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Cu–O–In Bridge Engineering in Cu2O/In2O3 Nanowires for Efficient CO2-to-CO Electroreduction 用于CO2-to-CO电还原的Cu2O/In2O3纳米线的Cu-O-In桥接工程
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202513217
Jiaomei Xiao, Guanfa Wang, Yan Chen, Gaixiu Yang, Jianlin Huang
Although modulating the d-band center (εd) is an effective strategy to improve electrocatalytic activity, precise regulation of εd for CO2 electroreduction to CO remains a substantial challenge. Here, we report a heterostructured catalyst consisting of In2O3-incorporated 3D nanowire copper foam (Cu2O/In2O3@CF), with tunable εd via Cu–O–In bridges for efficient electrocatalytic CO2 reduction (eCO2R) to CO. The optimized Cu2O/In2O3@CF delivers impressive CO Faradaic efficiency (FECO) exceeding 90% over a broad potential range from −0.47 to −0.87 V (vs. reversible hydrogen electrode, RHE), with a peak FECO of 95.8% at −0.67 V (vs. RHE), and a high production rate of 1035.3 µmol cm−2 h−1, along with stable operation for over 130 h. In situ Raman and Fourier transform infrared spectroscopy (FTIR) analyses combined with density functional theory (DFT) calculations reveal that the formation of Cu2O/In2O3 heterointerface with Cu–O–In bridge facilitates charge redistribution, upshifting the εd of Cu sites and downshifting that of In sites, thereby optimizing the adsorption-desorption energies of reaction intermediates during eCO2R. This synergistic design of oxide-oxide heterointerface with an interconnected 1D nanowires architecture offers an innovative strategy for enhancing eCO2R performance.
虽然调节d波段中心(εd)是提高电催化活性的有效策略,但精确调节CO2电还原为CO的εd仍然是一个重大挑战。在这里,我们报告一个用In2O3-incorporated 3 d纳米线组成的催化剂铜泡沫(Cu2O / In2O3@CF),通过高效electrocatalytic Cu-O-In桥梁与可调εd减少二氧化碳(eCO2R)有限公司优化Cu2O / In2O3@CF提供令人印象深刻的公司感应电流的效率(摘要)超过90%在一个广泛的潜在范围从0.47−−0.87 V (vs可逆氢电极,流值),所以峰值的95.8%−0.67 V(和流值)和高产量的1035.3µ摩尔厘米−2 h−1,原位拉曼和傅里叶变换红外光谱(FTIR)分析结合密度泛函理论(DFT)计算表明,Cu2O/In2O3异质界面与Cu - o - In桥的形成促进了电荷的重新分配,提高了Cu位的εd,降低了In位的εd,从而优化了反应中间体在eCO2R过程中的吸附-解吸能。这种氧化物-氧化物异质界面与相互连接的一维纳米线结构的协同设计为提高eCO2R性能提供了一种创新策略。
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引用次数: 0
Optimizing HostGuest Interaction Sites in Metal-Organic Frameworks for Benchmark One-Step Ethylene Purification 优化主客体相互作用的金属-有机框架的基准一步乙烯净化
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202514034
Yan-Fei Li, Jiao Lei, Zhang-Lei Zhong, Li-Qiu Yang, Ying Wang, Wenyu Yuan, Quan-Guo Zhai
Purifying ethylene from ternary acetylene/ethylene/ethane (C2H2/C2H4/C2H6) mixture in one-step requires preferential adsorption for C2H2 and C2H6, which is challenging due to the intermediate physicochemical property of C2H4. To address this problem, a synergistic host-guest interaction strategy is proposed for metal-organic frameworks (MOFs) by taking open metal site (OMS) to preferentially bind with electron-rich C2H2 through π-coordination interaction, while saturated hydrocarbon C2H6 primarily adsorbed via C-H∙∙∙π interactions with aromatic rings (AR). The feasibility of this strategy was demonstrated by three conformational isomeric 8-connected [Fe3(µ3-O)(COO)6] trigonal prismatic trinuclear cluster-based robust MOFs (denoted as SNNU-705-α/β/γ regulated by amino groups). Combining one unoccupied OMS site and occupying AR groups in SNNU-705-α/β/γ boosts the C2H2 and C2H6 affinity and binds C2H4 the weakest. Aided by amino Lewis basic sites (LBSs) furtherly, SNNU-705-γ exhibits the highest C2H6 uptake at 298 K and 1 atm (6.13 mmol g−1) among all reported MOFs for one-step C2H4 purification. Breakthrough experiments indicate that all SNNU-705-α/β/γ can separate C2H4 from C2H2/C2H4/C2H6 mixture in one-step with exceptional productivity (purity > 99.9999%) of 7.07, 6.75, and 5.46 mmol g−1, far surpassing all adsorbents reported so far. In situ FT–IR spectra and DFT calculation validates this strategy and indicate their potential in industry applications.
