Xuan Shu,Yongbin Chen,Minjie Hou,Jiarui Liang,Xinyu Yan,Huiyang Bian,Chuanfu Liu
Nanoplastics (NPs) pose growing environmental and health concerns owing to their small size, high mobility, and ability to penetrate biological barriers. However, efficient NP separation remains challenging because conventional membrane filtration often suffers from the trade-off between separation efficiency and water flux. Herein, a bioinspired composite membrane was developed by integrating a polydopamine/polyethylenimine (PDA/PEI) interfacial layer and a TEMPO-oxidized cellulose nanofiber (TCNF) functional coating onto a poly(vinylidene fluoride) (PVDF) ultrafiltration membrane. The PDA/PEI layer provided robust interfacial adhesion and abundant active sites for TCNF immobilization, while the hydroxyl- and carboxyl-rich TCNF network established a highly accessible hydrated interface that promoted nanoplastic capture through enhanced interfacial interactions. The optimized membrane achieved a high pure-water flux of 9857.3 L m⁻² h⁻¹ and nanoplastic rejection efficiencies exceeding 99.0% for 100 nm amino-functionalized polystyrene nanoparticles. Hermia model analysis revealed that nanoplastic rejection was dominated by cake filtration, with nanoparticles preferentially retained on the membrane surface rather than penetrating into the membrane interior. Molecular dynamics simulations further demonstrated that the hydrated TCNF interface strengthened hydrogen bonding, electrostatic attraction, and interfacial contact with nanoplastics, thereby stabilizing retained particles and promoting surface capture. Moreover, the excellent interfacial stability and reusability of the membrane enabled robust performance across diverse filtration scenarios, while maintaining an intact coating structure and stable separation efficiency throughout repeated filtration cycles. This work provides an effective bioinspired interfacial engineering strategy for constructing high-flux membranes with enhanced nanoplastic rejection and offers mechanistic insights into interfacial regulation for advanced water purification.
{"title":"Bioinspired Nanocellulose-Functionalized PVDF Membrane for Simultaneously Maintaining High-Flux and Efficient Nanoplastics Filtration","authors":"Xuan Shu,Yongbin Chen,Minjie Hou,Jiarui Liang,Xinyu Yan,Huiyang Bian,Chuanfu Liu","doi":"10.1039/d6ta05928g","DOIUrl":"https://doi.org/10.1039/d6ta05928g","url":null,"abstract":"Nanoplastics (NPs) pose growing environmental and health concerns owing to their small size, high mobility, and ability to penetrate biological barriers. However, efficient NP separation remains challenging because conventional membrane filtration often suffers from the trade-off between separation efficiency and water flux. Herein, a bioinspired composite membrane was developed by integrating a polydopamine/polyethylenimine (PDA/PEI) interfacial layer and a TEMPO-oxidized cellulose nanofiber (TCNF) functional coating onto a poly(vinylidene fluoride) (PVDF) ultrafiltration membrane. The PDA/PEI layer provided robust interfacial adhesion and abundant active sites for TCNF immobilization, while the hydroxyl- and carboxyl-rich TCNF network established a highly accessible hydrated interface that promoted nanoplastic capture through enhanced interfacial interactions. The optimized membrane achieved a high pure-water flux of 9857.3 L m⁻² h⁻¹ and nanoplastic rejection efficiencies exceeding 99.0% for 100 nm amino-functionalized polystyrene nanoparticles. Hermia model analysis revealed that nanoplastic rejection was dominated by cake filtration, with nanoparticles preferentially retained on the membrane surface rather than penetrating into the membrane interior. Molecular dynamics simulations further demonstrated that the hydrated TCNF interface strengthened hydrogen bonding, electrostatic attraction, and interfacial contact with nanoplastics, thereby stabilizing retained particles and promoting surface capture. Moreover, the excellent interfacial stability and reusability of the membrane enabled robust performance across diverse filtration scenarios, while maintaining an intact coating structure and stable separation efficiency throughout repeated filtration cycles. This work provides an effective bioinspired interfacial engineering strategy for constructing high-flux membranes with enhanced nanoplastic rejection and offers mechanistic insights into interfacial regulation for advanced water purification.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"33 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152051","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 redox-active oxides, the same metal–oxygen redox chemistry that stores the charge can drive catalytic reactions at the electrolyte interface. In nickel oxide, anodic Ni–O redox produces electrochromic coloration and overlaps with the oxygen evolution reaction (OER) at higher potentials. This overlap limits coloration efficiency because the OER proceeds as a parasitic side reaction. The two responses have distinct structural requirements: coloration depends on the oxidation state of the Ni site and ion-coupled charge compensation in the lattice, whereas the OER depends on adjacent oxidized Ni–O sites at the surface. Here, we substitute Ni2+ with transparent redox-inactive cations (Zn2+, Mg2+, or Ca2+) with different size mismatch relative to Ni2+, which perturb the lattice and dilute surface Ni sites. In all three dopant series, the optical contrast increases at moderate content and decreases at 10% nominal doping; the enhancement is the largest for Ca2+, which produces the largest lattice expansion. The OER-region current instead decreases monotonically across the Zn series and at 10% for Mg and Ca, with the strongest suppression for Ca2+ despite its lowest incorporated dopant content. Operando UV-vis spectroelectrochemistry shows that the OER reaction order with respect to oxidized Ni–O species increases toward the pair-site value of two for all three dopants, consistent with reduced cooperativity among oxidized Ni–O species after substitution. Redox-inactive modification at moderate content thus enhances the electrochromic response through the lattice expansion and suppresses oxygen evolution through the dilution and disruption of the surface Ni network.
