Jin Zhang, Bing Wang, Zhen Sun, Jiayin Ye, Jiahui Chen, Abhinandan Kumar, Peng Ren, Guan Zhang
The piezocatalytic efficiency of metal–organic frameworks (MOFs) is often limited by their weak piezoresponse. Herein, using UiO-66 as a model system, we demonstrate that defect engineering can effectively enhance both the piezoelectric and piezocatalytic performance of MOFs. Piezoresponse force microscopy reveals that the piezoelectric coefficient of defect-engineered UiO-66 increases up to 6.25 times compared with the pristine crystal. Molecular dynamics simulations attribute this enhancement to additional polarization generated by the flexoelectric effect near defects. Piezocatalytic hydrogen evolution experiments, supported by electrochemical analyses and density functional theory calculations, confirm that the improved catalytic activity arises from the synergistic effects of defect-induced charge separation, enhanced carrier transport, and a reduced energy barrier for hydrogen adsorption. The optimized defective UiO-66 achieves nearly twice the hydrogen production rate of its pristine counterpart under identical conditions. This study provides mechanistic insight into the role of defects in modulating piezoelectricity and catalytic performance, and highlights defect engineering as an effective strategy to boost the piezocatalytic hydrogen evolution activity of MOFs.
{"title":"Optimizing the piezocatalytic hydrogen production activity of metal-organic frameworks through precise defect engineering","authors":"Jin Zhang, Bing Wang, Zhen Sun, Jiayin Ye, Jiahui Chen, Abhinandan Kumar, Peng Ren, Guan Zhang","doi":"10.1039/d5ta10240e","DOIUrl":"https://doi.org/10.1039/d5ta10240e","url":null,"abstract":"The piezocatalytic efficiency of metal–organic frameworks (MOFs) is often limited by their weak piezoresponse. Herein, using UiO-66 as a model system, we demonstrate that defect engineering can effectively enhance both the piezoelectric and piezocatalytic performance of MOFs. Piezoresponse force microscopy reveals that the piezoelectric coefficient of defect-engineered UiO-66 increases up to 6.25 times compared with the pristine crystal. Molecular dynamics simulations attribute this enhancement to additional polarization generated by the flexoelectric effect near defects. Piezocatalytic hydrogen evolution experiments, supported by electrochemical analyses and density functional theory calculations, confirm that the improved catalytic activity arises from the synergistic effects of defect-induced charge separation, enhanced carrier transport, and a reduced energy barrier for hydrogen adsorption. The optimized defective UiO-66 achieves nearly twice the hydrogen production rate of its pristine counterpart under identical conditions. This study provides mechanistic insight into the role of defects in modulating piezoelectricity and catalytic performance, and highlights defect engineering as an effective strategy to boost the piezocatalytic hydrogen evolution activity of MOFs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"49 3 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489725","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}
In this study, Aminosulfamic acid (SA) was proposed and validated as a multifunctional electrolyte additive to enhance the stability and reversibility of aqueous zinc-ion batteries (AZIBs), and the optimal concentration ratio of the additive was obtained via a scientific single-factor sequential search method. Endowed with a unique molecular structure, SA constructs a "bulk-interface" synergistic regulation mechanism: in the bulk electrolyte, SA molecules effectively reconstruct the hydrogen bond network, confine free water molecules, and participate in the primary solvation shell of Zn²⁺, forming a more stable solution system that significantly suppresses various water-induced side reactions. At the zinc anode interface, the amino and sulfonic acid groups in SA are anchored on the zinc anode surface via chemical adsorption, constructing an ordered interfacial layer and forming a water-deficient composite interfacial adsorption layer. This layer preferentially covers highly active sites and promotes zinc deposition along the dense, flat (002) crystal plane. Such oriented growth inhibits zinc dendrite formation, enabling high reversibility of zinc deposition/stripping processes and significantly enhancing the battery's cycling stability and Coulombic efficiency (CE). After SA modification, under the test conditions of 1 mA cm⁻²/1 mAh cm⁻² and 5 mA cm⁻²/1 mAh cm⁻², the Zn//Zn symmetric cell displays long cycling stability in excess of 3200 h and 2000 h, respectively. Furthermore, the SA additive significantly enhances the performance of the Zn//VO₂ full cell, delivering an initial capacity as high as 305.6 mAh g⁻¹ at a current density of 1 A g⁻¹, with a capacity retention rate of 85.21% after 1200 cycles.