一步法提纯三元乙炔/乙烯/乙烷(C2H2/C2H4/C2H6)混合物中的乙烯需要对C2H2和C2H6进行优先吸附,这是由于C2H4的中间物理化学性质而具有挑战性。为了解决这一问题,提出了一种金属-有机框架(MOFs)的主客体协同作用策略,即开放金属位点(OMS)通过π-配位作用优先与富电子C2H2结合,而饱和烃C2H6主要通过C-H∙∙∙π与芳香环(AR)相互作用吸附。该策略的可行性通过三个构象异构的8连接[Fe3(µ3-O)(COO)6]基于三角柱状三核簇的鲁棒mof(标记为SNNU-705-α/β/γ,由氨基调节)得到验证。SNNU-705-α/β/γ结合一个未占用的OMS位点并占用AR基团可增强C2H2和C2H6的亲和力,而C2H4的结合最弱。在氨基刘易斯碱基位点(LBSs)的辅助下,SNNU-705-γ在298 K和1 atm (6.13 mmol g−1)条件下,在所有已报道的一步C2H4纯化mof中,C2H6吸收率最高。突破性实验表明,所有SNNU-705-α/β/γ都能一步分离C2H4和C2H2/C2H4/C2H6混合物,其产率(纯度>; 99.9999%)分别为7.07、6.75和5.46 mmol g−1,远远超过目前报道的所有吸附剂。原位FT-IR光谱和DFT计算验证了该策略,并表明其在工业应用中的潜力。
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引用次数: 0
Regioisomeric Engineering of Covalent Organic Frameworks toward Enhanced Photocatalytic Performance 共价有机框架的区域异构体工程增强光催化性能
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202512472
Guoye Yu, Guangchao Han, Xin Zhao, Jialin Cui, Yingjie Zhao, Yuancheng Wang
The photocatalytic performance of covalent organic frameworks (COFs) is often restricted by the inefficient utilization of photogenerated charge carriers. Achieving precise regulation of their electronic structures to facilitate charge separation and transport remains a great challenge. Herein, two regioisomeric COFs bearing pyrene units substituted at the 1,6- or 2,7-positions were rationally designed and synthesized to elucidate the influence of isomerism on electron distribution and photocatalytic behavior. Despite their comparable chemical composition and framework topology, the two regioisomeric COFs exhibited distinct photocatalytic activities. The 2,7-substituted P-COF exhibited a remarkable hydrogen evolution rate of 12.3 mmol h−1 g−1, whereas the 1,6-substituted D-COF displayed only negligible activity of 0.42 mmol h−1 g−1. Furthermore, P-COF achieved a H2O2 generation rate of 4.25 mmol h−1 g−1 using benzyl alcohol as sacrificial agent, much higher than that of D-COF (0.64 mmol h−1 g−1). A combination of experimental characterization and theoretical analysis revealed that regioisomerism exerts a decisive effect on the electronic structures as well as charge separation and transport dynamics, thereby substantially enhancing photocatalytic performance of pyrene-based COFs.
