically. Furthermore, practical applications of this self-charging battery are vividly demonstrated.
{"title":"A Triple Strategy to Enhance Energy Storage and Power Generation Performances of a Rechargeable Zn-H2O Fuel Cell.","authors":"Mi Gan,Wenbo Dong,Xiaofei Zhao,Maria Manzoor,Yingxue Xia,Jinzhang Liu","doi":"10.1002/smll.73208","DOIUrl":"https://doi.org/10.1002/smll.73208","url":null,"abstract":"Aqueous rechargeable Zn-organic batteries at discharged state can self-charge through the spontaneous O2-oxidation of organic cathode, and the self-charged energy originates from the consumption of Zn anode, as the stripped Zn is converted into complex compounds on cathode surface. These byproducts block ion diffusion and shorten cycle life. Additional drawbacks include the semi-open battery case for air uptake, which leads to electrolyte evaporation, and the low discharge voltage plateau. To address these challenges, herein a triple strategy is presented: (i) The fabrication of a bicomponent organic cathode comprising a polymer and small molecules, achieving a synergistic effect by the regulation of molecular orbital levels; (ii) The incorporation of Pt nanoparticles into the organic blend to modulate redox reactions, thereby enhancing capacity and enabling self-charging capability based on proton chemistry, without the O2-oxidation mechanism; (iii) The implementation of an electrolyte decoupling strategy, which not only elevates the self-charged voltage to 2.1 V but also prevents byproduct formation on cathode surface. The hermetically sealed cell can self-charge to generate power by consuming the Zn anode. The role of Pt nanocatalyst in augmenting capacity and self-charging performance is investigated both experimentally and theoretically. Furthermore, practical applications of this self-charging battery are vividly demonstrated.","PeriodicalId":228,"journal":{"name":"Small","volume":"20 1","pages":"e73208"},"PeriodicalIF":13.3,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495099","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}
Haolin Wu,Xinying Li,Bin Wang,Hongbin Liu,Fan Wang,Amr F M Ibrahim,Shenglai Zhong,Rongfei Zhou,Weihong Xing,Miao Yu
Assembling the nanochannels of microporous crystalline materials in continuous membranes/coatings has broad applications for separation, selective catalysis, and sensing. Current hydrothermal/solvothermal synthesis methods, however, suffer from long synthesis time, typically hours or days, leading to low fabrication efficiency and intensive energy consumption. Herein, we report an ultrafast synthesis strategy to prepare continuous molecular-sieving membranes, reducing synthesis time to just one to a few minutes-nearly two orders of magnitude faster than traditional ones. This was realized through a combination of a nuclei-loaded seed layer and a drastically increased crystallization rate, preventing substantial dissolution of the seed layer and successfully incorporating it into the resulting membranes. Utilizing this strategy, high-quality zeolite membranes-exhibiting breakthrough separation performance compared to previously reported ones, were rapidly prepared. Interestingly, ultrathin oriented zeolite membranes with ultrahigh separation performance were also prepared in as little as one minute. The drastically shortened synthesis time, together with the demonstrated reproducibility, highlights the practical potential of the UFS strategy for molecular-sieving membranes and coatings.
