Yang Bai, Yuxin Shi, Xuchao Li, Yucong Zhang, Yaqi Wang
Conductive hydrogels (CHs) are attracted more attention in the flexible wearable sensors field, however, how to stably apply CHs underwater is still a big challenge. In order to achieve the usage of CHs in aquatic environments, the integrated properties such as water retention ability, resistance to swelling, toughness, adhesiveness, linear GF sensing, and long-term usage are necessary to consider, but rarely reported in the previous reports. This paper proposes CHs prepared using cationic and aromatic monomers along with polyrotaxanes-based crosslinkers. Due to the intermolecular cation-π interactions and topological slide-ring-based polyrotaxanes, the CHs exhibit good mechanical performance, adhesive nature, and anti-swelling properties. The presence of slide-ring-based topological architecture effectively mitigates stress concentration. Additionally, the encapsulation of PA allows CHs to maintain functionality even after 240 days of direct placement at room temperature. Notably, the designed CHs exhibit linear sensitivity in detecting land/underwater human motions, and serve as Morse code signal transmitters for information transmission. Thus, the designed CHs may have broad applications in the underwater wearable sensors field.
{"title":"Cation-π Interactions Based Conductive Hydrogels with Slide-Ring Structure Toward Super Long-Time in-air/Underwater Linear Sensing and Communication.","authors":"Yang Bai, Yuxin Shi, Xuchao Li, Yucong Zhang, Yaqi Wang","doi":"10.1002/smll.202406902","DOIUrl":"https://doi.org/10.1002/smll.202406902","url":null,"abstract":"<p><p>Conductive hydrogels (CHs) are attracted more attention in the flexible wearable sensors field, however, how to stably apply CHs underwater is still a big challenge. In order to achieve the usage of CHs in aquatic environments, the integrated properties such as water retention ability, resistance to swelling, toughness, adhesiveness, linear GF sensing, and long-term usage are necessary to consider, but rarely reported in the previous reports. This paper proposes CHs prepared using cationic and aromatic monomers along with polyrotaxanes-based crosslinkers. Due to the intermolecular cation-π interactions and topological slide-ring-based polyrotaxanes, the CHs exhibit good mechanical performance, adhesive nature, and anti-swelling properties. The presence of slide-ring-based topological architecture effectively mitigates stress concentration. Additionally, the encapsulation of PA allows CHs to maintain functionality even after 240 days of direct placement at room temperature. Notably, the designed CHs exhibit linear sensitivity in detecting land/underwater human motions, and serve as Morse code signal transmitters for information transmission. Thus, the designed CHs may have broad applications in the underwater wearable sensors field.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370405","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}
Guolong Wang, Jingqi Wang, Jiale Song, Yuxi Tai, Junwen Ren, Jiamei Liu, Xiaowei Shi, Zehua Zhao, Lei Li
Symmetrical batteries hold great promise as cost-effective and safe candidates for future battery technology. However, they realistically suffer low energy density due to the challenge in integrating high specific capacity with high voltage plateau from the limited choice of bipolar electrodes. Herein, a high-voltage all-V2O5 symmetrical battery with clear voltage plateau is conceptualized by decoupling the cathodic/anodic redox reactions based upon the episteme of V2O5 intercalation chemistry. As the proof-of-concept, a hierarchical V2O5-carboncomposite (VO-C) bipolar electrode with boosted electron/ion transport kinetics is fabricated, which shows high performance as both cathode and anode in their precisely clamped working potential windows. Accordingly, the symmetrical full-battery exhibits a high capacity of 174 mAh g-1 along with peak voltage output of above 2.9 V at 0.5C, remarkable capacity retention of 81% from 0.5C to 10C, and good cycling stability of 70% capacity retention after 300 cycles at 5C. Notably, its energy density reaches 429 Wh kg-1 at 0.5C estimated by the cathode mass, which outperforms most of the existing Li/Na/K-based symmetrical batteries. This study leaps forward the performance of symmetrical battery and provides guidance to extend the scope of future battery designs.