本研究提出并验证了氨基磺胺酸（SA）作为一种增强水性锌离子电池（AZIBs）稳定性和可逆性的多功能电解质添加剂，并通过科学的单因素顺序搜索方法获得了该添加剂的最佳浓度比。SA具有独特的分子结构，构建了“体-界面”协同调节机制：在体电解质中，SA分子有效地重构了氢键网络，限制了自由水分子，并参与了Zn 2 +的初级溶剂化壳层，形成了更稳定的溶液体系，显著抑制了各种水诱导的副反应。在锌阳极界面处，SA中的氨基和磺酸基团通过化学吸附被锚定在锌阳极表面，构建有序的界面层，形成缺水复合界面吸附层。该层优先覆盖高活性位点，促进锌沿着致密、平坦的（002）晶体平面沉积。这种定向生长抑制了锌枝晶的形成，使锌沉积/剥离过程具有高可逆性，并显著提高了电池的循环稳定性和库仑效率（CE）。经SA修饰后，在1 mA cm⁻²/1 mAh cm⁻²和5 mA cm⁻²/1 mAh cm⁻²的测试条件下，锌/锌对称电池分别表现出超过3200 h和2000 h的长周期稳定性。此外，SA添加剂显著提高了Zn//VO 2填充电池的性能，在电流密度为1 a g⁻¹的情况下，其初始容量高达305.6 mAh g⁻¹，在1200次循环后容量保持率为85.21%。
{"title":"Multifunctional Sulfamic Acid Additive for Synergistic Electrolyte Regulation toward Long-Cycling Aqueous Zinc-Ion Batteries","authors":"Zeqi Liu, Guopei Qiu, Kaihuan Liu, Wentao Li, Xinruo Xie, Yixin Zhou, Aokui Sun","doi":"10.1039/d6ta00616g","DOIUrl":"https://doi.org/10.1039/d6ta00616g","url":null,"abstract":"In this study, Aminosulfamic acid (SA) was proposed and validated as a multifunctional electrolyte additive to enhance the stability and reversibility of aqueous zinc-ion batteries (AZIBs), and the optimal concentration ratio of the additive was obtained via a scientific single-factor sequential search method. Endowed with a unique molecular structure, SA constructs a \"bulk-interface\" synergistic regulation mechanism: in the bulk electrolyte, SA molecules effectively reconstruct the hydrogen bond network, confine free water molecules, and participate in the primary solvation shell of Zn²⁺, forming a more stable solution system that significantly suppresses various water-induced side reactions. At the zinc anode interface, the amino and sulfonic acid groups in SA are anchored on the zinc anode surface via chemical adsorption, constructing an ordered interfacial layer and forming a water-deficient composite interfacial adsorption layer. This layer preferentially covers highly active sites and promotes zinc deposition along the dense, flat (002) crystal plane. Such oriented growth inhibits zinc dendrite formation, enabling high reversibility of zinc deposition/stripping processes and significantly enhancing the battery's cycling stability and Coulombic efficiency (CE). After SA modification, under the test conditions of 1 mA cm⁻²/1 mAh cm⁻² and 5 mA cm⁻²/1 mAh cm⁻², the Zn//Zn symmetric cell displays long cycling stability in excess of 3200 h and 2000 h, respectively. Furthermore, the SA additive significantly enhances the performance of the Zn//VO₂ full cell, delivering an initial capacity as high as 305.6 mAh g⁻¹ at a current density of 1 A g⁻¹, with a capacity retention rate of 85.21% after 1200 cycles.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"12 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489726","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}
Jingyan Liu, Julia M Barker, Jiabin Xu, Yining Huang, Yang Song
Understanding how mechanical stress reshapes flexible metal–organic frameworks (MOFs) is important for designing robust, stimuli‑responsive CO₂ sorbents. Here we compare the high‑pressure flexibility of the elastic layered MOF ELM‑11 and its hydrated precursor pre‑ELM‑11 using in situ synchrotron powder X‑ray diffraction (PXRD) and Fourier‑transform infrared (FTIR) spectroscopy. Pre‑ELM‑11 shows a pronounced change in anisotropic response at 2.15 GPa: compression along the c axis switches from positive linear compressibility (PLC) to negative linear compressibility (NLC), consistent with a transition from interlayer compression to pressure‑driven layer sliding. In contrast, activated ELM‑11 undergoes continuous anisotropic compression from 0.12 to 4.28 GPa dominated by interlayer contraction, and principal‑axis analysis reveals near‑zero linear compressibility (ZLC) along X3. To probe pressure‑tuned host–guest interactions, we further monitor CO₂‑loaded ELM‑11 by in situ FTIR. Deconvolution of the ν₃ band of natural‑abundance ¹³CO₂ resolves an increase in distinct adsorption environments from two to three at 3.44 GPa, with additional sites appearing above 9.59 GPa. Together, these results map distinct pressure‑activated deformation pathways in closely related layered frameworks and demonstrate that mechanical pressure can reveal and create new CO₂ binding environments, informing the design of flexible 2D MOFs for pressure‑responsive gas adsorption. More broadly, the comparative results identify interlayer hydrogen‑bond pinning and initial interlayer spacing as key molecular levers that select pressure‑activated deformation pathways and thereby tune pressure‑dependent CO₂ site heterogeneity in layered flexible MOFs.