{"title":"Lattice expansion enhances electrochromism while surface Ni-site dilution suppresses oxygen evolution in divalent-doped NiO","authors":"Muhammad Waseem Yaseen,Xuefei Li","doi":"10.1039/d6ta05737c","DOIUrl":"https://doi.org/10.1039/d6ta05737c","url":null,"abstract":"In redox-active oxides, the same metal–oxygen redox chemistry that stores the charge can drive catalytic reactions at the electrolyte interface. In nickel oxide, anodic Ni–O redox produces electrochromic coloration and overlaps with the oxygen evolution reaction (OER) at higher potentials. This overlap limits coloration efficiency because the OER proceeds as a parasitic side reaction. The two responses have distinct structural requirements: coloration depends on the oxidation state of the Ni site and ion-coupled charge compensation in the lattice, whereas the OER depends on adjacent oxidized Ni–O sites at the surface. Here, we substitute Ni2+ with transparent redox-inactive cations (Zn2+, Mg2+, or Ca2+) with different size mismatch relative to Ni2+, which perturb the lattice and dilute surface Ni sites. In all three dopant series, the optical contrast increases at moderate content and decreases at 10% nominal doping; the enhancement is the largest for Ca2+, which produces the largest lattice expansion. The OER-region current instead decreases monotonically across the Zn series and at 10% for Mg and Ca, with the strongest suppression for Ca2+ despite its lowest incorporated dopant content. Operando UV-vis spectroelectrochemistry shows that the OER reaction order with respect to oxidized Ni–O species increases toward the pair-site value of two for all three dopants, consistent with reduced cooperativity among oxidized Ni–O species after substitution. Redox-inactive modification at moderate content thus enhances the electrochromic response through the lattice expansion and suppresses oxygen evolution through the dilution and disruption of the surface Ni network.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"6 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152793","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}
Incorporating a secondary organic solvent into aqueous electrolytes is a promising strategy for tuning solvent structure, suppressing parasitic reactions, and improving electrodeposition performance. Rational co-solvent selection requires mechanistic understanding of how the additive modifies metal-ion solvation, bulk electrolyte chemistry and transport, and interfacial electrochemistry. Here, we investigate dimethylformamide (DMF)/water mixed solvents for Fe electrodeposition from FeSO₄ electrolytes by testing these mechanisms. XANES and EXAFS show that below 50 vol% DMF, Fe(II) remains predominantly aqua-coordinated, indicating little change in the primary Fe(II) coordination environment. FTIR shows that DMF measurably reorganizes the DMF-H₂O hydrogen-bond network, consistent with reduced bulk-water-like activity. Electrochemical measurements show that DMF suppresses both HER and Fe deposition, while deposition efficiencies collapse approximately onto a common trend when normalized by the Fe limiting current, indicating that performance is governed primarily by bulk transport with changed viscosity and resistance. XPS detects no DMF-derived nitrogen on deposited Fe, and cathodic stability measurements indicate that DMF decomposition occurs well beyond the Fe deposition potential window, arguing against a dominant interfacial decomposition mechanism. Instead, the main practical benefit of DMF is bulk electrolyte stabilization that DMF suppresses Fe(III)-driven hydrolysis, raises the natural pH, and shifts the electrolyte open-circuit potential farther from the Fe(II)/Fe₂O₃·xH₂O instability boundary without substantially altering Fe(II)/Fe(0) thermodynamics. These findings show that DMF acts primarily through bulk solvent reorganization, Fe(III) stabilization, and transport modification rather than through strong direct Fe(II) solvation or persistent interfacial restructuring, and they provide a mechanistic framework for co-solvent design in aqueous Fe electrosynthesis.