{"title":"High-Energy-Density All-V<sub>2</sub>O<sub>5</sub> Battery.","authors":"Guolong Wang, Jingqi Wang, Jiale Song, Yuxi Tai, Junwen Ren, Jiamei Liu, Xiaowei Shi, Zehua Zhao, Lei Li","doi":"10.1002/smll.202407159","DOIUrl":"https://doi.org/10.1002/smll.202407159","url":null,"abstract":"<p><p>Symmetrical batteries hold great promise as cost-effective and safe candidates for future battery technology. However, they realistically suffer low energy density due to the challenge in integrating high specific capacity with high voltage plateau from the limited choice of bipolar electrodes. Herein, a high-voltage all-V<sub>2</sub>O<sub>5</sub> symmetrical battery with clear voltage plateau is conceptualized by decoupling the cathodic/anodic redox reactions based upon the episteme of V<sub>2</sub>O<sub>5</sub> intercalation chemistry. As the proof-of-concept, a hierarchical V<sub>2</sub>O<sub>5</sub>-carboncomposite (VO-C) bipolar electrode with boosted electron/ion transport kinetics is fabricated, which shows high performance as both cathode and anode in their precisely clamped working potential windows. Accordingly, the symmetrical full-battery exhibits a high capacity of 174 mAh g<sup>-1</sup> along with peak voltage output of above 2.9 V at 0.5C, remarkable capacity retention of 81% from 0.5C to 10C, and good cycling stability of 70% capacity retention after 300 cycles at 5C. Notably, its energy density reaches 429 Wh kg<sup>-1</sup> at 0.5C estimated by the cathode mass, which outperforms most of the existing Li/Na/K-based symmetrical batteries. This study leaps forward the performance of symmetrical battery and provides guidance to extend the scope of future battery designs.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370407","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}
All-solid-state lithium metal batteries (ASSLMBs) are renowned for their high energy density and safety, positioning them as leading candidates for next-generation energy storage solutions. In this study, pure polymer solid-state electrolytes are developed using the solution casting method, optimized for room temperature operation. The base material, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), is enhanced with succinonitrile (SN) and polyacrylonitrile (PAN) to improve its electrochemical performance at room temperature. The optimized electrolyte, PSP-0.05, demonstrated superior characteristics, including an ionic conductivity (σ) of 3.2 × 10-4 S cm-1 and a wide voltage window of up to 5 V. When integrated into full batteries, PSP-0.05 exhibited exceptional performance in multiplicative cycling tests at room temperature, achieving discharge specific capacities of 132 and 113 mAh g-1 at 3 and 5 C rates, respectively. Additionally, long-term cycling at 1 C rate resulted in an initial discharge-specific capacity of 145.2 mAh g-1 with over 94.9% capacity retention after 1000 cycles. Given the simplicity of the preparation process and its impressive electrochemical properties, the PSP-0.05 electrolyte holds significant potential for practical applications in safer ASSLMBs.