了解机械应力如何重塑柔性金属有机框架（mof）对于设计坚固，响应刺激的CO₂吸附剂非常重要。本文采用原位同步加速器粉末X射线衍射（PXRD）和傅里叶变换红外光谱（FTIR）比较了弹性层状MOF ELM - 11及其水合前驱体pre - ELM - 11的高压柔韧性。Pre - ELM - 11在2.15 GPa时显示出明显的各向异性响应变化：沿c轴的压缩从正线性压缩率（PLC）转变为负线性压缩率（NLC），与层间压缩向压力驱动层滑动的转变相一致。相比之下，活化后的ELM - 11经历了0.12 - 4.28 GPa的连续各向异性压缩，主要是层间收缩，主轴分析显示沿X3的线性压缩率（ZLC）接近于零。为了探测压力调节的主客相互作用，我们进一步通过原位FTIR监测CO₂负载的ELM - 11。自然丰度¹³CO₂的ν₃波段的反卷积解决了在3.44 GPa下不同的吸附环境从2个增加到3个的问题，另外的位置出现在9.59 GPa以上。总之，这些结果在密切相关的层状框架中绘制了不同的压力激活变形路径，并证明了机械压力可以揭示和创造新的CO₂结合环境，为设计用于压力响应气体吸附的柔性二维mof提供了信息。更广泛地说，比较结果确定层间氢键钉住和初始层间间距是选择压力激活变形途径的关键分子杠杆，从而调节层状柔性mof中压力依赖的CO₂位点异质性。
{"title":"From layer sliding to near-zero compressibility: novel high-pressure flexibility and CO₂ site evolution in pre-ELM-11 and ELM-11","authors":"Jingyan Liu, Julia M Barker, Jiabin Xu, Yining Huang, Yang Song","doi":"10.1039/d5ta10521h","DOIUrl":"https://doi.org/10.1039/d5ta10521h","url":null,"abstract":"Understanding how mechanical stress reshapes flexible metal–organic frameworks (MOFs) is important for designing robust, stimuli‑responsive CO₂ sorbents. Here we compare the high‑pressure flexibility of the elastic layered MOF ELM‑11 and its hydrated precursor pre‑ELM‑11 using in situ synchrotron powder X‑ray diffraction (PXRD) and Fourier‑transform infrared (FTIR) spectroscopy. Pre‑ELM‑11 shows a pronounced change in anisotropic response at 2.15 GPa: compression along the c axis switches from positive linear compressibility (PLC) to negative linear compressibility (NLC), consistent with a transition from interlayer compression to pressure‑driven layer sliding. In contrast, activated ELM‑11 undergoes continuous anisotropic compression from 0.12 to 4.28 GPa dominated by interlayer contraction, and principal‑axis analysis reveals near‑zero linear compressibility (ZLC) along X3. To probe pressure‑tuned host–guest interactions, we further monitor CO₂‑loaded ELM‑11 by in situ FTIR. Deconvolution of the ν₃ band of natural‑abundance ¹³CO₂ resolves an increase in distinct adsorption environments from two to three at 3.44 GPa, with additional sites appearing above 9.59 GPa. Together, these results map distinct pressure‑activated deformation pathways in closely related layered frameworks and demonstrate that mechanical pressure can reveal and create new CO₂ binding environments, informing the design of flexible 2D MOFs for pressure‑responsive gas adsorption. More broadly, the comparative results identify interlayer hydrogen‑bond pinning and initial interlayer spacing as key molecular levers that select pressure‑activated deformation pathways and thereby tune pressure‑dependent CO₂ site heterogeneity in layered flexible MOFs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"282 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466049","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}
Harishchandra S Nishad, Rajesh R. Jaiswar, Diwakar Singh, Shekhar Bhame, Shashikant P. Patole, Pravin S. Walke
The development of high-performance electrode materials remains a critical challenge in advancing next-generation pseudocapacitors due to its low electrical conductivity, slow ion diffusion, and structural instability during long-term cycling. The hydrated tungsten oxide (WO3·H2O) has emerged as a promising candidate owing to its layered structure and abundant interlayer water. However, its electrochemical performance is still constrained by limited active sites and inefficient charge-transfer kinetics. To overcome these limitation, Sn doping and controlled phase engineering of WO3·H2O have been implemented to enhance the intrinsic electrochemical properties. Sn-doped WO3·H2O was synthesized at various doping concentrations via a simple wet chemical method, followed by annealing to achieve mixed phases of Sn-doped WO3·H2O and WO3. Furthermore, the electrochemical measurements exhibited a significant enhancement in specific capacitance, with doping concentration i.e. W0, SnW5, and SnW25 delivering specific capacitance of 115 F g-1, 146 F g-1, and 182 F g-1 at 1 A g-1, respectively. Similarly, among annealed samples (SnW200, SnW400 and SnW600), SnW200 exhibited the highest capacitance of 323 F g-1, demonstrating the synergestic effect of defect modulation and mixed-phase interaction. Eventually, the fabricated quasi-solid-state asymmetric supercapacitor (QSSAS) device achieved 36 F g-1, an energy density of 11 W h kg-1, and a power density of 5795 W kg-1, while retaining 72% capacitance over 10,000 cycles. This work highlights Sn-doped tungsten oxides as a promising and scalable route for developing durable, high-energy-density pseudocapacitors.