共价有机骨架(COFs)的光催化性能经常受到光生成载流子利用率低的限制。实现它们的电子结构的精确调节以促进电荷分离和传输仍然是一个巨大的挑战。本文合理设计和合成了两个在1,6-或2,7位取代芘单元的区域异构体COFs,以阐明异构体对电子分布和光催化行为的影响。尽管两种区域异构体COFs具有相似的化学成分和结构拓扑结构,但它们表现出不同的光催化活性。2,7取代的P-COF的析氢速率为12.3 mmol h−1 g−1,而1,6取代的D-COF的析氢速率为0.42 mmol h−1 g−1,可以忽略。以苯甲醇为牺牲剂,P-COF的H2O2生成速率为4.25 mmol h−1 g−1,远高于D-COF的0.64 mmol h−1 g−1。实验表征和理论分析相结合表明,区域异构对电子结构、电荷分离和输运动力学具有决定性影响,从而大大提高了芘基COFs的光催化性能。
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引用次数: 0
Biomimetic, Hierarchical-Porous Composite Aerogel Fiber with Spectral Selectivity and Water Microchannels for Synergistic Radiative-Evaporative Passive Cooling Textile 具有光谱选择性和水微通道的仿生、分层多孔复合气凝胶纤维用于协同辐射蒸发被动冷却纺织品
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202514581
Yuhang Wang, Xinge Chen, Xiaoyun Zhang, Jianbin Zang, Lin Lu, Weizhong Yuan
Inspired by the hair structure of desert animals, the structure-engineered aerogel fiber (SAF) has effectively prepared through the utilization of the double-diffusion process in wet spinning. The SAF fabric exhibit high emissivity (96.1%) within the atmospheric window and high reflectivity (92.3%) within the solar spectrum, thereby effectively mitigating the impact of solar radiation on human thermal balance. Additionally, the fibers exhibit an internal porosity of ∼93.9%, which functions to reduce the penetration of external heat and facilitates the instantaneous absorption (over 80% of self-weight) and evaporation (∼5.7 g h−1) of sweat through capillary effect, thereby further enhancing the dissipation of heat from human body. The continuous and scalable technical routes also endow SAFs with outstanding mechanical strength, water resistance, and breathability. Practical application tests demonstrate that the temperature of SAF fabric is ∼10.6°C lower than the commercialized cotton fabric under direct sunlight (solar irradiation: ∼1511 W m−2) and ∼12.0°C under the simultaneous action of direct sunlight (solar irradiation: ∼1091 W m−2) and simulated sweat infiltration. These results underscore the cost-effectiveness and high performance of SAF fabric, which offers substantial solutions and broad application prospects for multifunctional textiles and evaporative and radiative synergistic cooling applications.
受沙漠动物毛发结构的启发,利用湿法纺丝的双扩散工艺制备了结构工程气凝胶纤维(SAF)。SAF织物在大气窗口内具有高发射率(96.1%),在太阳光谱内具有高反射率(92.3%),从而有效地减轻了太阳辐射对人体热平衡的影响。此外,纤维的内部孔隙率为~ 93.9%,这有助于减少外部热量的渗透,并通过毛细管效应促进汗液的瞬时吸收(超过自重的80%)和蒸发(~ 5.7 gh−1),从而进一步增强人体热量的散失。连续和可扩展的技术路线也赋予了SAFs出色的机械强度,耐水性和透气性。实际应用试验表明,在阳光直射(太阳照射:~ 1511 W m−2)下,SAF织物的温度比商品化棉织物低~ 10.6°C,在阳光直射(太阳照射:~ 1091 W m−2)和模拟汗液渗透同时作用下,SAF织物的温度比商品化棉织物低~ 12.0°C。这些结果表明,SAF织物的高性价比和高性能为多功能纺织品以及蒸发和辐射协同冷却应用提供了坚实的解决方案和广阔的应用前景。
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引用次数: 0
Cyano-Ether Bifunctional Deep Eutectic Electrolytes for Stable Quasi-Solid Lithium Metal Batteries 稳定准固态锂金属电池用氰基醚双功能深共晶电解质
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202513016
Nannan Geng, Chenkai Lu, Jiong Zheng, Ziqi Cai, Jiachen Wan, Guowei Geng, Tao Yang, Guobin Zhang, Yin Cui, E. Lora da Silva, Xidong Lin, Tao Liu
Lithium metal batteries (LMBs) are promising for high energy density but suffer from safety issues, dendrite growth and interfacial instability. Deep eutectic electrolytes (DEEs) offer potential solutions, yet their practical application is limited by their unsatisfactory interfacial compatibility. This study develops a non-flammable quasi-solid electrolyte for LMBs, via incorporating a novel 3,3′-[oxybis(2,1-ethanediyloxy)]bispropanenitrile (OCN)-based DEE into a poly(butyl acrylate) (PBA) matrix, denoted as OCN-PBA. By integrating both cyano and ether functional groups, the designed OCN molecule enables dual stabilization of both the cathode and anode interfaces, as the cyano group enhances oxidation stability while the ether chains improve lithium compatibility. OCN-PBA possesses a unique aggregated solvation structure, which results in a high ionic conductivity (2.0 × 10−4 S cm−1), a Li+ transference number (0.66), and a wide electrochemical window (5.0 V). Consequently, Li|OCN-PBA|Li symmetric cell delivers stable plating/stripping over 1500 h, and Li|OCN-PBA|LiFePO4 cell demonstrates over 2000 stable cycles. Moreover, the OCN-PBA enables excellent cyclic stability in high-voltage Li|LiNi0.8Co0.1Mn0.1O2 and Li|LiCoO2 cells. This work proposes a novel electrolyte design strategy, providing a feasible approach for developing practical high-performance LMBs with improved safety.