{"title":"From Molecular Reorganization to Nanoscale Heterogeneity: The Role of DMF in Aqueous Fe Electrodeposition Electrolytes","authors":"Yunkai Sun,Nguyen Huong,Shivam Singh,Xingyi Lyu,Álvaro Vázquez-Mayagoitia,Jordi Cabana,Tao Li,Brian J Ingram,Zhenzhen Yang","doi":"10.1039/d6ta06484a","DOIUrl":"https://doi.org/10.1039/d6ta06484a","url":null,"abstract":"Incorporating a secondary organic solvent into aqueous electrolytes is a promising strategy for tuning solvent structure, suppressing parasitic reactions, and improving electrodeposition performance. Rational co-solvent selection requires mechanistic understanding of how the additive modifies metal-ion solvation, bulk electrolyte chemistry and transport, and interfacial electrochemistry. Here, we investigate dimethylformamide (DMF)/water mixed solvents for Fe electrodeposition from FeSO₄ electrolytes by testing these mechanisms. XANES and EXAFS show that below 50 vol% DMF, Fe(II) remains predominantly aqua-coordinated, indicating little change in the primary Fe(II) coordination environment. FTIR shows that DMF measurably reorganizes the DMF-H₂O hydrogen-bond network, consistent with reduced bulk-water-like activity. Electrochemical measurements show that DMF suppresses both HER and Fe deposition, while deposition efficiencies collapse approximately onto a common trend when normalized by the Fe limiting current, indicating that performance is governed primarily by bulk transport with changed viscosity and resistance. XPS detects no DMF-derived nitrogen on deposited Fe, and cathodic stability measurements indicate that DMF decomposition occurs well beyond the Fe deposition potential window, arguing against a dominant interfacial decomposition mechanism. Instead, the main practical benefit of DMF is bulk electrolyte stabilization that DMF suppresses Fe(III)-driven hydrolysis, raises the natural pH, and shifts the electrolyte open-circuit potential farther from the Fe(II)/Fe₂O₃·xH₂O instability boundary without substantially altering Fe(II)/Fe(0) thermodynamics. These findings show that DMF acts primarily through bulk solvent reorganization, Fe(III) stabilization, and transport modification rather than through strong direct Fe(II) solvation or persistent interfacial restructuring, and they provide a mechanistic framework for co-solvent design in aqueous Fe electrosynthesis.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"33 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152794","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}
The sustainable reutilization of waste graphite from used lithium-ion batteries represents an important strategy for eco-friendly resource recovery. In this work, we successfully convert the graphite into N-doped expanded holey graphene (N-EhGH) as a cathode for lithium–oxygen batteries (LOBs) through H2O activation and nitrogen doping techniques. The synthesized N-EhGH possesses an expanded holey architecture with an ultrahigh specific surface area, which significantly facilitates the mass transport and storage of Li+ and O2. Experimental characterization studies combined with theoretical calculations demonstrate that the synergistic effect between carbon defects and pyrrolic-N species optimizes the electronic configuration and strengthens Li2O2 binding, thereby promoting oxygen redox kinetics. Benefiting from these structural and electronic advantages, the N-EhGH cathode exhibits exceptional electrochemical performance, achieving a maximum specific capacity of 11 816 mAh g−1 at 300 mA g−1 and maintaining remarkable cycling stability over 800 cycles with a limited capacity of 1000 mAh g−1 at 1000 mA g−1.