高性能电极材料的开发仍然是推进下一代伪电容器的关键挑战，因为它的电导率低，离子扩散缓慢，并且在长期循环过程中结构不稳定。水合氧化钨（WO3·H2O）由于其层状结构和丰富的层间水而成为有前途的候选材料。然而，它的电化学性能仍然受到有限的活性位点和低效的电荷转移动力学的限制。为了克服这些限制，采用了锡掺杂和WO3·H2O的控制相工程来提高其固有的电化学性能。采用简单的湿法化学方法在不同掺杂浓度下合成掺锡WO3·H2O，然后退火得到掺锡WO3·H2O和WO3的混合相。此外，电化学测量结果显示，掺杂浓度W0、SnW5和SnW25在1 a g-1时的比电容分别为115、146和182 F -1，比电容显著增强。同样，在退火样品（SnW200、SnW400和SnW600）中，SnW200的电容最高，达到323 F -1，显示出缺陷调制和混相相互作用的协同效应。最终，制备的准固态非对称超级电容器（QSSAS）器件实现了36 gf -1，能量密度为11 W h kg-1，功率密度为5795 W kg-1，在10,000次循环中保持72%的电容。这项工作强调了锡掺杂钨氧化物作为开发耐用、高能量密度伪电容器的有前途和可扩展的途径。
{"title":"Tuning Electrochemical Properties of Tungsten Oxides Nanoplates via Sn Doping and Mixed-Phase Formation for Superior Quasi-Solid-State Asymmetric Supercapacitor","authors":"Harishchandra S Nishad, Rajesh R. Jaiswar, Diwakar Singh, Shekhar Bhame, Shashikant P. Patole, Pravin S. Walke","doi":"10.1039/d5ta10336c","DOIUrl":"https://doi.org/10.1039/d5ta10336c","url":null,"abstract":"The development of high-performance electrode materials remains a critical challenge in advancing next-generation pseudocapacitors due to its low electrical conductivity, slow ion diffusion, and structural instability during long-term cycling. The hydrated tungsten oxide (WO3·H2O) has emerged as a promising candidate owing to its layered structure and abundant interlayer water. However, its electrochemical performance is still constrained by limited active sites and inefficient charge-transfer kinetics. To overcome these limitation, Sn doping and controlled phase engineering of WO3·H2O have been implemented to enhance the intrinsic electrochemical properties. Sn-doped WO3·H2O was synthesized at various doping concentrations via a simple wet chemical method, followed by annealing to achieve mixed phases of Sn-doped WO3·H2O and WO3. Furthermore, the electrochemical measurements exhibited a significant enhancement in specific capacitance, with doping concentration i.e. W0, SnW5, and SnW25 delivering specific capacitance of 115 F g-1, 146 F g-1, and 182 F g-1 at 1 A g-1, respectively. Similarly, among annealed samples (SnW200, SnW400 and SnW600), SnW200 exhibited the highest capacitance of 323 F g-1, demonstrating the synergestic effect of defect modulation and mixed-phase interaction. Eventually, the fabricated quasi-solid-state asymmetric supercapacitor (QSSAS) device achieved 36 F g-1, an energy density of 11 W h kg-1, and a power density of 5795 W kg-1, while retaining 72% capacitance over 10,000 cycles. This work highlights Sn-doped tungsten oxides as a promising and scalable route for developing durable, high-energy-density pseudocapacitors.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"234 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466053","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}
Qingyuan Song, Jinshou Yao, Liujun Jin, Peiyang Gu, Ye Wang, Ping Liu, Congping Chen, Guohong Dai
Dibutyl phthalate (DBP), a ubiquitous plasticizer pollutant, poses severe risks to environmental and human health, yet its high chemical stability makes valorization highly challenging. Herein, we report a one-pot, mild, and green strategy that directly upcycles DBP as an organic ligand to construct a ferroferric oxide functional Ni-based MOF framework nanocomposite (Fe3O4-Ni-MOF(DBP)) on nickel foam (NF), enabling the simultaneous detoxification of DBP and fabrication of a high-performance electrocatalyst. The in-situ integration of Fe3O4 nanoparticles with the Ni-MOF(DBP) endows the hybrid catalyst with accelerated charge-transfer kinetics, enhanced electrical conductivity, and abundant accessible active sites, leading to remarkable bifunctional activity for overall water splitting. In an alkaline electrolyte, Fe3O4-Ni-MOF(DBP)/NF exhibits outstanding bifunctional electrocatalytic performance, delivering low overpotentials of 233 mV for the OER and 42 mV for the HER at 10 mA cm -2 , along with excellent durability over continuous operation exceeding 40 h. In-situ Raman analysis reveals that the superior catalytic performance of Fe3O4-Ni-MOF(DBP)/NF is attributed to the dynamic reconstruction of surface metal sites into active (oxy)hydroxide intermediates. This work presents an innovative strategy for the valorization of toxic plastic pollutants, thus advancing the cross integration of environmental remediation and clean energy technologies.
邻苯二甲酸二丁酯（DBP）是一种普遍存在的增塑剂污染物，对环境和人类健康构成严重威胁，但其高化学稳定性使其增值极具挑战性。在此，我们报告了一种一锅，温和和绿色的策略，直接将DBP作为有机配体进行循环，在泡沫镍（NF）上构建铁氧化物功能镍基MOF框架纳米复合材料（Fe3O4-Ni-MOF(DBP)），同时实现DBP的解毒和高性能电催化剂的制造。Fe3O4纳米颗粒与Ni-MOF（DBP）的原位集成使杂化催化剂具有加速的电荷转移动力学，增强的电导率和丰富的可达活性位点，从而具有显著的双功能活性。在碱性电解液中，Fe3O4-Ni-MOF(DBP)/NF表现出出色的双功能电催化性能，在10 mA cm -2下，OER和HER的过电位分别为233 mV和42 mV，并且在连续运行超过40小时的情况下具有优异的耐久性。原位拉曼分析表明，Fe3O4-Ni-MOF(DBP)/NF的优异催化性能归因于表面金属位点动态重构为活性（氧）氢氧化物中间体。这项工作提出了有毒塑料污染物增值的创新策略，从而推动了环境修复和清洁能源技术的交叉整合。