锂金属电池(lmb)具有很高的能量密度,但存在安全问题、枝晶生长和界面不稳定等问题。深共晶电解质(dee)提供了潜在的解决方案,但其实际应用受到其不理想的界面兼容性的限制。本研究通过将一种新型的3,3 ' -[氧双(2,1-乙二氧基)]双丙腈(OCN)基DEE加入到聚丙烯酸丁酯(PBA)基体(记为OCN-PBA)中,开发了一种用于lmb的非易燃准固体电解质。通过整合氰基和醚官能团,设计的OCN分子实现了阴极和阳极界面的双重稳定,因为氰基增强了氧化稳定性,而醚链提高了锂的相容性。OCN-PBA具有独特的聚合溶剂化结构,具有较高的离子电导率(2.0 × 10−4 S cm−1)、Li+转移数(0.66)和宽的电化学窗口(5.0 V)。因此,Li|OCN-PBA|锂对称电池可提供超过1500小时的稳定镀/剥离,Li|OCN-PBA|LiFePO4电池可提供超过2000个稳定循环。此外,OCN-PBA在高压Li|LiNi0.8Co0.1Mn0.1O2和Li|LiCoO2电池中具有优异的循环稳定性。这项工作提出了一种新的电解质设计策略,为开发具有更高安全性的高性能lmb提供了可行的方法。
{"title":"Cyano-Ether Bifunctional Deep Eutectic Electrolytes for Stable Quasi-Solid Lithium Metal Batteries","authors":"Nannan Geng, Chenkai Lu, Jiong Zheng, Ziqi Cai, Jiachen Wan, Guowei Geng, Tao Yang, Guobin Zhang, Yin Cui, E. Lora da Silva, Xidong Lin, Tao Liu","doi":"10.1002/smll.202513016","DOIUrl":"https://doi.org/10.1002/smll.202513016","url":null,"abstract":"Lithium metal batteries (LMBs) are promising for high energy density but suffer from safety issues, dendrite growth and interfacial instability. Deep eutectic electrolytes (DEEs) offer potential solutions, yet their practical application is limited by their unsatisfactory interfacial compatibility. This study develops a non-flammable quasi-solid electrolyte for LMBs, via incorporating a novel 3,3′-[oxybis(2,1-ethanediyloxy)]bispropanenitrile (OCN)-based DEE into a poly(butyl acrylate) (PBA) matrix, denoted as OCN-PBA. By integrating both cyano and ether functional groups, the designed OCN molecule enables dual stabilization of both the cathode and anode interfaces, as the cyano group enhances oxidation stability while the ether chains improve lithium compatibility. OCN-PBA possesses a unique aggregated solvation structure, which results in a high ionic conductivity (2.0 × 10<sup>−4</sup> S cm<sup>−1</sup>), a Li<sup>+</sup> transference number (0.66), and a wide electrochemical window (5.0 V). Consequently, Li|OCN-PBA|Li symmetric cell delivers stable plating/stripping over 1500 h, and Li|OCN-PBA|LiFePO<sub>4</sub> cell demonstrates over 2000 stable cycles. Moreover, the OCN-PBA enables excellent cyclic stability in high-voltage Li|LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> and Li|LiCoO<sub>2</sub> cells. This work proposes a novel electrolyte design strategy, providing a feasible approach for developing practical high-performance LMBs with improved safety.","PeriodicalId":228,"journal":{"name":"Small","volume":"9 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146134303","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}
引用次数: 0
Dual Therapeutic Effects of Ultra-Small Platinum-Selenium Nanoparticles on Oxalate-Induced Acute Kidney Injury 超小铂硒纳米颗粒对草酸盐诱导急性肾损伤的双重治疗作用
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202514825
Nannan Zheng, Qiuyue Ma, Renkai Zhang, Jikang Zhang, Qinghui Wang, Yuxin He, Bin Yang, Stefanie Steiger, Liangcan He, Shaoqin Liu
Serum oxalate levels can rapidly increase due to specific dietary factors or ethylene glycol exposure, triggering acute kidney injury (AKI). Disorders like nephrocalcinosis and calcium oxalate (CaOx) nephropathy cause inflammation and renal failure without effective therapy. To address this challenge, ultra-small platinum-selenium (Pt-Se) nanoparticles (NPs) were synthesized to inhibit CaOxcrystallization by adsorbing C2O42− to block nucleation and by binding to crystal growth sites. in vitro and in vivo studies were performed to assess the inhibition of CaOx crystallization and oxalate-induced AKI. Pt-Se NPs not only suppressed CaOx crystallization but also inhibited crystal-cell interactions, thereby reducing CaOx-induced cell damage. Furthermore, in a hyperoxaluria mouse model, these NPs significantly decreased renal CaOx crystal deposition and attenuated kidney injury with excellent biocompatibility. In conclusion, ultra-small Pt-Se NPs represent a promising therapeutic strategy for acute CaOx crystal-induced nephropathy.