废旧锂离子电池石墨的可持续再利用是生态资源回收的重要策略。在这项工作中，我们通过水活化和氮掺杂技术成功地将石墨转化为n掺杂膨胀多孔石墨烯（N-EhGH）作为锂氧电池（lob）的阴极。合成的N-EhGH具有膨胀的孔洞结构，具有超高的比表面积，显著促进了Li+和O2的质量传输和储存。实验表征研究结合理论计算表明，碳缺陷与吡咯烷- n之间的协同效应优化了电子构型，加强了Li2O2的结合，从而促进了氧氧化还原动力学。得益于这些结构和电子方面的优势，N-EhGH阴极表现出优异的电化学性能，在300 mA g - 1时达到11816 mAh g - 1的最大比容量，在1000 mA g - 1时保持800次循环的显着稳定性。
{"title":"Engineering a triple-enhanced graphite cathode from waste: holey, defective, and N-doped architectures for stable Li–O batteries","authors":"Jiakui Zhang,Ran Bi,Lingyun Zhou,Liang Liu,Qinghua Fan,Jianyuming Zhang,Jiantie Xu","doi":"10.1039/d6ta04966d","DOIUrl":"https://doi.org/10.1039/d6ta04966d","url":null,"abstract":"The sustainable reutilization of waste graphite from used lithium-ion batteries represents an important strategy for eco-friendly resource recovery. In this work, we successfully convert the graphite into N-doped expanded holey graphene (N-EhGH) as a cathode for lithium–oxygen batteries (LOBs) through H2O activation and nitrogen doping techniques. The synthesized N-EhGH possesses an expanded holey architecture with an ultrahigh specific surface area, which significantly facilitates the mass transport and storage of Li+ and O2. Experimental characterization studies combined with theoretical calculations demonstrate that the synergistic effect between carbon defects and pyrrolic-N species optimizes the electronic configuration and strengthens Li2O2 binding, thereby promoting oxygen redox kinetics. Benefiting from these structural and electronic advantages, the N-EhGH cathode exhibits exceptional electrochemical performance, achieving a maximum specific capacity of 11 816 mAh g−1 at 300 mA g−1 and maintaining remarkable cycling stability over 800 cycles with a limited capacity of 1000 mAh g−1 at 1000 mA g−1.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"1 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152796","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}
Mikołaj Kozak,Oleg Tkachenko,Marta Gajewska,Mateusz M. Marzec,Łukasz Pięta,Krystian Sokołowski,Grzegorz D. Sulka,Agnieszka Brzózka
Transition metal selenides have been intensively investigated due to their promising applications in energy conversion and storage technologies. In line with this interest, the development of simple and cost-effective methods for synthesizing these materials directly on conductive substrates is highly desirable. Here, we report the preparation of CoSe2 films by pulse electrodeposition from a solution based on a Deep Eutectic Solvent (DES). The resulting material consists of a rough, grainy, amorphous cobalt diselenide layer deposited directly onto graphite foil without the need for binders or additional conductive additives. The electrochemical performance of the prepared CoSe2 films was examined in 5 M LiNO3 within the three different potential ranges. A mixed charge storage mechanism was evidenced, whereby the faradaic contribution remarkably decreased with narrowing of the potential window. Those findings were in full agreement with the material's post-mortem analysis, which indicated smaller degradation in a narrow potential range. The abovementioned measurements proved the suitability of the deposited CoSe2 as an electrode material for supercapacitors. The specific capacity, determined in 5 M LiNO3 in three-electrode configuration at 1 mV s−1 was 13.5 F g−1.
过渡金属硒化物由于在能量转换和存储技术中具有广阔的应用前景而受到广泛的研究。根据这一兴趣，开发简单且具有成本效益的方法直接在导电基板上合成这些材料是非常可取的。在这里，我们报道了用脉冲电沉积方法从基于深度共晶溶剂（DES）的溶液中制备CoSe2薄膜。所得到的材料由粗糙的、粒状的、无定形的二硒化钴层直接沉积在石墨箔上，而不需要粘合剂或额外的导电添加剂。在5 M LiNO3中，在三个不同电位范围内测试了制备的CoSe2薄膜的电化学性能。证明了一种混合电荷存储机制，其中法拉第贡献随着电位窗口的缩小而显著降低。这些发现与材料的尸检分析完全一致，后者表明在狭窄的潜在范围内降解较小。上述测量证明了沉积的CoSe2作为超级电容器电极材料的适用性。在5 M LiNO3三电极配置下，在1 mV s−1下测定的比容量为13.5 F g−1。
{"title":"Efficient synthesis of electroactive CoSe from a deep eutectic solvent","authors":"Mikołaj Kozak,Oleg Tkachenko,Marta Gajewska,Mateusz M. Marzec,Łukasz Pięta,Krystian Sokołowski,Grzegorz D. Sulka,Agnieszka Brzózka","doi":"10.1039/d6ta05472b","DOIUrl":"https://doi.org/10.1039/d6ta05472b","url":null,"abstract":"Transition metal selenides have been intensively investigated due to their promising applications in energy conversion and storage technologies. In line with this interest, the development of simple and cost-effective methods for synthesizing these materials directly on conductive substrates is highly desirable. Here, we report the preparation of CoSe2 films by pulse electrodeposition from a solution based on a Deep Eutectic Solvent (DES). The resulting material consists of a rough, grainy, amorphous cobalt diselenide layer deposited directly onto graphite foil without the need for binders or additional conductive additives. The electrochemical performance of the prepared CoSe2 films was examined in 5 M LiNO3 within the three different potential ranges. A mixed charge storage mechanism was evidenced, whereby the faradaic contribution remarkably decreased with narrowing of the potential window. Those findings were in full agreement with the material's post-mortem analysis, which indicated smaller degradation in a narrow potential range. The abovementioned measurements proved the suitability of the deposited CoSe2 as an electrode material for supercapacitors. The specific capacity, determined in 5 M LiNO3 in three-electrode configuration at 1 mV s−1 was 13.5 F g−1.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"8 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173194","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}