{"title":"From Toxic Pollutant to Catalyst: One-Pot Synthesis of Fe3O4-Ni-DBP/NF for Efficient Overall Water Splitting","authors":"Qingyuan Song, Jinshou Yao, Liujun Jin, Peiyang Gu, Ye Wang, Ping Liu, Congping Chen, Guohong Dai","doi":"10.1039/d5ta10477g","DOIUrl":"https://doi.org/10.1039/d5ta10477g","url":null,"abstract":"Dibutyl phthalate (DBP), a ubiquitous plasticizer pollutant, poses severe risks to environmental and human health, yet its high chemical stability makes valorization highly challenging. Herein, we report a one-pot, mild, and green strategy that directly upcycles DBP as an organic ligand to construct a ferroferric oxide functional Ni-based MOF framework nanocomposite (Fe3O4-Ni-MOF(DBP)) on nickel foam (NF), enabling the simultaneous detoxification of DBP and fabrication of a high-performance electrocatalyst. The in-situ integration of Fe3O4 nanoparticles with the Ni-MOF(DBP) endows the hybrid catalyst with accelerated charge-transfer kinetics, enhanced electrical conductivity, and abundant accessible active sites, leading to remarkable bifunctional activity for overall water splitting. In an alkaline electrolyte, Fe3O4-Ni-MOF(DBP)/NF exhibits outstanding bifunctional electrocatalytic performance, delivering low overpotentials of 233 mV for the OER and 42 mV for the HER at 10 mA cm -2 , along with excellent durability over continuous operation exceeding 40 h. In-situ Raman analysis reveals that the superior catalytic performance of Fe3O4-Ni-MOF(DBP)/NF is attributed to the dynamic reconstruction of surface metal sites into active (oxy)hydroxide intermediates. This work presents an innovative strategy for the valorization of toxic plastic pollutants, thus advancing the cross integration of environmental remediation and clean energy technologies.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"11 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466054","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}
Electrode materials critically influence the performance of energy storage devices such as supercapacitors and batteries. Graphene quantum dots (GQDs) are a promising material for next-generation systems due to their high surface-to-volume ratio, tunable bandgaps, and stability. Their nanoscale size creates numerous edge sites with zigzag (ZZ) or armchair (AC) configurations. Yet, the role of edge shape in electrochemical behavior remains largely unexplored. Likewise, the correlation between synthesis methods and edge configurations is unclear, hindering the development of targeted fabrication approaches. In this study, nitrogen-doped GQDs (N-GQDs) with ZZ and AC edges were synthesized via hydrothermal and electrochemical methods. They were subsequently characterized using physical methods (XRD, TEM, UV-Vis, Raman spectroscopy). They were then electrodeposited onto carbon fibers and their electrochemical properties were analyzed (CV, EIS). We examined the N-GQD size, edge configuration, bandgap, charge transport, and process parameters such as pH and electrolyte choice. The results show that ZZ-edged N-GQDs outperform AC-edged counterparts in capacitance (double-layer, pseudocapacitance, quantum capacitance) due to a higher density of states originating from dispersionless edge states, which are absent at AC edges. Additionally, pH variations affect ZZ N-GQDs by modulating their energy bandgap, informing electrolyte selection and material tuning to deliver target applications such as batteries or supercapacitors. This work establishes performance differences between ZZ and AC edged N-GQDs, enabling precise nanoparticle design for optimized energy storage, and opens opportunities in bandgap-engineered applications such as solar cells, LEDs, lasers, and photodetectors.
电极材料对超级电容器和电池等储能设备的性能有着至关重要的影响。石墨烯量子点（GQDs）由于其高表面体积比、可调带隙和稳定性而成为下一代系统中很有前途的材料。它们的纳米级尺寸创建了许多锯齿状（ZZ）或扶手椅状（AC）配置的边缘位点。然而，边缘形状在电化学行为中的作用在很大程度上仍未被探索。同样，合成方法和边缘构型之间的相关性也不清楚，阻碍了有针对性的制造方法的发展。本研究通过水热法和电化学方法合成了具有ZZ边和AC边的氮掺杂GQDs （N-GQDs）。随后用物理方法（XRD， TEM, UV-Vis，拉曼光谱）对其进行了表征。然后将它们电沉积在碳纤维上，并分析了它们的电化学性能（CV， EIS）。我们研究了N-GQD的尺寸、边缘结构、带隙、电荷输运和工艺参数，如pH和电解质的选择。结果表明，zz边缘的N-GQDs在电容（双层、伪电容、量子电容）方面优于交流边缘的N-GQDs，这是由于来自无色散边缘态的态密度更高，而这些态在交流边缘是不存在的。此外，pH变化通过调节ZZ - N-GQDs的能带隙来影响它们，从而为电解质选择和材料调整提供信息，以提供诸如电池或超级电容器等目标应用。这项工作建立了ZZ和交流边缘N-GQDs之间的性能差异，实现了精确的纳米颗粒设计，以优化能量存储，并为带隙工程应用（如太阳能电池，led，激光器和光电探测器）开辟了机会。
{"title":"Impact of graphene quantum dot edge shapes on high-performance energy storage devices","authors":"Grainne Gilleece, Natasha Shirshova, Ensieh Hosseini, Karl Coleman, Marcos Perez-Pucheta, Dagou Zeze","doi":"10.1039/d5ta09677d","DOIUrl":"https://doi.org/10.1039/d5ta09677d","url":null,"abstract":"Electrode materials critically influence the performance of energy storage devices such as supercapacitors and batteries. Graphene quantum dots (GQDs) are a promising material for next-generation systems due to their high surface-to-volume ratio, tunable bandgaps, and stability. Their nanoscale size creates numerous edge sites with zigzag (ZZ) or armchair (AC) configurations. Yet, the role of edge shape in electrochemical behavior remains largely unexplored. Likewise, the correlation between synthesis methods and edge configurations is unclear, hindering the development of targeted fabrication approaches. In this study, nitrogen-doped GQDs (N-GQDs) with ZZ and AC edges were synthesized <em>via</em> hydrothermal and electrochemical methods. They were subsequently characterized using physical methods (XRD, TEM, UV-Vis, Raman spectroscopy). They were then electrodeposited onto carbon fibers and their electrochemical properties were analyzed (CV, EIS). We examined the N-GQD size, edge configuration, bandgap, charge transport, and process parameters such as pH and electrolyte choice. The results show that ZZ-edged N-GQDs outperform AC-edged counterparts in capacitance (double-layer, pseudocapacitance, quantum capacitance) due to a higher density of states originating from dispersionless edge states, which are absent at AC edges. Additionally, pH variations affect ZZ N-GQDs by modulating their energy bandgap, informing electrolyte selection and material tuning to deliver target applications such as batteries or supercapacitors. This work establishes performance differences between ZZ and AC edged N-GQDs, enabling precise nanoparticle design for optimized energy storage, and opens opportunities in bandgap-engineered applications such as solar cells, LEDs, lasers, and photodetectors.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"419 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489806","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}