{"title":"Ultrafast, Minute-Level Synthesis of Ultrathin Molecular-Sieving Membranes with Breakthrough Performance.","authors":"Haolin Wu,Xinying Li,Bin Wang,Hongbin Liu,Fan Wang,Amr F M Ibrahim,Shenglai Zhong,Rongfei Zhou,Weihong Xing,Miao Yu","doi":"10.1002/smll.202513698","DOIUrl":"https://doi.org/10.1002/smll.202513698","url":null,"abstract":"Assembling the nanochannels of microporous crystalline materials in continuous membranes/coatings has broad applications for separation, selective catalysis, and sensing. Current hydrothermal/solvothermal synthesis methods, however, suffer from long synthesis time, typically hours or days, leading to low fabrication efficiency and intensive energy consumption. Herein, we report an ultrafast synthesis strategy to prepare continuous molecular-sieving membranes, reducing synthesis time to just one to a few minutes-nearly two orders of magnitude faster than traditional ones. This was realized through a combination of a nuclei-loaded seed layer and a drastically increased crystallization rate, preventing substantial dissolution of the seed layer and successfully incorporating it into the resulting membranes. Utilizing this strategy, high-quality zeolite membranes-exhibiting breakthrough separation performance compared to previously reported ones, were rapidly prepared. Interestingly, ultrathin oriented zeolite membranes with ultrahigh separation performance were also prepared in as little as one minute. The drastically shortened synthesis time, together with the demonstrated reproducibility, highlights the practical potential of the UFS strategy for molecular-sieving membranes and coatings.","PeriodicalId":228,"journal":{"name":"Small","volume":"15 1","pages":"e13698"},"PeriodicalIF":13.3,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495208","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}
Peng Sun,Yunze Luo,Ziyuan Wang,Xiaoke Li,Xijier Chen,Jianguo Liu
Photoelectrochemical (PEC) selective oxidation of glycerol offers a sustainable strategy to obtain dihydroxyacetone (DHA) as a value-added chemical, which remains challenging owing to the slow kinetics and low selectivity. We construct a Z-scheme heterojunction consisting of an amorphous vanadium oxide nanolayer on BiVO4 nanoparticles (BiVO4-VOx) for glycerol oxidation by a spatially confined photoelectron deposition method. BiVO4-VOx photoanode achieves a high DHA evolution rate of 400.4 mmol m-2 h-1 and a selectivity of 65.6% at 1.2 V vs. RHE. Femtosecond transient absorption spectroscopy analysis demonstrates superior charge separation efficiency and ultrafast interfacial transfer kinetics, enabling long-lived photogenerated electrons and holes accumulated in BiVO4 conduction band and VOx valence band, respectively. Furthermore, in situ Fourier transform infrared spectroscopy and theoretical calculations reveal that the synergy between the optimized electronic structure of amorphous VOx and Z-scheme heterojunction promotes preferential adsorption of glycerol middle hydroxyl groups and lowers the energy barrier of the rate-determining step, thus facilitating selective DHA production. We fabricated a self-powered device with a DHA productivity of 122.0 mmol m-2 h-1, a H2 productivity of 1.33 mL cm-2 h-1 and a solar-to-H2 conversion efficiency of 4.7%. This work highlights the potential of heterojunction engineering for PEC biomass valorization toward value-added products.
{"title":"Ultrafast Electron Transfer at BiVO4-VOx Z-Scheme Interface for Enhanced Selective Oxidation of Glycerol to Dihydroxyacetone.","authors":"Peng Sun,Yunze Luo,Ziyuan Wang,Xiaoke Li,Xijier Chen,Jianguo Liu","doi":"10.1002/smll.73167","DOIUrl":"https://doi.org/10.1002/smll.73167","url":null,"abstract":"Photoelectrochemical (PEC) selective oxidation of glycerol offers a sustainable strategy to obtain dihydroxyacetone (DHA) as a value-added chemical, which remains challenging owing to the slow kinetics and low selectivity. We construct a Z-scheme heterojunction consisting of an amorphous vanadium oxide nanolayer on BiVO4 nanoparticles (BiVO4-VOx) for glycerol oxidation by a spatially confined photoelectron deposition method. BiVO4-VOx photoanode achieves a high DHA evolution rate of 400.4 mmol m-2 h-1 and a selectivity of 65.6% at 1.2 V vs. RHE. Femtosecond transient absorption spectroscopy analysis demonstrates superior charge separation efficiency and ultrafast interfacial transfer kinetics, enabling long-lived photogenerated electrons and holes accumulated in BiVO4 conduction band and VOx valence band, respectively. Furthermore, in situ Fourier transform infrared spectroscopy and theoretical calculations reveal that the synergy between the optimized electronic structure of amorphous VOx and Z-scheme heterojunction promotes preferential adsorption of glycerol middle hydroxyl groups and lowers the energy barrier of the rate-determining step, thus facilitating selective DHA production. We fabricated a self-powered device with a DHA productivity of 122.0 mmol m-2 h-1, a H2 productivity of 1.33 mL cm-2 h-1 and a solar-to-H2 conversion efficiency of 4.7%. This work highlights the potential of heterojunction engineering for PEC biomass valorization toward value-added products.","PeriodicalId":228,"journal":{"name":"Small","volume":"82 1","pages":"e73167"},"PeriodicalIF":13.3,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495210","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}
Efficient photocatalysis requires coordinated regulation of charge transport across both bulk and interfacial regions. Here, we introduce an in situ hydrothermal-solvothermal method that simultaneously creates a defect-induced p-n homojunction in ZnIn2S4 (ZIS) and a type-II heterojunction with hybrid 1T-2H WS2, forming antiparallel internal-interfacial built-in electric fields (BIEF) that are confirmed by spectroscopic, electronic, optical, and theoretical analyses. Under the guidance of this dual-field coupling effect, photoexcited carriers undergo more efficient separation, enabling the effective modulation of bulk carrier migration and directing electrons toward sulfur-vacancy (Sv) sites in ZIS for efficient hydrogen evolution. The hybrid 1T-2H phases of WS2 further enhance light absorption and facilitate rapid charge generation and transfer, reinforcing the dual-BIEF-driven transport pathway. The optimized ZIS/WS2 photocatalyst achieves a hydrogen evolution rate of 44.97 mmol g-1 h-1 and an apparent quantum efficiency of 24.54% at 400 nm. This work establishes antiparallel dual-BIEF engineering combined with 1T-2H hybrid-phase modulation as a platform for directional charge-dynamic control, offering a pathway toward efficient solar-to-hydrogen conversion.
