Materials Chemistry Frontiers最新文献

{"title":"Sulfur-doped carbon interface modification for high-performance silicon anodes in lithium-ion batteries†","authors":"Jingyuan Li, Shuqi Wang, Fei Wang, Zhendong Liu, Zhuorui Tang, Weidong Zhang, Dai Dang, Chunyang Pan, Quanbing Liu and Chengzhi Zhang","doi":"10.1039/D5QM00230C","DOIUrl":"https://doi.org/10.1039/D5QM00230C","url":null,"abstract":"<p >Silicon anodes are extensively investigated as a leading candidate for next-generation lithium-ion battery anode materials. However, challenges, including severe side reactions and substantial volume expansion, which result in rapid capacity fading, remain significant obstacles to their further application, particularly under high-rate charge/discharge conditions. In this study we designed a multifunctional sulfur-doped carbon layer (SDCL) on the silicon of particle surfaces. DFT demonstrates that sulfur doping modifies the carbon layer's electron cloud distribution to enhance electronic conductivity while reducing lithium-ion diffusion energy barriers, thereby facilitating fast-charging of the silicon anode. Moreover, the incorporation of sulfur promotes the formation of a more stable solid electrolyte interphase, which stabilizes the silicon structure and improves cycling durability. The resulting silicon-based anode material exhibits superior rate capability and retains 95% of its capacity after 200 cycles, with a specific capacity of 920 mA h g<small>⁻¹</small>. Finally, the full cell displays a capacity retention of 72.9% after 100 cycles at 2 C. In summary, this work highlights the impact of interface modification by sulfur doping on the silicon anode materials, hence offering a new approach for the development of fast-charging and durable silicon anodes in lithium-ion batteries.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 12","pages":" 1896-1905"},"PeriodicalIF":6.0,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144244043","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}

{"title":"A chiral metal–organic framework fluorescent sensor incorporating H8-BINOL†","authors":"Pattara Siripanich, Jierui Zhang, Martina Lessio and Carol Hua","doi":"10.1039/D5QM00277J","DOIUrl":"https://doi.org/10.1039/D5QM00277J","url":null,"abstract":"<p >Fluorescent chiral chemical sensors with high enantioselectivity enable the identification of enantiomers in an inexpensive, accessible, and rapid manner even at low analyte concentrations. The discrimination of enantiomeric systems is of high importance in pharmaceutical and health sciences due to potential deleterious side effects of specific enantiomers and the potential for disease detection. In this work, the first metal–organic frameworks (MOFs) containing H<small>₈</small>-BINOL showed impressive enantioselective ratios (er) of 14.97 and 12.41 toward aspartic acid dimethyl ester exhibiting unique non-inverted enantioselectivity. The fluorescence behaviour with amino acids and their derivatives are examined with consideration of amino acid side chains, polarity, and intermolecular interactions. We demonstrate that the incorporation of additional steric hindrance with axial chirality is a powerful strategy for enhancing enantioselectivity in fluorescent chiral chemical sensors.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 13","pages":" 2087-2098"},"PeriodicalIF":6.0,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144367145","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}

{"title":"Deposition of N-doped graphene and its mechanism study via in situ mass spectrometry†","authors":"Limin Wang, Xi Wu, Tao Cheng, Han Xue, Bernd Abel, Jia Li, Jianfeng Li, Liying Ma, Jia Ding, Wenqi Wang, Shaopeng Fu, Yong Hou, Kailang Wang, La Zhu and Xubin Lu","doi":"10.1039/D5QM00013K","DOIUrl":"https://doi.org/10.1039/D5QM00013K","url":null,"abstract":"<p >Nitrogen doping of graphene is one of the most effective methods to open the zero-band gap of graphene, presenting a promising approach to modify its electronic structure. In this report, we introduce a novel method for growing large-area N-doped graphene directly on copper foil using atmospheric-pressure chemical vapor deposition (APCVD) using the pyrolysis of acetonitrile. <em>In situ</em> mass spectrometry combined with APCVD gave insights into the contribution and behavior of different species during the formation of N-doped graphene. Density functional theory calculations, paired with experimental results, were employed to study the growth mechanism of N-doped graphene with acetonitrile. Furthermore, the synthesized N-doped graphene was investigated as an electrode material for vanadium redox flow batteries (VRFB), focusing on its catalytic activity for the V(<small>IV</small>)/V(<small>V</small>) redox reaction. These findings not only deepen our understanding of the growth mechanisms of N-doped graphene but also provide a foundation for its application in energy storage systems, offering guidance for the synthesis of doped graphene and carbon nanotubes for advanced electrode materials in VRFB and beyond.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 12","pages":" 1933-1944"},"PeriodicalIF":6.0,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144244032","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}