Hong Liu,Xinhao Zhao,Xin Kong,Zhenhua Ge,Rui Bao,Junpeng Li
Commercialization of high-capacity silicon (Si) anodes is hampered by fragile physical contacts with the conductive matrix, which inevitably induce irreversible lithium consumption and low initial coulombic efficiency (ICE). To overcome this bottleneck, we first perform density functional theory (DFT) calculations, which predict that constructing nitrogen-induced Si–N–C covalent bridges at the Si/carbon interface dramatically enhances the Li+ adsorption energy (−5.28 eV) and redistributes the interfacial charge density, while synergistically lowering the diffusion barrier (0.9799 eV). Guided by these insights, we design an in situ chemical welding strategy using melamine as the nitrogen source to synthesize a dual-layer Si@SiOx/N-rGO composite. The optimized anode delivers an outstanding ICE of 93.01%, with a high initial discharge capacity of 2244.70 mAh g−1 at 0.1 A g−1 and retains 735.48 mAh g−1 after 500 cycles at 1.0 A g−1, significantly outperforming the undoped control. Multi-scale characterization (EIS-DRT and AFM) studies jointly demonstrate that the interfacial Si–N–C covalent bond acts as a mechanical anchor to suppress volume strain and SEI reconstruction, fundamentally reducing irreversible lithium loss and enhancing kinetics. This work provides atomic-scale insights into covalent interface design and gives a universally applicable, theory-guided strategy for high-energy-density lithium-ion batteries.
高容量硅（Si）阳极与导电基体的物理接触脆弱，不可避免地导致不可逆的锂消耗和较低的初始库仑效率（ICE），阻碍了高容量硅（Si）阳极的商业化。为了克服这一瓶颈，我们首先进行了密度功能理论（DFT）计算，预测在Si/碳界面上构建氮诱导的Si - n- c共价桥可以显著提高Li+吸附能（- 5.28 eV），并重新分配界面电荷密度，同时协同降低扩散势垒（0.9799 eV）。在这些见解的指导下，我们设计了一种原位化学焊接策略，使用三聚氰胺作为氮源合成双层Si@SiOx/N-rGO复合材料。优化后的阳极提供了93.01%的出色ICE，在0.1 a g - 1下具有2244.70 mAh g - 1的高初始放电容量，在1.0 a g - 1下循环500次后仍保持735.48 mAh g - 1，显著优于未掺杂的阳极。多尺度表征（EIS-DRT和AFM）研究共同表明，界面Si-N-C共价键作为机械锚，抑制了体积应变和SEI重建，从根本上减少了不可逆的锂损失，增强了动力学。这项工作为共价界面设计提供了原子尺度的见解，并为高能量密度锂离子电池提供了普遍适用的理论指导策略。
{"title":"Nitrogen-engineered covalent synergy in dual-layer encapsulated silicon anodes for superior initial coulombic efficiency","authors":"Hong Liu,Xinhao Zhao,Xin Kong,Zhenhua Ge,Rui Bao,Junpeng Li","doi":"10.1039/d6ta06320a","DOIUrl":"https://doi.org/10.1039/d6ta06320a","url":null,"abstract":"Commercialization of high-capacity silicon (Si) anodes is hampered by fragile physical contacts with the conductive matrix, which inevitably induce irreversible lithium consumption and low initial coulombic efficiency (ICE). To overcome this bottleneck, we first perform density functional theory (DFT) calculations, which predict that constructing nitrogen-induced Si–N–C covalent bridges at the Si/carbon interface dramatically enhances the Li+ adsorption energy (−5.28 eV) and redistributes the interfacial charge density, while synergistically lowering the diffusion barrier (0.9799 eV). Guided by these insights, we design an in situ chemical welding strategy using melamine as the nitrogen source to synthesize a dual-layer Si@SiOx/N-rGO composite. The optimized anode delivers an outstanding ICE of 93.01%, with a high initial discharge capacity of 2244.70 mAh g−1 at 0.1 A g−1 and retains 735.48 mAh g−1 after 500 cycles at 1.0 A g−1, significantly outperforming the undoped control. Multi-scale characterization (EIS-DRT and AFM) studies jointly demonstrate that the interfacial Si–N–C covalent bond acts as a mechanical anchor to suppress volume strain and SEI reconstruction, fundamentally reducing irreversible lithium loss and enhancing kinetics. This work provides atomic-scale insights into covalent interface design and gives a universally applicable, theory-guided strategy for high-energy-density lithium-ion batteries.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"53 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152797","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}
Charge transfer at perovskite–molecule interfaces is commonly interpreted using static frontier energy-level alignment. However, this framework often fails to explain experimentally observed interfacial charge-transfer behaviour because it overlooks the decisive roles of molecular binding geometry, adsorption-induced electronic redistribution, and interfacial electronic coupling. Developing molecular design principles that can simultaneously control these factors remains a fundamental challenge for perovskite photocatalysis. Here, we demonstrate that multidentate imidazophenanthroline (ImPheZ) scaffolds regulate charge separation at CsPbBr3 perovskite interfaces through cooperative control of molecular anchoring, substituent electronics, and metal coordination. A library of electron-donating and electron-withdrawing ImPheZ ligands and their Ru(ii) and Ir(iii) complexes was rationally designed to establish structure–interfacial property relationships. Our spectroscopic, electrochemical, and theoretical studies reveal that efficient interfacial hole extraction is governed not simply by energetic driving forces. Instead, it arises from the synergistic interplay of multidentate binding, interfacial electronic coupling, and metal-induced charge redistribution. Electron-rich ligands, particularly L1, exhibit