{"title":"Efficient Photocatalytic Hydrogen Evolution Enabled by Defect- and Interface-Induced Dual Built-in Electric Fields in a ZnIn2S4/1T-2H WS2 Heterojunction.","authors":"Ning Li,Jinyu Zhang,Jiafeng Ma,Chaorui Xue,Qing Chang,Lei Liu,Xiangqian Fan,Caihong Hao,Shaobin Wang,Shengliang Hu,Wenjie Tian","doi":"10.1002/smll.202514954","DOIUrl":"https://doi.org/10.1002/smll.202514954","url":null,"abstract":"Efficient photocatalysis requires coordinated regulation of charge transport across both bulk and interfacial regions. Here, we introduce an in situ hydrothermal-solvothermal method that simultaneously creates a defect-induced p-n homojunction in ZnIn2S4 (ZIS) and a type-II heterojunction with hybrid 1T-2H WS2, forming antiparallel internal-interfacial built-in electric fields (BIEF) that are confirmed by spectroscopic, electronic, optical, and theoretical analyses. Under the guidance of this dual-field coupling effect, photoexcited carriers undergo more efficient separation, enabling the effective modulation of bulk carrier migration and directing electrons toward sulfur-vacancy (Sv) sites in ZIS for efficient hydrogen evolution. The hybrid 1T-2H phases of WS2 further enhance light absorption and facilitate rapid charge generation and transfer, reinforcing the dual-BIEF-driven transport pathway. The optimized ZIS/WS2 photocatalyst achieves a hydrogen evolution rate of 44.97 mmol g-1 h-1 and an apparent quantum efficiency of 24.54% at 400 nm. This work establishes antiparallel dual-BIEF engineering combined with 1T-2H hybrid-phase modulation as a platform for directional charge-dynamic control, offering a pathway toward efficient solar-to-hydrogen conversion.","PeriodicalId":228,"journal":{"name":"Small","volume":"83 1","pages":"e14954"},"PeriodicalIF":13.3,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495093","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}
Peroxymonosulfate (PMS) activation by metal-based catalysts has attracted increasing attention as an effective approach for advanced oxidation processes (AOPs). However, the practical implementation remains limited by inefficient reaction activity, uncontrolled reactive species generation selectivity and unsatisfied long-term stability. Recent studies have demonstrated that electronic structure regulation of metal-based catalysts has emerged as a central strategy to address these challenges by regulating PMS adsorption behavior, interfacial electron transfer, and activation pathways. Hence, this review provides a systematic overview of recent advances in PMS activation from an electronic-structure-centered perspective, covering key modulation strategies including coordination environment regulation, metal doping, defect engineering and electron-buffering metal-support interactions. Particular emphasis is placed on elucidating how electronic structure descriptors, such as charge distribution, orbital hybridization, spin state, and d-band center position, govern the PMS adsorption and reaction kinetics, charge transfer and recycle, selective generation of radical and non-radical reactive species. Finally, current challenges related to green synthesis, mechanistic understanding, dynamic electronic evolution, and practical application are highlighted. This review aims to provide a mechanistic clarity and design principles to guide metal-based catalyst construction for more controllable and efficient PMS-based water treatment processes.