由于特定的饮食因素或乙二醇暴露,血清草酸水平可迅速升高,引发急性肾损伤(AKI)。肾钙质沉着症和草酸钙肾病等疾病会引起炎症和肾功能衰竭,而没有有效的治疗方法。为了解决这一挑战,合成了超小铂硒(Pt-Se)纳米颗粒(NPs),通过吸附C2O42−阻止成核和结合晶体生长位点来抑制cao氧化结晶。体外和体内研究评估对CaOx结晶和草酸盐诱导的AKI的抑制作用。Pt-Se NPs不仅抑制了CaOx的结晶,还抑制了晶体与细胞的相互作用,从而减少了CaOx诱导的细胞损伤。此外,在高血氧小鼠模型中,这些NPs显著减少肾CaOx晶体沉积,减轻肾损伤,具有良好的生物相容性。总之,超小Pt-Se NPs是治疗急性CaOx晶体肾病的一种有前景的治疗策略。
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引用次数: 0
Dynamically Reprograms Mitochondrial Respiration to Augment Cuproptosis in Cancer Therapy 动态重编程线粒体呼吸以增加癌症治疗中的铜增生
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202513435
Haohan Zhou, Ruijue Wang, Fang Zhu, Jia Lv, Lanfang Ren, Binnian Yu, Jianru Xiao, Yiyun Cheng, Hui Wang
Cuproptosis, a newly identified form of regulated cell death, relies on copper ions and elevated mitochondrial respiration. This study elucidates the role of lactate oxidase in modulating cuproptosis by converting lactate to pyruvate, reprogramming energy metabolism, and thereby facilitating copper-induced cell death. Here, this work develops a copper-coordinated polymer for efficient delivery of lactate oxidase into cancer cells. The nanoparticles modulate the activities of pyruvate dehydrogenase and pyruvate kinase, and reshape the energy metabolism of tumor cells. This metabolic reprogramming initiates a boost in mitochondrial function that subsequently promotes cuproptosis through copper-dependent dihydrolipoamide S-acetyltransferase (DLAT) oligomerization and disruption of the tricarboxylic acid cycle. In addition to inducing cuproptosis, the nanoparticles also activate a noniron-dependent Fenton-like reaction, thereby promoting ferroptosis. The nanoparticles exhibit potent antitumor efficacy in vivo, underscoring the potential of exploiting metabolic vulnerabilities to enhance cuproptosis. This study introduces a novel therapeutic avenue that leverages metabolic reprogramming to initiate regulated cell death pathways in cancer treatment.