全固态锂金属电池(ASSLMB)以其高能量密度和安全性而著称,是下一代能源存储解决方案的主要候选材料。本研究采用溶液浇铸法开发了纯聚合物固态电解质,并针对室温操作进行了优化。基础材料聚偏氟乙烯-六氟丙烯(PVDF-HFP)用琥珀腈(SN)和聚丙烯腈(PAN)进行了增强,以改善其室温下的电化学性能。优化后的电解质 PSP-0.05 显示出卓越的特性,包括 3.2 × 10-4 S cm-1 的离子电导率 (σ)和高达 5 V 的宽电压窗口。当 PSP-0.05 集成到完整电池中时,在室温下的倍率循环测试中表现出卓越的性能,在 3 C 和 5 C 速率下的放电比容量分别达到 132 mAh g-1 和 113 mAh g-1。此外,在 1 C 速率下进行长期循环时,初始放电比容量为 145.2 mAh g-1,1000 次循环后容量保持率超过 94.9%。考虑到制备过程的简便性及其令人印象深刻的电化学特性,PSP-0.05 电解质在更安全的 ASSLMB 的实际应用中具有巨大的潜力。
{"title":"High-Performance Pure Polymer Electrolytes with Enhanced Ionic Conductivity for Room-Temperature Applications.","authors":"Yongquan Zhang, Zengxu Chen, Jingshun Wang, Shuo Fan, Tiandong Zhang, Changhai Zhang, Yue Zhang, Qingguo Chi","doi":"10.1002/smll.202405565","DOIUrl":"https://doi.org/10.1002/smll.202405565","url":null,"abstract":"<p><p>All-solid-state lithium metal batteries (ASSLMBs) are renowned for their high energy density and safety, positioning them as leading candidates for next-generation energy storage solutions. In this study, pure polymer solid-state electrolytes are developed using the solution casting method, optimized for room temperature operation. The base material, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), is enhanced with succinonitrile (SN) and polyacrylonitrile (PAN) to improve its electrochemical performance at room temperature. The optimized electrolyte, PSP-0.05, demonstrated superior characteristics, including an ionic conductivity (σ) of 3.2 × 10<sup>-4</sup> S cm<sup>-1</sup> and a wide voltage window of up to 5 V. When integrated into full batteries, PSP-0.05 exhibited exceptional performance in multiplicative cycling tests at room temperature, achieving discharge specific capacities of 132 and 113 mAh g<sup>-1</sup> at 3 and 5 C rates, respectively. Additionally, long-term cycling at 1 C rate resulted in an initial discharge-specific capacity of 145.2 mAh g<sup>-1</sup> with over 94.9% capacity retention after 1000 cycles. Given the simplicity of the preparation process and its impressive electrochemical properties, the PSP-0.05 electrolyte holds significant potential for practical applications in safer ASSLMBs.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370409","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}
Sanshuang Gao, Kang Lian, Xinzhong Wang, Xijun Liu, Abdukader Abdukayum, Qingquan Kong, Guangzhi Hu
Rechargeable Zn-air batteries (ZABs) hold promise as the next-generation energy-storage devices owing to their affordability, environmental friendliness, and safety. However, cathodic catalysts are easily inactivated in prolonged redox potential environments, resulting in inadequate energy efficiency and poor cycle stability. To address these challenges, anodic active sites require multiple-atom combinations, that is, ensembles of metals. Heterogeneous bimetallic atomically dispersed catalysts (HBADCs), consisting of heterogeneous isolated single atoms and atomic pairs, are expected to synergistically boost the cyclic oxygen reduction and evolution reactions of ZABs owing to their tuneable microenvironments. This minireview revisits recent achievements in HBADCs for ZABs. Coordination environment engineering and catalytic substrate structure optimization strategies are summarized to predict the innovation direction for HBADCs in ZAB performance enhancement. These HBADCs are divided into ferrous and nonferrous dual sites with unique microenvironments, including synergistic effects, ion modulation, electronic coupling, and catalytic activity. Finally, conclusions and perspectives relating to future challenges and potential opportunities are provided to optimise the performance of ZABs.