Layered O3–NaNi1/3Fe1/3Mn1/3O2 (NMF) is a promising cathode material for commercialization of sodium-ion batteries (SIBs), but it still faces challenges due to its poor cycling stability and air instability. Herein, we demonstrate that through optimized synthesis conditions (sintering and composition), a single Ca-dopant additive can synergistically achieve bulk-doping and surface-modification effects. Microscopic characterizations reveal that a robust rock-salt structure is constructed on the non-(003) surface facets due to Ca surface enrichment, which is developed through the Ca dopant exsolution process during high-temperature sintering. Combining bulk-doping and surface-modification effects, the 3% Ca-doped NFM cathode demonstrates superb cycling stability and improved rate capability, boosting the capacity retention from 61.4% to 90.5% after 200 cycles at 2.0–4.0 V. Further microanalysis reveals that the surface Ca-enriched modification layer not only effectively suppresses the cycling-induced surface degradation but also significantly improves the air storage stability by acting as a physical barrier layer to prevent moisture degradation. This work offers a new pathway to achieve bulk and surface modifications by a simple doping strategy and reveals the dual effects of Ca-doping for enhanced performance of O3-type layered oxide cathodes.
{"title":"Bulk Ca-doping-induced surface modification enabling high-performance O3-type layered cathodes for sodium-ion batteries","authors":"Guoliang Liu, Xuejiao Zhao, Lihan Zhang, Xiaoqi Wang, Manling Sui, Pengfei Yan","doi":"10.1039/d6ta00644b","DOIUrl":"https://doi.org/10.1039/d6ta00644b","url":null,"abstract":"Layered O3–NaNi<small><sub>1/3</sub></small>Fe<small><sub>1/3</sub></small>Mn<small><sub>1/3</sub></small>O<small><sub>2</sub></small> (NMF) is a promising cathode material for commercialization of sodium-ion batteries (SIBs), but it still faces challenges due to its poor cycling stability and air instability. Herein, we demonstrate that through optimized synthesis conditions (sintering and composition), a single Ca-dopant additive can synergistically achieve bulk-doping and surface-modification effects. Microscopic characterizations reveal that a robust rock-salt structure is constructed on the non-(003) surface facets due to Ca surface enrichment, which is developed through the Ca dopant exsolution process during high-temperature sintering. Combining bulk-doping and surface-modification effects, the 3% Ca-doped NFM cathode demonstrates superb cycling stability and improved rate capability, boosting the capacity retention from 61.4% to 90.5% after 200 cycles at 2.0–4.0 V. Further microanalysis reveals that the surface Ca-enriched modification layer not only effectively suppresses the cycling-induced surface degradation but also significantly improves the air storage stability by acting as a physical barrier layer to prevent moisture degradation. This work offers a new pathway to achieve bulk and surface modifications by a simple doping strategy and reveals the dual effects of Ca-doping for enhanced performance of O3-type layered oxide cathodes.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"10 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466051","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}
THIEN AN LE, Youngmin Kim, Seung Ju Han, Young Hwan Im, Min Sik Kim, You-Jin Lee, Ho-Jeong Chae
Growing attention to using ammonia (NH3) as an energy carrier to produce COx-free H2 at low temperatures and supply it on demand at sites has renewed research interest. This study utilizes N-doped CeO2 material to support Ru via a solvothermal process for NH3 decomposition. The synergistic integration of N-doped CeO2 as a support and cesium (Cs) as a promoter has led to a breakthrough in catalytic activity. Advanced analysis techniques, including N2 physisorption, ICP, HAADF-STEM, CO pulse chemisorption, XRD, XPS, XAS, Raman, EPR, and temperature-programmed analysis, are employed to elucidate the beneficial properties of catalysts for the NH3 decomposition. Additionally, density functional theory (DFT) calculations provided atomic-scale insights, revealing that N-doping modulates the electronic properties of the Ru sites, thereby lowering the energy barrier for recombinative N2* desorption and enhancing high NH3 decomposition activity at low temperatures. Ru/2N-CeO2 and Cs-Ru/2N-CeO2 exhibited superior catalytic efficiency with a H2 yield of approximately 1,407 mmol/min/gRu and 2,115 mmol/min/gRu , respectively, and excellent stability during 100 h at 450 oC with WHSV = 30,000 mL NH3/gcat./h. This study demonstrates that the syngenetic effects of increased oxygen vacancies (Ov) and the effective modulation of the electronic environment of Ru sites, which are optimal for enhancing recombinative N2 desorption, are vital for developing Ru-based catalysts for NH3 decomposition.