铜增生是一种新发现的受调控的细胞死亡形式,它依赖于铜离子和线粒体呼吸作用的升高。本研究阐明了乳酸氧化酶通过将乳酸转化为丙酮酸,重编程能量代谢,从而促进铜诱导的细胞死亡来调节铜还原的作用。在这里,本研究开发了一种铜配位聚合物,用于将乳酸氧化酶有效地递送到癌细胞中。纳米颗粒调节丙酮酸脱氢酶和丙酮酸激酶的活性,重塑肿瘤细胞的能量代谢。这种代谢重编程启动了线粒体功能的增强,随后通过铜依赖的二氢脂酰胺s -乙酰转移酶(DLAT)寡聚和三羧酸循环的破坏促进铜还原。除了诱导铁下垂外,纳米颗粒还激活非铁依赖性芬顿样反应,从而促进铁下垂。纳米颗粒在体内表现出强大的抗肿瘤功效,强调了利用代谢脆弱性来增强铜质增生的潜力。本研究介绍了一种新的治疗途径,利用代谢重编程来启动癌症治疗中受调节的细胞死亡途径。
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引用次数: 0
Synthesis of Zirconium Boron-Oxo Clusters With Tunable Third-Order Nonlinear Optical Response 具有可调谐三阶非线性光学响应的锆硼氧团簇的合成
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202514893
Pan-Pan Zhao, Xiang-Ming Zhang, Xiao-Lan Zheng, Qiao-Hong Li, Hai-Xia Zhang, Jian Zhang
Due to the weak coordination ability with metals and the easy self-condensation of arylboronic acids, the development of organic–inorganic hybrid metal boron-oxo clusters is still challenging. In this study, by leveraging the in situ condensation reaction between boron sources (e.g., trimethyl borate and arylboronic acids) and dioxime, a series of dioxime-modified zirconium boron-oxo clusters (Zr-BOCs) was synthesized via a pyrazole-thermal condition. In these structures, dioximes not only induce the polymerization of boric acid into clusters but also chelate Zr ions, enabling electronic coupling between B-O and Zr-O moieties and resulting in a nearly planar cluster core Zr2B8O10. Taking advantage of the open Zr sites and the boron atom hybridization change from sp2 to sp3, we sequentially introduced aromatic carboxylic acids and arylboronic acids to controllably modulate both the planarity and the electronic structure of the Zr2B8O10 core. In particular, the Zr-O quadrilateral ring in BOC-13 (Zr2(Dmg)4(CH3OB4O5)2(BA)2) demonstrates aromaticity revealed by DFT calculations. Its conjugation with planar B-O clusters extends electron delocalization from a p-p-π to a d-p-π system, significantly enhancing third-order nonlinear optical (NLO) properties and achieving a minimum normalized transmittance (Tmin) of 0.20. The present work establishes a modular synthesis strategy for organic-inorganic hybrid boron-oxo clusters with a d-p-π delocalization system.
由于芳香硼酸与金属的配位能力较弱,且容易自缩合,因此有机-无机杂化金属硼氧团簇的开发仍然具有挑战性。本研究利用硼源(如硼酸三甲酯和芳基硼酸)与二肟的原位缩合反应,在吡唑-热条件下合成了一系列二肟修饰的锆硼氧簇(Zr-BOCs)。在这些结构中,二氧肟不仅能诱导硼酸聚合成簇,还能螯合Zr离子,使B-O和Zr- o基团之间发生电子偶联,形成近平面的簇核Zr2B8O10。利用开放的Zr位点和硼原子杂化从sp2到sp3的变化,我们依次引入芳香羧酸和芳基硼酸来调控Zr2B8O10芯的平面度和电子结构。特别是,BOC-13中的Zr-O四边形环(Zr2(Dmg)4(CH3OB4O5)2(BA)2)显示了DFT计算显示的芳构性。它与平面B-O簇的共轭将电子离域从p-p-π扩展到d-p-π体系,显著提高了三阶非线性光学(NLO)性能,并实现了0.20的最小归一化透射率(Tmin)。本工作建立了一种具有d-p-π离域系统的有机-无机杂化硼氧簇的模块化合成策略。
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引用次数: 0
Bioinspired and Engineered Ion-Selective Membranes Toward High-Flux and High-Selectivity Energy Devices 面向高通量和高选择性能源装置的生物启发和工程离子选择膜
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202510500
Rockson Kwesi Tonnah, Sahar Foorginezhad, Baggie W. Nyande, Faezeh Arshadi, Milad Razbin, Milton Chai, Amir Razmjou, Mohsen Asadnia
Nanofluidic membranes with precise ion selectivity and ultrahigh permeability are central to advancing electromembrane technologies for energy generation, storage, water purification, and environmental monitoring. The performance of these systems hinges on the ability of membranes to efficiently and selectively transport ions. However, synthetic ion-selective membranes (ISMs) face a fundamental trade-off: increasing ion selectivity typically reduces permeability, and vice versa. Overcoming this trade-off is essential for realizing next-generation ISMs with enhanced performance. This review summarizes recent progress in addressing the selectivity–permeability trade-off through innovative membrane architectures, advanced fabrication methods, material engineering strategies, and modeling tools that clarify structure–property–performance relationships. Biological ion channels serve as benchmarks, offering ultra-efficient ion transport via precise control of pore size, surface charge, pathway length, and rectification effects. Drawing on these natural systems, we highlight bio-inspired strategies for enhancing synthetic membrane performance. We also discuss the role of ISMs in electrochemical applications and assess remaining challenges in achieving high ion flux without compromising selectivity. Emerging solutions including hybrid membrane systems, advanced nanomaterials, and AI-assisted design present promising pathways forward. The review concludes by outlining future directions that integrate computational modeling with experimental validation to develop efficient, scalable, and sustainable membrane technologies.