{"title":"Recent Achievements in Heterogeneous Bimetallic Atomically Dispersed Catalysts for Zn-Air Batteries: A Minireview.","authors":"Sanshuang Gao, Kang Lian, Xinzhong Wang, Xijun Liu, Abdukader Abdukayum, Qingquan Kong, Guangzhi Hu","doi":"10.1002/smll.202406776","DOIUrl":"https://doi.org/10.1002/smll.202406776","url":null,"abstract":"<p><p>Rechargeable Zn-air batteries (ZABs) hold promise as the next-generation energy-storage devices owing to their affordability, environmental friendliness, and safety. However, cathodic catalysts are easily inactivated in prolonged redox potential environments, resulting in inadequate energy efficiency and poor cycle stability. To address these challenges, anodic active sites require multiple-atom combinations, that is, ensembles of metals. Heterogeneous bimetallic atomically dispersed catalysts (HBADCs), consisting of heterogeneous isolated single atoms and atomic pairs, are expected to synergistically boost the cyclic oxygen reduction and evolution reactions of ZABs owing to their tuneable microenvironments. This minireview revisits recent achievements in HBADCs for ZABs. Coordination environment engineering and catalytic substrate structure optimization strategies are summarized to predict the innovation direction for HBADCs in ZAB performance enhancement. These HBADCs are divided into ferrous and nonferrous dual sites with unique microenvironments, including synergistic effects, ion modulation, electronic coupling, and catalytic activity. Finally, conclusions and perspectives relating to future challenges and potential opportunities are provided to optimise the performance of ZABs.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370412","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}
Le Kuai, Fang Huang, Lijie Mao, Yi Ru, Jingsi Jiang, Jiankun Song, Si Chen, Ke Li, Yongyong Li, Haiqing Dong, Xiangyu Lu, Bin Li, Jianlin Shi
Atopic dermatitis (AD) is one of the most common allergic skin disorders affecting over 230 million people worldwide, while safe and efficient therapeutic options for AD are currently rarely available. Reactive oxygen species (ROS) accumulation plays a key role in AD's disease progression. Therefore, a novel single-atom catalyst is designed with isolated Cu1-N4 sites anchored on carbon support (Cu1-N4 ISAC), featuring triple antioxidant enzyme-mimicking activities, for efficient AD cascade catalytic therapy (CCT). The excellent superoxide dismutase (SOD)-, glutathione peroxidase (GPx)-, and ascorbate peroxidase (APx)-like activities of Cu1-N4 ISACs enable the sequential conversion of O2•- to H2O2 and then to harmless H2O, thereby protecting keratinocytes from oxidative stress damage. Notably, two novel experimental methods are developed to directly prove the SOD-GPx and SOD-APx cascade catalytic activities for the first time. In vivo experiments show that Cu1-N4 ISACs are more potent than a recommended typical medicine (halcinonide solution). Additionally, RNA sequencing and bioinformatic analysis reveal that Cu1-N4 ISACs reduce inflammation and inhibit ROS production by activating PPAR signaling, which is aberrantly reduced in AD. Therefore, the synthesized catalytic medicine offers an alternative to alleviate AD and has the potential to serve as PPAR agonists for treating similar diseases.
特应性皮炎(AD)是最常见的过敏性皮肤病之一,影响着全球超过 2.3 亿人,但目前很少有安全有效的 AD 治疗方案。活性氧(ROS)的积累在过敏性皮炎的发病过程中起着关键作用。因此,我们设计了一种新型单原子催化剂,它在碳载体上锚定了孤立的 Cu1-N4 位点(Cu1-N4 ISAC),具有三重抗氧化酶模拟活性,可用于高效的 AD 级联催化治疗(CCT)。Cu1-N4 ISACs具有出色的超氧化物歧化酶(SOD)、谷胱甘肽过氧化物酶(GPx)和抗坏血酸过氧化物酶(APx)模拟活性,能将O2依次转化为H2O2,再转化为无害的H2O,从而保护角质细胞免受氧化应激损伤。值得注意的是,研究人员开发了两种新的实验方法,首次直接证明了 SOD-GPx 和 SOD-APx 级联催化活性。体内实验表明,Cu1-N4 ISACs 比推荐的典型药物(卤西尼特溶液)更有效。此外,RNA 测序和生物信息学分析表明,Cu1-N4 ISACs 可通过激活 PPAR 信号减少炎症反应和抑制 ROS 的产生,而 PPAR 信号在 AD 中异常减少。因此,合成的催化药物为缓解阿德氏病提供了一种替代方法,并有可能成为治疗类似疾病的 PPAR 激动剂。