{"title":"Recent progress in electrochemical synthesis of hypochlorite and its future outlook","authors":"Liuyu Ji, Junyang Ding, Caiyun Wang, Yang Luo, Qian Liu, Guangzhi Hu and Xijun Liu","doi":"10.1039/D5QM00299K","DOIUrl":"https://doi.org/10.1039/D5QM00299K","url":null,"abstract":"<p >Disinfection plays a critical role in ensuring the safety of drinking water during treatment. Sodium hypochlorite disinfection, a method that has been demonstrated to be both cost-effective and safe, exhibits considerable promise for widespread implementation when compared to alternative methods. Electrochemical synthesis of sodium hypochlorite solution has emerged as a preferred alternative to traditional chemical methods due to its numerous advantages, including high current efficiency, low energy consumption, ease of operation, accessible raw materials, high purity, and controllable safety. Nevertheless, the instability of the reaction in the electrochemical synthesis process poses a significant challenge to its broader implementation. This study explores the underlying principles of electrochemical synthesis for sodium hypochlorite solution and investigates the impact of various conditions on electrolysis efficiency. The objective of this study is to ascertain the most optimal electrolysis conditions. The study also examines various electrode materials for the anode and cathode, and it summarizes typical strategies for enhancing electrode performance. Furthermore, the study investigates the factors influencing the stability of sodium hypochlorite solution to enable precise regulation of its efficacy, thereby promoting the advancement of electrochemical synthesis technology for sodium hypochlorite solution.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 13","pages":" 1997-2017"},"PeriodicalIF":6.0,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144367090","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}

{"title":"A π-bridge strategy for asymmetric small molecule acceptors in organic photovoltaics†","authors":"Kun Wang, Cheng Zhang, Jingshun Gao, Weijie Qin, Jianan Hu, Yan Gao, Longxin Li, Lei Meng and Yongfang Li","doi":"10.1039/D5QM00244C","DOIUrl":"https://doi.org/10.1039/D5QM00244C","url":null,"abstract":"<p >Asymmetric small molecule acceptors (<em>as</em>-SMAs) offer advantages in photovoltaics <em>via</em> enhanced dipole moments and strong intermolecular interactions, promoting accelerated exciton dissociation and efficient charge transport. We design four A–D–π–A type <em>as</em>-SMAs of <strong>IDT-2Cl2F</strong>, <strong>IDT-S-2Cl2F</strong>, <strong>IDT-S-2F2Cl</strong>, and <strong>IDT-S-4F</strong> with an indaceno[1,2-<em>b</em>:5,6-<em>b</em>′]dithiophene (IDT) central D-core, asymmetric halogen substituents on their A-end group and an asymmetric alkylthio-thiophene π-bridge between the D-core and A-end group in <strong>IDT-S-2Cl2F</strong>, <strong>IDT-S-2F2Cl</strong>, and <strong>IDT-S-4F</strong>. The O⋯S, O⋯H, and S⋯S bonds ensure a coplanar molecular structure of the <em>as</em>-SMAs. Compared to <strong>IDT-2Cl2F</strong>, the π-bridge in <strong>IDT-S-2Cl2F</strong>, <strong>IDT-S-2F2Cl</strong>, and <strong>IDT-S-4F</strong> facilitates smoother electron transitions and broader spectral absorption due to their extended conjugation. Organic solar cells (OSCs) with PM6 as a polymer donor and <strong>IDT-S-2Cl2F</strong>, <strong>IDT-S-2F2Cl</strong>, or <strong>IDT-S-4F</strong> as an acceptor exhibit more uniform phase separation, lower surface roughness, faster exciton dissociation, and higher charge collection efficiency, resulting in improved current density, than those devices with <strong>IDT-2Cl2F</strong> as the acceptor. Additionally, shorter π–π stacking distances and larger dipole moments contribute to a higher open-circuit voltage (<em>V</em><small>_oc</small>) for the OSCs based on <strong>IDT-S-2Cl2F</strong>, <strong>IDT-S-2F2Cl</strong>, and <strong>IDT-S-4F</strong>. Consequently, the power conversion efficiencies (PCEs) of the OSCs based on <strong>IDT-S-2Cl2F</strong>, <strong>IDT-S-2F2Cl</strong>, and <strong>IDT-S-4F</strong> reach 10.95%, 11.39%, and 12.18%, respectively, significantly surpassing the 5.01% PCE of the device based on <strong>IDT-2Cl2F</strong>. This study proposes π-bridge engineering strategies to optimize molecular packing and energy alignment, for developing high-efficiency <em>as</em>-SMAs.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 14","pages":" 2190-2199"},"PeriodicalIF":6.0,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144566813","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}