越来越多的人关注使用氨（NH3）作为能量载体，在低温下生产不含cox的H2，并在现场按需供应，这重新引起了研究兴趣。本研究利用n掺杂的CeO2材料通过溶剂热过程支持Ru进行NH3分解。n掺杂CeO2作为载体和铯（Cs）作为促进剂的协同集成导致了催化活性的突破。采用先进的分析技术，包括N2物理吸附、ICP、HAADF-STEM、CO脉冲化学吸附、XRD、XPS、XAS、Raman、EPR和温度程序分析，来阐明催化剂对NH3分解的有利性质。此外，密度泛函理论（DFT）计算提供了原子尺度的见解，揭示了n掺杂调节Ru位点的电子性质，从而降低了重组N2*解吸的能垒，增强了低温下高NH3分解活性。Ru/2N-CeO2和Cs-Ru/2N-CeO2表现出优异的催化效率，H2产率分别约为1,407 mmol/min/gRu和2,115 mmol/min/gRu，并且在450℃、WHSV = 30,000 mL NH3/gcat./h条件下具有良好的100 h稳定性。该研究表明，增加氧空位（Ov）的同生效应和对Ru位点电子环境的有效调节是增强重组N2解吸的最佳选择，这对于开发Ru基NH3分解催化剂至关重要。
{"title":"Synergistic Electronic Modulation of Ru Sites via N-Doped CeO2 and Cs Promotion for High Efficiency H2 Generation from Ammonia Decomposition","authors":"THIEN AN LE, Youngmin Kim, Seung Ju Han, Young Hwan Im, Min Sik Kim, You-Jin Lee, Ho-Jeong Chae","doi":"10.1039/d5ta10316a","DOIUrl":"https://doi.org/10.1039/d5ta10316a","url":null,"abstract":"Growing attention to using ammonia (NH<small><sub>3</sub></small>) as an energy carrier to produce CO<small><sub>x</sub></small>-free H<small><sub>2</sub></small> at low temperatures and supply it on demand at sites has renewed research interest. This study utilizes N-doped CeO<small><sub>2</sub></small> material to support Ru via a solvothermal process for NH<small><sub>3</sub></small> decomposition. The synergistic integration of N-doped CeO<small><sub>2</sub></small> as a support and cesium (Cs) as a promoter has led to a breakthrough in catalytic activity. Advanced analysis techniques, including N<small><sub>2</sub></small> physisorption, ICP, HAADF-STEM, CO pulse chemisorption, XRD, XPS, XAS, Raman, EPR, and temperature-programmed analysis, are employed to elucidate the beneficial properties of catalysts for the NH<small><sub>3</sub></small> decomposition. Additionally, density functional theory (DFT) calculations provided atomic-scale insights, revealing that N-doping modulates the electronic properties of the Ru sites, thereby lowering the energy barrier for recombinative N<small><sub>2</sub></small>* desorption and enhancing high NH<small><sub>3</sub></small> decomposition activity at low temperatures. Ru/2N-CeO<small><sub>2</sub></small> and Cs-Ru/2N-CeO<small><sub>2</sub></small> exhibited superior catalytic efficiency with a H<small><sub>2</sub></small> yield of approximately 1,407 mmol/min/g<small><sub>Ru</sub></small> and 2,115 mmol/min/g<small><sub>Ru</sub></small> , respectively, and excellent stability during 100 h at 450 <small><sup>o</sup></small>C with WHSV = 30,000 mL NH<small><sub>3</sub></small>/g<small><sub>cat.</sub></small>/h. This study demonstrates that the syngenetic effects of increased oxygen vacancies (Ov) and the effective modulation of the electronic environment of Ru sites, which are optimal for enhancing recombinative N<small><sub>2</sub></small> desorption, are vital for developing Ru-based catalysts for NH<small><sub>3</sub></small> decomposition.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"77 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479025","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}
Die Luo, Ben Niu, Qiurui Lin, Pan Du, Chen Peng, Xian-ru He
Polymers are emerging as powerful modulators of both bulk electrolyte structure and interfacial chemistry at zinc-metal anodes, enabling substantial improvements in battery performance. Among their structural parameters, polymer chain length, spanning tens to thousands of repeating units, critically governs both ion migration networks in the bulk electrolyte and adsorption dynamics at zinc-metal anodes, thereby determining electrochemical behavior. Despite its importance, the mechanistic role of chain length remains poorly understood. Here, we synthesize a series of poly(N-vinylpyrrolidone) (PNVP) with systematically varied chain lengths to investigate their effects on Zn2+ transport, interfacial adsorption, and battery performance. Medium-chain PNVP optimally balances bulk network formation and interfacial regulation, simultaneously establishing efficient Zn2+ migration pathways and an in situ dense, ion-channel-rich interfacial adsorption layer, enabling stable cycling for over 3600 h. In contrast, short-chain PNVP yields weak ion networks and poor adsorption, restricting lifespan to 1100 h, while long-chain PNVP suffers from excessive entanglement and a thick interfacial layer, limiting lifespan to 1700 h. These findings reveal a chain-length-dependent mechanism that couples bulk ion transport with interfacial regulation, offering molecular-level guidance for the rational design of high-performance aqueous zinc-metal batteries.