{"title":"Single-Atom Catalysts with Isolated Cu<sub>1</sub>-N<sub>4</sub> Sites for Atopic Dermatitis Cascade Catalytic Therapy via Activating PPAR Signaling.","authors":"Le Kuai, Fang Huang, Lijie Mao, Yi Ru, Jingsi Jiang, Jiankun Song, Si Chen, Ke Li, Yongyong Li, Haiqing Dong, Xiangyu Lu, Bin Li, Jianlin Shi","doi":"10.1002/smll.202407365","DOIUrl":"https://doi.org/10.1002/smll.202407365","url":null,"abstract":"<p><p>Atopic dermatitis (AD) is one of the most common allergic skin disorders affecting over 230 million people worldwide, while safe and efficient therapeutic options for AD are currently rarely available. Reactive oxygen species (ROS) accumulation plays a key role in AD's disease progression. Therefore, a novel single-atom catalyst is designed with isolated Cu<sub>1</sub>-N<sub>4</sub> sites anchored on carbon support (Cu<sub>1</sub>-N<sub>4</sub> ISAC), featuring triple antioxidant enzyme-mimicking activities, for efficient AD cascade catalytic therapy (CCT). The excellent superoxide dismutase (SOD)-, glutathione peroxidase (GPx)-, and ascorbate peroxidase (APx)-like activities of Cu<sub>1</sub>-N<sub>4</sub> ISACs enable the sequential conversion of O<sub>2</sub>•<sup>-</sup> to H<sub>2</sub>O<sub>2</sub> and then to harmless H<sub>2</sub>O, thereby protecting keratinocytes from oxidative stress damage. Notably, two novel experimental methods are developed to directly prove the SOD-GPx and SOD-APx cascade catalytic activities for the first time. In vivo experiments show that Cu<sub>1</sub>-N<sub>4</sub> ISACs are more potent than a recommended typical medicine (halcinonide solution). Additionally, RNA sequencing and bioinformatic analysis reveal that Cu<sub>1</sub>-N<sub>4</sub> ISACs reduce inflammation and inhibit ROS production by activating PPAR signaling, which is aberrantly reduced in AD. Therefore, the synthesized catalytic medicine offers an alternative to alleviate AD and has the potential to serve as PPAR agonists for treating similar diseases.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370450","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 electrochemical deintercalation method has been considered as an effective way to address the demand for lithium resources due to its environmental friendliness, high selectivity, and high efficiency. However, the performance of electrochemical lithium extraction is closely dependent on the electrode material and needs to be compatible under plateau environments with high-altitude and low-temperature. Herein, an in situ self-oxidation method is conducted to construct a hybrid conductive network on the surface of LiFePO4 (LFP-HN). The introduction of a hybrid conductive network enhanced the interfacial electron/lithium-ion transfer. In addition, structural stability is strengthened through suppressing the intercalation of impurity cations. Consequently, the LFP-HN delivered extremely high lithium extraction capacity (27.42 mg g-1), low energy consumption (4.91 Wh mol-1), and superior purity (91.05%) in Baqiancuo real brine (4788 m, -10 °C). What's more, LFP-HN-based large-scale prototypes are constructed and operated at Baqiancuo, which is calculated to extract 25 kg Lithium Carbonate Equivalent per cycle (4.55 h, 100 pairs of plates). Based on the excellent performance, the modification strategy developed in this work can be a promising solution for industrial lithium extraction under high-altitude environment.