{"title":"Pyrazine-based sensitizers for dye-sensitized solar cells","authors":"Ravulakollu Srinivasa Rao, Jonnadula Venkata Suman Krishna, Upendar Reddy Gandra, Igor F. Perepichka and Janah Shaya","doi":"10.1039/D4QM01100G","DOIUrl":"https://doi.org/10.1039/D4QM01100G","url":null,"abstract":"<p >Dye-sensitized solar cells (DSSCs) have emerged as a major technology in solar energy conversion. Ruthenium dyes are commonly used in DSSCs due to their high stability and power conversion efficiency (PCE), but the complex and costly synthesis of ruthenium complexes hinders their commercialization. Metal-free sensitizers attract significant attention in DSSC technologies. They are eco-friendlier with more facile synthesis and offer diverse structural designs for tuning electronic, optical and morphological properties. Metal-free dyes have been reported with PCEs surpassing Ru-based N3 and N719 benchmark sensitizers in DSSCs. Pyrazine-based sensitizers demonstrate favorable photophysical and electrochemical properties due to their unique structural features and versatile synthetic approaches enabling functionalization at different positions. Several pyrazine sensitizers have been reported with strong absorption extending to the near-infrared region, high molar extinction coefficients, and balanced hole and electron transport. The donor–π–acceptor (D–π–A) design with pyrazine as the π-bridge is conventional to favor intramolecular charge transfer in DSSCs. Other pyrazine architectures, <em>e.g.</em>, D–A–π–A′, demonstrated high PCEs, reaching up to 12.5%. This review highlights the advances in pyrazine-based sensitizers focusing on the pyrazine core as a principal electron acceptor, π-auxiliary acceptor, and even as a unit for functionalization as an electron-donating moiety. The reported sensitizers for DSSCs since 2008 are summarized, including metal-free dyes and pyrazines conjugated to Ru and porphyrin dyes. The dyes are classified into quinoxaline, thienopyrazine, pyridopyrazine, and pyrrolopyrazine cores in different sections. The DSSC parameters are summarized, discussing the electronic structure–property and structure–function relationships and offering insights into future architectures that accelerate their commercialization.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 14","pages":" 2120-2160"},"PeriodicalIF":6.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144566811","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}

{"title":"In situ polymerization-driven quasi-solid electrolytes for Li-metal batteries","authors":"Jinxuan Liu, Yinglei Wu, Zhenying Chen, Zhixin Xu, Jinhui Zhu and Xiaodong Zhuang","doi":"10.1039/D5QM00116A","DOIUrl":"https://doi.org/10.1039/D5QM00116A","url":null,"abstract":"<p >Li-metal batteries (LMBs) have emerged as the most promising energy storage technology to achieve high energy density exceeding 400 W h kg<small>⁻¹</small>. However, the conventional liquid electrolytes in LMBs present significant challenges, including severe reactivity with Li metal anodes and substantial safety risks. Quasi-solid electrolytes (QSEs), which combine the advantages of both solid and liquid electrolytes, have been identified as an ideal alternative for practical LMB applications. In particular, QSEs fabricated through <em>in situ</em> polymerization strategies offer enhanced interfacial compatibility, simplified manufacturing processes, reduced production costs, and represent one of the most commercially viable pathways for QSE development. This review provides a comprehensive analysis of <em>in situ</em> polymerization-driven QSEs and their application in LMBs. QSEs are systematically categorized based on the polymerization mechanisms of the polymer matrix, including free radical, cationic, anionic, and electrochemical polymerizations. Furthermore, the strategies for improving the performance of QSE-based LMBs are thoroughly discussed, with a focus on enhancing flame-retardant properties, high-voltage compatibility, and low-temperature operation. Finally, the review concludes with a critical assessment of the current state and future prospects of QSE-based LMBs, providing valuable insights into the future development of safer and more efficient energy storage systems.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 13","pages":" 1971-1996"},"PeriodicalIF":6.0,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144367089","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}