the most efficient charge separation, while metal coordination further reprograms binding modes and electronic communication, leading to enhanced interfacial charge transfer. These molecularly engineered interfaces translate directly into improved photocatalytic benzylamine oxidation, with the CsPbBr3-RuL1 hybrid achieving the highest conversion (38%) together with enhanced E/Z selectivity. Beyond demonstrating a new ligand platform for the CsPbBr3 system, this work establishes multidentate molecular engineering of ImPheZ scaffolds as an effective strategy for regulating charge separation at CsPbBr3 perovskite interfaces beyond conventional energy-level design. The principles developed here may be explored for other perovskite–molecule interfaces, providing a blueprint for the design of highly efficient and selective hybrid photocatalysts for solar-driven organic transformations.
{"title":"Beyond static energy-level alignment: multidentate molecular engineering of imidazophenanthroline scaffolds regulates charge separation at CsPbBr interfaces for selective photocatalysis","authors":"Shivani Gupta,Megha,Himanshu Sonker,Ritika Gautam Singh,Vishal Govind Rao","doi":"10.1039/d6ta05677f","DOIUrl":"https://doi.org/10.1039/d6ta05677f","url":null,"abstract":"Charge transfer at perovskite–molecule interfaces is commonly interpreted using static frontier energy-level alignment. However, this framework often fails to explain experimentally observed interfacial charge-transfer behaviour because it overlooks the decisive roles of molecular binding geometry, adsorption-induced electronic redistribution, and interfacial electronic coupling. Developing molecular design principles that can simultaneously control these factors remains a fundamental challenge for perovskite photocatalysis. Here, we demonstrate that multidentate imidazophenanthroline (ImPheZ) scaffolds regulate charge separation at CsPbBr3 perovskite interfaces through cooperative control of molecular anchoring, substituent electronics, and metal coordination. A library of electron-donating and electron-withdrawing ImPheZ ligands and their Ru(ii) and Ir(iii) complexes was rationally designed to establish structure–interfacial property relationships. Our spectroscopic, electrochemical, and theoretical studies reveal that efficient interfacial hole extraction is governed not simply by energetic driving forces. Instead, it arises from the synergistic interplay of multidentate binding, interfacial electronic coupling, and metal-induced charge redistribution. Electron-rich ligands, particularly L1, exhibit the most efficient charge separation, while metal coordination further reprograms binding modes and electronic communication, leading to enhanced interfacial charge transfer. These molecularly engineered interfaces translate directly into improved photocatalytic benzylamine oxidation, with the CsPbBr3-RuL1 hybrid achieving the highest conversion (38%) together with enhanced E/Z selectivity. Beyond demonstrating a new ligand platform for the CsPbBr3 system, this work establishes multidentate molecular engineering of ImPheZ scaffolds as an effective strategy for regulating charge separation at CsPbBr3 perovskite interfaces beyond conventional energy-level design. The principles developed here may be explored for other perovskite–molecule interfaces, providing a blueprint for the design of highly efficient and selective hybrid photocatalysts for solar-driven organic transformations.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"43 1 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152798","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}
Bifunctional oxygen electrocatalysts with low cost, high activity, and long-term durability hold critical significance for rechargeable zinc-air batteries (RZABs), yet the design of such catalysts still confronts enormous challenges. Herein, a novel bifunctional electrocatalyst consisted of NiFe metal-organic framework (NiFe-MOF) grown on carbon black with highly dispersed FeN4 single sites (NiFe-MOF/FeN4C) is reported for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) involved in liquid and flexible RZABs. The catalyst is prepared via the pyrolysis of hemin chloride adsorbed on carbon black, followed by the growth of NiFe-MOF through a hydrothermal method. The pyrolysis of hemin chloride produces single Fe atoms coordinated with four pyrrolic N atom onto carbon black. The grown NiFe-MOF has strong electronic interaction with the FeN4 sites. The cooperative effect between NiFe-MOF and FeN4C delivers outstanding bifunctional catalytic activity toward ORR and OER, with an ultrasmall potential gap of 0.64 V between half-wave potential of ORR and the potential at OER current density of 10 mA cm-2. Liquid RZAB assembled with NiFe-MOF/FeN4C shows an open-circuit potential (OCV) of 1.516 V, a peak power density of 173.2 mW cm-2, and outstanding cycling stability within 400 h (1200 cycles). The NiFe-MOF/FeN4C-based flexible solid-state RZAB also exhibits an OCV of 1.527 V, a peak power density of 103.1 mW cm-2, and stable operation at diverse bending angles. This work demonstrates a new strategy to improving the poor OER activity of single FeN4-based catalysts to obtain superior bifunctional OER and ORR catalysts for both liquid and flexible solid RZAB applications.