{"title":"Self-Oxidated Hybrid Conductive Network Enables Efficient Electrochemical Lithium Extraction Under High-Altitude Environment.","authors":"Zhixin Wan, Ziqi Liu, Yiyang Xiao, Qinqin Ruan, Qian Wang, Haitao Zhang, Meng Yao, Yun Zhang","doi":"10.1002/smll.202406607","DOIUrl":"https://doi.org/10.1002/smll.202406607","url":null,"abstract":"<p><p>The electrochemical deintercalation method has been considered as an effective way to address the demand for lithium resources due to its environmental friendliness, high selectivity, and high efficiency. However, the performance of electrochemical lithium extraction is closely dependent on the electrode material and needs to be compatible under plateau environments with high-altitude and low-temperature. Herein, an in situ self-oxidation method is conducted to construct a hybrid conductive network on the surface of LiFePO<sub>4</sub> (LFP-HN). The introduction of a hybrid conductive network enhanced the interfacial electron/lithium-ion transfer. In addition, structural stability is strengthened through suppressing the intercalation of impurity cations. Consequently, the LFP-HN delivered extremely high lithium extraction capacity (27.42 mg g<sup>-1</sup>), low energy consumption (4.91 Wh mol<sup>-1</sup>), and superior purity (91.05%) in Baqiancuo real brine (4788 m, -10 °C). What's more, LFP-HN-based large-scale prototypes are constructed and operated at Baqiancuo, which is calculated to extract 25 kg Lithium Carbonate Equivalent per cycle (4.55 h, 100 pairs of plates). Based on the excellent performance, the modification strategy developed in this work can be a promising solution for industrial lithium extraction under high-altitude environment.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370449","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 nature, active Mn3+ -ligand complexes produced by laccase catalyzed oxidation can act as the low-molecular mass, diffusible redox mediators to oxidize the phenolic substrates overcoming the limitations of natural enzymes. Learning from the metal-ligand coordination of natural functional units, high-valence Mn metal-organic framework (Mn MOF) is constructed to simulate the catalysis in natural mediator system. Benefiting from the characteristics of nanoscale size, rich metal coordination unsaturated sites, and mixed valence state dominated by Mn(III), Nano Mn(III)-TP exhibits superior laccase-mimicking activity, whose Vmax (maximal reaction rate) is much higher than that of natural laccase. Referring to natural systems, relevant free radical experiments prove that the material induces the production of active oxygen species with the assistance of carboxylic acid, and active oxygen species further oxidize phenolic substrates. Based on its robust performances, the primary oxidative degradation of an emerging pollutant triclosan (TCS) is creatively applied, an important antiasthmatic medicine terbutaline sulfate (TBT) detection, and the synthesis of non-toxic and black near-natural dyes for dyeing. By simulating the essential mediators of natural enzymatic catalysis, an Mn MOF-based material that demonstrates multiple novel applications is successfully developed, which introduces a new reliable strategy for achieving versatile nature-mimicking catalysis.
{"title":"High-Valence Mn MOF Inspired by Laccase Mediators Enables Versatile Nature-Mimicking Catalysis.","authors":"Lili Xu, Jianli Nan, Songxue Han, Zhixuan Yu, Shuangli Wu, Youxing Fang, Shaojun Dong","doi":"10.1002/smll.202405293","DOIUrl":"https://doi.org/10.1002/smll.202405293","url":null,"abstract":"<p><p>In nature, active Mn<sup>3+</sup> -ligand complexes produced by laccase catalyzed oxidation can act as the low-molecular mass, diffusible redox mediators to oxidize the phenolic substrates overcoming the limitations of natural enzymes. Learning from the metal-ligand coordination of natural functional units, high-valence Mn metal-organic framework (Mn MOF) is constructed to simulate the catalysis in natural mediator system. Benefiting from the characteristics of nanoscale size, rich metal coordination unsaturated sites, and mixed valence state dominated by Mn(III), Nano Mn(III)-TP exhibits superior laccase-mimicking activity, whose V<sub>max</sub> (maximal reaction rate) is much higher than that of natural laccase. Referring to natural systems, relevant free radical experiments prove that the material induces the production of active oxygen species with the assistance of carboxylic acid, and active oxygen species further oxidize phenolic substrates. Based on its robust performances, the primary oxidative degradation of an emerging pollutant triclosan (TCS) is creatively applied, an important antiasthmatic medicine terbutaline sulfate (TBT) detection, and the synthesis of non-toxic and black near-natural dyes for dyeing. By simulating the essential mediators of natural enzymatic catalysis, an Mn MOF-based material that demonstrates multiple novel applications is successfully developed, which introduces a new reliable strategy for achieving versatile nature-mimicking catalysis.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370410","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}