{"title":"Polymer Chain Length Governs Ion Transport and Interfacial Dynamics in Aqueous Zinc-Metal Batteries","authors":"Die Luo, Ben Niu, Qiurui Lin, Pan Du, Chen Peng, Xian-ru He","doi":"10.1039/d6ta00241b","DOIUrl":"https://doi.org/10.1039/d6ta00241b","url":null,"abstract":"Polymers are emerging as powerful modulators of both bulk electrolyte structure and interfacial chemistry at zinc-metal anodes, enabling substantial improvements in battery performance. Among their structural parameters, polymer chain length, spanning tens to thousands of repeating units, critically governs both ion migration networks in the bulk electrolyte and adsorption dynamics at zinc-metal anodes, thereby determining electrochemical behavior. Despite its importance, the mechanistic role of chain length remains poorly understood. Here, we synthesize a series of poly(N-vinylpyrrolidone) (PNVP) with systematically varied chain lengths to investigate their effects on Zn2+ transport, interfacial adsorption, and battery performance. Medium-chain PNVP optimally balances bulk network formation and interfacial regulation, simultaneously establishing efficient Zn2+ migration pathways and an in situ dense, ion-channel-rich interfacial adsorption layer, enabling stable cycling for over 3600 h. In contrast, short-chain PNVP yields weak ion networks and poor adsorption, restricting lifespan to 1100 h, while long-chain PNVP suffers from excessive entanglement and a thick interfacial layer, limiting lifespan to 1700 h. These findings reveal a chain-length-dependent mechanism that couples bulk ion transport with interfacial regulation, offering molecular-level guidance for the rational design of high-performance aqueous zinc-metal batteries.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"50 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466069","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}
Chonghan Xia, Junhao Ma, Qihang Chen, Yee Yan Tay, Lydia H. Wong, Kwan W. Tan
The synthesis of ordered mesoporous multimetallic alloys (MMAs) with controlled composition remains challenging due to disparate reduction kinetics of multimetal precursors. Here we report a one-pot nanocasting approach in which PtFeCoNiCu salts are co-infiltrated and co-reduced within a gyroidal KIT-6 mesoporous silica scaffold, followed by template removal and acid etching, yielding single phase fcc mesoporous alloys with a 3D bicontinuous network morphology. By tuning the reduction conditions, we regulate the incorporation of Fe, Co and Ni around a PtCu-rich solid-solution lattice and remove FeCoNi overgrowths, exposing an ordered Pt-based mesoporous framework with excellent HER performance. The optimized ordered MMA catalyst, delivers an overpotential of 25 mV at 10 mA cm−2, a Tafel slope of 49.1 mV dec−1, and negligible degradation over 100 000 cycles, outperforming both commercial Pt/C and mesoporous Pt controls. This work demonstrates a general route to compositionally tuned ordered mesoporous multimetallic solid-solution alloys suitable for catalysis, sensing and related functional materials.
由于多金属前驱体的不同还原动力学，合成具有控制成分的有序介孔多金属合金（MMAs）仍然具有挑战性。在这里，我们报告了一种单锅纳米铸造方法，其中PtFeCoNiCu盐在一个螺旋形KIT-6介孔硅支架内共浸润和共还原，然后去除模板和酸蚀刻，产生具有三维双连续网络形态的单相fcc介孔合金。通过调整还原条件，我们调节了富ptcu固溶体晶格周围Fe， Co和Ni的掺入，并去除了FeCoNi的过度生长，从而暴露出具有优异HER性能的有序pt基介孔框架。优化后的有序MMA催化剂在10 mA cm−2下的过电位为25 mV， Tafel斜率为49.1 mV dec−1，在10万次循环中降解可以忽略，优于商业Pt/C和介孔Pt控制。这项工作展示了一种适合于催化、传感和相关功能材料的组合调谐有序介孔多金属固溶体合金的一般途径。
{"title":"One-pot nanocasting of 3D ordered bicontinuous mesoporous Pt-based multimetallic alloys for efficient hydrogen evolution","authors":"Chonghan Xia, Junhao Ma, Qihang Chen, Yee Yan Tay, Lydia H. Wong, Kwan W. Tan","doi":"10.1039/d5ta09402j","DOIUrl":"https://doi.org/10.1039/d5ta09402j","url":null,"abstract":"The synthesis of ordered mesoporous multimetallic alloys (MMAs) with controlled composition remains challenging due to disparate reduction kinetics of multimetal precursors. Here we report a one-pot nanocasting approach in which PtFeCoNiCu salts are co-infiltrated and co-reduced within a gyroidal KIT-6 mesoporous silica scaffold, followed by template removal and acid etching, yielding single phase fcc mesoporous alloys with a 3D bicontinuous network morphology. By tuning the reduction conditions, we regulate the incorporation of Fe, Co and Ni around a PtCu-rich solid-solution lattice and remove FeCoNi overgrowths, exposing an ordered Pt-based mesoporous framework with excellent HER performance. The optimized ordered MMA catalyst, delivers an overpotential of 25 mV at 10 mA cm<small><sup>−2</sup></small>, a Tafel slope of 49.1 mV dec<small><sup>−1</sup></small>, and negligible degradation over 100 000 cycles, outperforming both commercial Pt/C and mesoporous Pt controls. This work demonstrates a general route to compositionally tuned ordered mesoporous multimetallic solid-solution alloys suitable for catalysis, sensing and related functional materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"80 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479021","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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