{"title":"Ultra-efficient rechargeable liquid and flexible zinc-air batteries enabled by cooperative functions of NiFe-MOF and single FeN4 sites","authors":"Yuqi Zhang,Jie Yang,Xuqian Zhao,Yinuo Su,Jianghao Kang,Xiaoya Qiao,Yu Chen,Xingming Ning,Ruibin Jiang","doi":"10.1039/d6ta06861h","DOIUrl":"https://doi.org/10.1039/d6ta06861h","url":null,"abstract":"Bifunctional oxygen electrocatalysts with low cost, high activity, and long-term durability hold critical significance for rechargeable zinc-air batteries (RZABs), yet the design of such catalysts still confronts enormous challenges. Herein, a novel bifunctional electrocatalyst consisted of NiFe metal-organic framework (NiFe-MOF) grown on carbon black with highly dispersed FeN4 single sites (NiFe-MOF/FeN4C) is reported for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) involved in liquid and flexible RZABs. The catalyst is prepared via the pyrolysis of hemin chloride adsorbed on carbon black, followed by the growth of NiFe-MOF through a hydrothermal method. The pyrolysis of hemin chloride produces single Fe atoms coordinated with four pyrrolic N atom onto carbon black. The grown NiFe-MOF has strong electronic interaction with the FeN4 sites. The cooperative effect between NiFe-MOF and FeN4C delivers outstanding bifunctional catalytic activity toward ORR and OER, with an ultrasmall potential gap of 0.64 V between half-wave potential of ORR and the potential at OER current density of 10 mA cm-2. Liquid RZAB assembled with NiFe-MOF/FeN4C shows an open-circuit potential (OCV) of 1.516 V, a peak power density of 173.2 mW cm-2, and outstanding cycling stability within 400 h (1200 cycles). The NiFe-MOF/FeN4C-based flexible solid-state RZAB also exhibits an OCV of 1.527 V, a peak power density of 103.1 mW cm-2, and stable operation at diverse bending angles. This work demonstrates a new strategy to improving the poor OER activity of single FeN4-based catalysts to obtain superior bifunctional OER and ORR catalysts for both liquid and flexible solid RZAB applications.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"1 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152049","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}
Perovskite-type energetic materials have emerged as promising alternatives to conventional nitro-rich heterocycles due to their rapid self-assembly and tunable performance. However, existing perovskite systems such as DAP-4 suffer from negative oxygen balance and high mechanical sensitivity. Herein, we report AMM-1, a novel ABX3 perovskite energetic material designed by replacing the A-site cation of DAP-4 with 3-(ammoniomethyl)morpholin-4-ium (H2amm 2+ ). This substitution reduces the carbon-to-oxygen ratio to achieve an oxygen balance of 1.8% and introduces additional N-H•••O hydrogen bonds (2.118 Å) that enhance mechanical stability. Moreover, AMM-1 exhibits excellent thermal stability (Td = 310 °C), low mechanical sensitivity (IS = 15 J, FS = 120 N). Its detonation velocity reaches 8700 m/s, surpassing conventional heatresistant explosives HNS (Dv: 7578 m/s) and TATB (Dv: 8033 m/s). This work demonstrates that A-site cation engineering is an effective strategy for developing high-performance, insensitive perovskite energetic materials.