纳米流体膜具有精确的离子选择性和超高渗透性,是推进电膜技术的核心,用于发电、储存、水净化和环境监测。这些系统的性能取决于膜有效和选择性运输离子的能力。然而,合成离子选择膜(ISMs)面临着一个基本的权衡:增加离子选择性通常会降低渗透性,反之亦然。克服这种权衡对于实现具有增强性能的下一代ISMs至关重要。本文通过创新的膜结构、先进的制造方法、材料工程策略和澄清结构-性能-性能关系的建模工具,总结了在解决选择性-渗透性权衡方面的最新进展。生物离子通道作为基准,通过精确控制孔径、表面电荷、路径长度和整流效应,提供超高效的离子传输。利用这些自然系统,我们强调了增强合成膜性能的仿生策略。我们还讨论了ISMs在电化学应用中的作用,并评估了在不影响选择性的情况下实现高离子通量的剩余挑战。新兴的解决方案包括混合膜系统、先进的纳米材料和人工智能辅助设计,为未来的发展提供了有希望的途径。本文最后概述了将计算建模与实验验证相结合的未来发展方向,以开发高效、可扩展和可持续的膜技术。
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引用次数: 0
Asymmetric Metal Oxide Electrodes for High-Efficiency Evaporation-Induced Energy Harvesting 用于高效蒸发能量收集的非对称金属氧化物电极
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1002/smll.202514290
Barsha Rani Bora, Bipasha Saikia, Mrityunjoy Dey, Kalyan Raidongia
In the domain of evaporation to electricity conversion, current research efforts are primarily focused on optimizing the permselectivity and evaporation efficiency of the fluid transferring medium. Here, we demonstrate that the output power of evaporation-induced energy harvesting devices can be significantly enhanced using suitable electrodes that complement the charge separation process and improve the ionic-electronic current conversion efficiency. The proof of concept was demonstrated by fabricating an energy device with the nanofluidic membrane of montmorillonite clay (MC-M). Upon replacing typically used Cu electrodes with surface-modified graphitic carbon strips with positively charged TiO2 nanowires as the bottom electrode, and negatively charged Co3O4 nanowires as the top electrode, nearly 8000 times enhancement in the power output was observed. Unlike redox-active metals, metal oxide nanostructures applied in the MC-M device are not consumed in the charge conversion process. Finally, replacing liquid water with a modified block of pottery clay as a self-replenishing water source at the bottom of the MC-M device improved the long-term device stability (uninterrupted power output up to 8 h) in addition to addressing issues like inconveniences of water replacement, variations in water levels, and dissolution of the charge-selective medium.
在蒸发转电领域,目前的研究工作主要集中在优化流体传递介质的选择性和蒸发效率上。在这里,我们证明了使用合适的电极可以显著增强蒸发诱导能量收集装置的输出功率,这些电极可以补充电荷分离过程并提高离子-电子电流转换效率。利用蒙脱土(MC-M)纳米流控膜制备能量装置,验证了概念的可行性。用带正电的TiO2纳米线作为下电极,带负电的Co3O4纳米线作为上电极,用表面修饰的石墨碳带代替常用的Cu电极,输出功率提高了近8000倍。与氧化还原活性金属不同,MC-M器件中应用的金属氧化物纳米结构在电荷转换过程中不会被消耗。最后,在MC-M装置底部用改性陶土块代替液态水作为自补充水源,提高了装置的长期稳定性(不间断输出功率长达8小时),并解决了水更换不便、水位变化和电荷选择介质溶解等问题。
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