{"title":"Engineering Electronic Structure of Metal-Based Catalysts Toward Selective Peroxymonosulfate Activation for Water Purification.","authors":"Zhiyuan Feng,Zonglin Li,Min Chen,Jiahui Liu,Hongying Zhao","doi":"10.1002/smll.202600054","DOIUrl":"https://doi.org/10.1002/smll.202600054","url":null,"abstract":"Peroxymonosulfate (PMS) activation by metal-based catalysts has attracted increasing attention as an effective approach for advanced oxidation processes (AOPs). However, the practical implementation remains limited by inefficient reaction activity, uncontrolled reactive species generation selectivity and unsatisfied long-term stability. Recent studies have demonstrated that electronic structure regulation of metal-based catalysts has emerged as a central strategy to address these challenges by regulating PMS adsorption behavior, interfacial electron transfer, and activation pathways. Hence, this review provides a systematic overview of recent advances in PMS activation from an electronic-structure-centered perspective, covering key modulation strategies including coordination environment regulation, metal doping, defect engineering and electron-buffering metal-support interactions. Particular emphasis is placed on elucidating how electronic structure descriptors, such as charge distribution, orbital hybridization, spin state, and d-band center position, govern the PMS adsorption and reaction kinetics, charge transfer and recycle, selective generation of radical and non-radical reactive species. Finally, current challenges related to green synthesis, mechanistic understanding, dynamic electronic evolution, and practical application are highlighted. This review aims to provide a mechanistic clarity and design principles to guide metal-based catalyst construction for more controllable and efficient PMS-based water treatment processes.","PeriodicalId":228,"journal":{"name":"Small","volume":"189 1","pages":"e00054"},"PeriodicalIF":13.3,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495096","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}
Fang Luo,Chang-Shin Park,Yeoung-Eun Seo,Xiaosong Jiang,Han-Ki Kim
Electrochromic devices offer immense potential for energy-saving and adaptive optics, yet their advancement is hindered by slow ion diffusion and low charge utilization, which critically limit the development of next-generation flexible optoelectronic technologies. In this study, a gradient-engineered Ti-doped WO3 architecture is developed to enable robust electron-ion coupling, leading to enhanced coloration efficiency and mechanical robustness. By dynamically modulating the sputtering powers of TiO2 and W metal targets, a continuous Ti concentration gradient was established, forming a self-built internal electric field that promotes electron-ion synergy and accelerates Li+ transport. The optimized gradient film delivers a large optical modulation of 78.9% and a high coloration efficiency (CE) of 137.4 cm2 C-1, outperforming uniformly doped counterparts. The gradient structure suppresses abrupt band offsets and induces smooth energy band bending across the film, facilitating fast redox kinetics and enhanced reversibility. Furthermore, after 500 bending cycles, the film retains over 82% of its modulation amplitude and exhibits an increased CE of 213.73 cm2 C-1, confirming outstanding flexibility and stress adaptability. This gradient doping strategy unites the structural continuity of homojunctions with band engineering of heterojunctions, offering a universal design paradigm for high-performance flexible electrochromic and photoelectronic systems.
{"title":"Compositional Gradient-Engineered Ti-WO3 Films for Simultaneous Enhancement of Coloration Efficiency and Mechanical Robustness.","authors":"Fang Luo,Chang-Shin Park,Yeoung-Eun Seo,Xiaosong Jiang,Han-Ki Kim","doi":"10.1002/smll.202514826","DOIUrl":"https://doi.org/10.1002/smll.202514826","url":null,"abstract":"Electrochromic devices offer immense potential for energy-saving and adaptive optics, yet their advancement is hindered by slow ion diffusion and low charge utilization, which critically limit the development of next-generation flexible optoelectronic technologies. In this study, a gradient-engineered Ti-doped WO3 architecture is developed to enable robust electron-ion coupling, leading to enhanced coloration efficiency and mechanical robustness. By dynamically modulating the sputtering powers of TiO2 and W metal targets, a continuous Ti concentration gradient was established, forming a self-built internal electric field that promotes electron-ion synergy and accelerates Li+ transport. The optimized gradient film delivers a large optical modulation of 78.9% and a high coloration efficiency (CE) of 137.4 cm2 C-1, outperforming uniformly doped counterparts. The gradient structure suppresses abrupt band offsets