{"title":"Modification of Perovskite A-Site Cations to Achieve Near-Zero Oxygen Balance in High-Energy and Heat-Resistant Energetic Materials","authors":"Caijin Lei,Yunfei An,Wei Hu,Jie Tang,Guangbin Cheng,Chuan Xiao,Hongwei Yang,Qinghua Zhang","doi":"10.1039/d6ta07378f","DOIUrl":"https://doi.org/10.1039/d6ta07378f","url":null,"abstract":"Perovskite-type energetic materials have emerged as promising alternatives to conventional nitro-rich heterocycles due to their rapid self-assembly and tunable performance. However, existing perovskite systems such as DAP-4 suffer from negative oxygen balance and high mechanical sensitivity. Herein, we report AMM-1, a novel ABX3 perovskite energetic material designed by replacing the A-site cation of DAP-4 with 3-(ammoniomethyl)morpholin-4-ium (H2amm 2+ ). This substitution reduces the carbon-to-oxygen ratio to achieve an oxygen balance of 1.8% and introduces additional N-H•••O hydrogen bonds (2.118 Å) that enhance mechanical stability. Moreover, AMM-1 exhibits excellent thermal stability (Td = 310 °C), low mechanical sensitivity (IS = 15 J, FS = 120 N). Its detonation velocity reaches 8700 m/s, surpassing conventional heatresistant explosives HNS (Dv: 7578 m/s) and TATB (Dv: 8033 m/s). This work demonstrates that A-site cation engineering is an effective strategy for developing high-performance, insensitive perovskite energetic materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"13 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152789","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}
Constructing Janus heterointerfaces is an effective strategy to change the electron cloud density of active sites, and thus largely optimizes the catalytic activity. Here, three types of transition metal/transition metal oxide nanoparticles with Janus heterointerfaces are constructed by an in situ separation of the active phase strategy. Notably, the Ni/NiO composite exhibits excellent activity in the basic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), which only requires overpotentials of 57 and 237 mV to achieve 10 mA cm−2, respectively. Meanwhile, Ni/NiO assembled in an alkaline water electrolyzer shows 400 h durability under a current density of 500 mA cm−2, exhibiting negligible cell voltage loss. In situ measurement analyses reveal that the Ni/NiO heterointerfaces show a higher electron transfer rate in comparison to Co/CoO and Fe/Fe2O3, improving the kinetics of water splitting reaction. Further density functional theory calculations uncover that the electron transfer at Ni/NiO heterointerfaces optimizes the d-band center position of the Ni phase, leading to moderate adsorption energies for reactive intermediates, thereby facilitating the water splitting.
构建Janus异质界面是改变活性位点电子云密度的有效策略，从而在很大程度上优化了催化活性。本文采用原位分离活性相的方法，构建了三种具有Janus异质界面的过渡金属/过渡金属氧化物纳米颗粒。值得注意的是，Ni/NiO复合材料在碱性析氢反应（HER）和析氧反应（OER）中表现出优异的活性，只需要57和237 mV的过电位就可以分别达到10 mA cm−2。同时，在碱性水电解槽中组装的Ni/NiO在500 mA cm−2的电流密度下具有400 h的耐久性，电池电压损失可以忽略不计。原位测量分析表明，与Co/CoO和Fe/Fe2O3相比，Ni/NiO异质界面表现出更高的电子转移速率，从而改善了水裂解反应的动力学。进一步的密度泛函理论计算表明，Ni/NiO异质界面上的电子转移优化了Ni相的d带中心位置，导致反应中间体的吸附能适中，从而促进了水的分裂。
{"title":"Fabricating highly active Ni/NiO bifunctional Janus heterojunctions for alkaline water electrolysis","authors":"Shiyu Wen,Xiaoyan Guo,Yunfan Zhou,Yang Song,Yu Ying,Shun Yao,Shixiong Hao,Dong Cao,Daojian Cheng","doi":"10.1039/d6ta04765c","DOIUrl":"https://doi.org/10.1039/d6ta04765c","url":null,"abstract":"Constructing Janus heterointerfaces is an effective strategy to change the electron cloud density of active sites, and thus largely optimizes the catalytic activity. Here, three types of transition metal/transition metal oxide nanoparticles with Janus heterointerfaces are constructed by an in situ separation of the active phase strategy. Notably, the Ni/NiO composite exhibits excellent activity in the basic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), which only requires overpotentials of 57 and 237 mV to achieve 10 mA cm−2, respectively. Meanwhile, Ni/NiO assembled in an alkaline water electrolyzer shows 400 h durability under a current density of 500 mA cm−2, exhibiting negligible cell voltage loss. In situ measurement analyses reveal that the Ni/NiO heterointerfaces show a higher electron transfer rate in comparison to Co/CoO and Fe/Fe2O3, improving the kinetics of water splitting reaction. Further density functional theory calculations uncover that the electron transfer at Ni/NiO heterointerfaces optimizes the d-band center position of the Ni phase, leading to moderate adsorption energies for reactive intermediates, thereby facilitating the water splitting.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"18 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152795","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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