{"title":"Accelerating the spin–flip process of multi-resonance emitters via an advanced nitrogen group heavy atom strategy†","authors":"Weibo Cui, Yexuan Pu, Linjie Li, Lixiao Guo, Pingping Zheng, Yun Geng and Chenglong Li","doi":"10.1039/D5QM00235D","DOIUrl":"https://doi.org/10.1039/D5QM00235D","url":null,"abstract":"<p >Multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters, characterized by their high photoluminescence quantum yields and narrowband emissions, have attracted increasing attention in organic light-emitting diodes (OLEDs). However, MR-TADF OLEDs often suffer from significant efficiency roll-offs at high brightness due to a relatively slow reverse intersystem crossing (RISC) rate, on the order of 10<small>²</small>–10<small>⁴</small> s<small>⁻¹</small>, which poses a significant challenge for their practical applications. In this study, we designed two series of MR-TADF molecules by introducing heavy atoms from the nitrogen (N) group (<em>i.e.</em>, phosphorus (P) and arsenic (As)) in place of the N atom in the classical MR skeletons. Highly correlated wave function-based calculations show that the introduction of P and As significantly enhances the spin–orbit coupling (SOC) matrix element while preserving narrowband emission compared to its N-containing analogue, resulting in a sharp increase in the RISC rate (<em>k</em><small>_RISC</small>). Notably, <strong>DABNA-As</strong> achieves an impressive RISC rate of 2.24 × 10<small>⁷</small> s<small>⁻¹</small>, which is four orders of magnitude higher than that of its N-containing analogue <strong>DABNA-1</strong> (1.14 × 10<small>³</small> s<small>⁻¹</small>). This study offers a valuable strategy for the development of MR-TADF emitters with an effective RISC process by introducing P/As atoms.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 13","pages":" 2054-2065"},"PeriodicalIF":6.0,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144367142","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}

{"title":"Mechanism of in situ confining carbon dots in phthalamide crystal for room-temperature phosphorescence†","authors":"Xingmei Li, Haixin Kang, Yingying Zhao, Tong Chen, Jingxia Zheng, Lin Chen, Bin Liu, Yongzhen Yang and Xuguang Liu","doi":"10.1039/D5QM00171D","DOIUrl":"https://doi.org/10.1039/D5QM00171D","url":null,"abstract":"<p >Carbon dot (CD)-based room temperature phosphorescence (RTP) materials have widespread applications in anti-counterfeiting, light-emitting diode (LED) lighting, and bioimaging due to their spectral tunability, long lifetime, and other excellent optical properties. However, challenges remain regarding their complicated preparation processes and unclear mechanism. In this work, we developed a one-step, <em>in situ</em> liquid-phase synthesis method using phthalic acid, formamide, and ethylene glycol to directly form RTP CDs@phthalamide composites with CD/organic crystal structures. The product required only filtration and drying without further post-processing, significantly simplifying the preparation procedure and facilitating large-scale production. The as-prepared CDs@phthalamide exhibit excitation-dependent phosphorescence with a naked-eye-visible afterglow of 5 s and a phosphorescence lifetime of 441 ms. The formation process and reaction mechanism of CDs@phthalamide were investigated by optimizing the reaction temperature and reaction time, calculating activation energies through theoretical simulations, and comparing the effect of different crystal structures of phthalamide and phthalimide crystals on luminescence. Unlike phthalimide, the phthalamide matrix effectively restricts the vibration and rotation of CD luminous centers, realizing efficient RTP emission. Density functional theory (DFT) calculations further verified that the N elements enhanced RTP performance. In addition, CDs@phthalamide shows potential application value in time-delayed LEDs and anti-counterfeiting.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 12","pages":" 1870-1881"},"PeriodicalIF":6.0,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144244035","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}

{"title":"Cysteine-responsive, cyano-functionalized acenaphthopyrazine derivative for tumor microenvironment modulation-based chemotherapy sensitization and side effect reduction†","authors":"Hanyi Gao, Yiliang Qin, Jiayi Li, Shuhong Xiong, Rong Sun, Xia He, Yaxin Wu, Ying Tian, Yi Yuan and Rong Hu","doi":"10.1039/D5QM00229J","DOIUrl":"https://doi.org/10.1039/D5QM00229J","url":null,"abstract":"<p >Drug resistance and serious side effects are persistent obstacles in chemotherapy. Tumor microenvironment modulation is an emerging strategy to sensitize chemotherapy; however, the relevant side effects caused by chemotherapeutic drugs remain non-negligible. Herein, we constructed a cysteine-reactive, cyano-functionalized acenaphthopyrazine derivative for cisplatin sensitization and side effect reduction by regulating the tumor microenvironment. The developed cyano-functionalized acenaphthopyrazine derivative exhibited appropriate reactivity toward cysteine <em>via</em> an addition reaction. The incorporation of the cyano group not only improved the cellular uptake efficiency of cisplatin but also suppressed the drug inactivation behavior of tumor cells by reducing the expression of GSH within tumor cells. Moreover, selective inhibition of tumor cells was achieved due to the differing GSH dependence between normal and tumor cells. Most importantly, <em>in vivo</em> experiments revealed that the combination of the cyano-functionalized acenaphthopyrazine derivative with cisplatin could efficiently reduce liver and kidney damage during treatment. Our results demonstrated that cysteine consumption could serve as a general strategy for chemotherapy sensitization.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 12","pages":" 1839-1849"},"PeriodicalIF":6.0,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144244031","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}