and induces smooth energy band bending across the film, facilitating fast redox kinetics and enhanced reversibility. Furthermore, after 500 bending cycles, the film retains over 82% of its modulation amplitude and exhibits an increased CE of 213.73 cm2 C-1, confirming outstanding flexibility and stress adaptability. This gradient doping strategy unites the structural continuity of homojunctions with band engineering of heterojunctions, offering a universal design paradigm for high-performance flexible electrochromic and photoelectronic systems.","PeriodicalId":228,"journal":{"name":"Small","volume":"269 1","pages":"e14826"},"PeriodicalIF":13.3,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495100","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}
Muhammad Zubair,Yongteng Qian,Kyung-Ho Park,Dae Joon Kang
High-entropy metal chalcogenides (HEMC), stabilized by their high configurational entropy and multi-element disorder, have emerged as promising materials for electrocatalysis. However, synthesizing high-entropy sulfide catalysts via bottom-up routes remains challenging due to the thermodynamic incompatibility of multiple metals, which promotes unwanted phase segregation and hinders controlled self-assembly for optimal electrocatalytic performance. In this study, we tackle this challenge by systematically optimizing the solvothermal synthesis parameters, including solvent ratio, reductants, and stabilizers, to produce a single-phase, strain-engineered HEMC nanoflower/nanoflake (VMoFeCoNi)Sx, as strain engineering has the potential to modify the adsorption process and enhance electrocatalytic activity. The Williamson-Hall analysis reveals a compressive micro strain of 0.67%, manifested as a blue shift of the (220) reflection (44.34° → 44.47°) and a slight lattice contraction relative to the control samples. The optimized HEMC-based anode exhibits top-level oxygen evolution reaction (OER) performance in alkaline media, achieving overpotentials of 210 mV and 250 mV at current densities of 50 mA cm-2 and 100 mA cm-2, respectively. Notably, it retains excellent OER stability with minimal degradation at 200 mA cm-2 over 120 h, demonstrating rapid reaction kinetics and durability at high current density, positioning it as a promising candidate for practical energy applications.
高熵金属硫族化合物（HEMC）由于其高构型熵和多元素无序性而稳定，是一种很有前途的电催化材料。然而，由于多种金属的热力学不相容，通过自下而上的途径合成高熵硫化物催化剂仍然具有挑战性，这会促进不必要的相分离，并阻碍控制自组装以获得最佳电催化性能。在这项研究中，我们通过系统地优化溶剂热合成参数，包括溶剂比、还原剂和稳定剂，来生产单相、菌株工程的HEMC纳米花/纳米片（VMoFeCoNi）Sx，因为菌株工程具有改变吸附过程和提高电催化活性的潜力。Williamson-Hall分析显示压缩微应变为0.67%，表现为（220）反射的蓝移（44.34°→44.47°）和相对于对照样品的轻微晶格收缩。优化后的hemc基阳极在碱性介质中表现出顶级的析氧反应（OER）性能，在电流密度为50 mA cm-2和100 mA cm-2时分别达到210 mV和250 mV的过电位。值得注意的是，它在200 mA cm-2下保持了出色的OER稳定性，在120小时内降解最小，在高电流密度下表现出快速的反应动力学和耐久性，使其成为实际能源应用的有希望的候选者。
{"title":"Strain-Modulated Engineering of High-Entropy Vanadium-Based Chalcogenide for Sustainable Water Oxidation.","authors":"Muhammad Zubair,Yongteng Qian,Kyung-Ho Park,Dae Joon Kang","doi":"10.1002/smll.73201","DOIUrl":"https://doi.org/10.1002/smll.73201","url":null,"abstract":"High-entropy metal chalcogenides (HEMC), stabilized by their high configurational entropy and multi-element disorder, have emerged as promising materials for electrocatalysis. However, synthesizing high-entropy sulfide catalysts via bottom-up routes remains challenging due to the thermodynamic incompatibility of multiple metals, which promotes unwanted phase segregation and hinders controlled self-assembly for optimal electrocatalytic performance. In this study, we tackle this challenge by systematically optimizing the solvothermal synthesis parameters, including solvent ratio, reductants, and stabilizers, to produce a single-phase, strain-engineered HEMC nanoflower/nanoflake (VMoFeCoNi)Sx, as strain engineering has the potential to modify the adsorption process and enhance electrocatalytic activity. The Williamson-Hall analysis reveals a compressive micro strain of 0.67%, manifested as a blue shift of the (220) reflection (44.34° → 44.47°) and a slight lattice contraction relative to the control samples. The optimized HEMC-based anode exhibits top-level oxygen evolution reaction (OER) performance in alkaline media, achieving overpotentials of 210 mV and 250 mV at current densities of 50 mA cm-2 and 100 mA cm-2, respectively. Notably, it retains excellent OER stability with minimal degradation at 200 mA cm-2 over 120 h, demonstrating rapid reaction kinetics and durability at high current density, positioning it as a promising candidate for practical energy applications.","PeriodicalId":228,"journal":{"name":"Small","volume":"31 1","pages":"e73201"},"PeriodicalIF":13.3,"publicationDate":"2026-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495127","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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