Breaking the trade-off between stability and switching functionality remains a pivotal challenge in substrate-supported molecular switches. Herein, we propose a design strategy using A3B-type intermetallic alloys as substrates to realize a hybrid-bonding precursor state that concurrently achieves robust interfacial stability and enhanced current-switching ratios. We demonstrate that this bistability can be directly predicted from the atomic covalent radius and d-band centers of surface metals. Remarkably, we uncover a distinctive V-shaped relationship between the d-band center of host metal and valence electron number of the guest metal, governed by the occupancy of d-d anti-bonding states. Furthermore, we elucidate the essential role of geometric and quantum primogenic effects in modulating d-d orbital interactions, resolving longstanding controversies regarding d-band modulation mechanisms for alloys. By incorporating intrinsic parameters, including valence electron number, atomic radius, and orbital radius of guest metals, we develop a generalizable descriptor for accurately predicting the d-band center of host metals (R2 > 0.90). This work not only accelerates the exploration of robust room-temperature molecular switches, but also establishes a rational design framework for high-performance intermetallic substrates with optimal adsorption properties, thereby significantly reducing reliance on costly density functional theory calculations.
{"title":"A Predictive Descriptor for d-Band Center in Intermetallic Alloys Accelerates the Design of Robust Molecular Switches","authors":"Sha Yang, Junjun Zhou, Yirong Zhang, Guolin Cao, Ji-Chang Ren, Wei Liu","doi":"10.1039/d5sc08297h","DOIUrl":"https://doi.org/10.1039/d5sc08297h","url":null,"abstract":"Breaking the trade-off between stability and switching functionality remains a pivotal challenge in substrate-supported molecular switches. Herein, we propose a design strategy using A<small><sub>3</sub></small>B-type intermetallic alloys as substrates to realize a hybrid-bonding precursor state that concurrently achieves robust interfacial stability and enhanced current-switching ratios. We demonstrate that this bistability can be directly predicted from the atomic covalent radius and d-band centers of surface metals. Remarkably, we uncover a distinctive V-shaped relationship between the d-band center of host metal and valence electron number of the guest metal, governed by the occupancy of d-d anti-bonding states. Furthermore, we elucidate the essential role of geometric and quantum primogenic effects in modulating d-d orbital interactions, resolving longstanding controversies regarding d-band modulation mechanisms for alloys. By incorporating intrinsic parameters, including valence electron number, atomic radius, and orbital radius of guest metals, we develop a generalizable descriptor for accurately predicting the d-band center of host metals (R<small><sup>2</sup></small> > 0.90). This work not only accelerates the exploration of robust room-temperature molecular switches, but also establishes a rational design framework for high-performance intermetallic substrates with optimal adsorption properties, thereby significantly reducing reliance on costly density functional theory calculations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955819","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The presence of trace amounts of impurities can have unprecedented effects on the luminescence features of organic room temperature phosphorescent (ORTP) materials, requiring conscientious investigation. In this study, we have compared the photoluminescence properties of biphenyl-4-carboxylic acid (BCA) and biphenyl-4,4′-dicarboxylic acid (BDCA), synthesized via two distinct synthetic routes-Friedel-Crafts (FC-BCA or FC-BDCA) and cross-coupling (cc-BCA or cc-BDCA) pathways and observed remarkable orange phosphorescence in FC-BCA or FC-BDCA which were absent in cc-BCA or cc-BDCA. Our investigations identified traces (<0.3 mol%) of diphenylbenzil based impurities, formed as byproducts during Friedel-Crafts acylation of biphenyl, responsible for the RTP activation in FC-BCA or FC-BDCA. Bicomponent solids prepared by deliberately doping traces of DPB into various organic matrices ensued tunable RTP color (green to red) with high quantum yield (26.4 %) and lifetime up to 1.6 ms. Comprehensive experimental investigations substantiated with theoretical studies revealed that photoexcited conformational dynamics of guest DPB are responsible for RTP color variation concertedly involving multiple energy transfer channels, e.g., singlet-to-singlet (SSET), triplet-to-triplet (TTET). It presents a novel trace doping strategy for developing RTP materials with tunable optical features by synergistically controlling the ground and excited state geometries of a single guest molecule, which is rarely reported in the literature. Furthermore, by employing a suitable host matrix, we successfully stabilized a linear conformer of guest DPB in the ground state, which is otherwise unstable, resulted in improved quantum yield. Simultaneously, we report an unusual RTP from commercial BDCA, which we suspect to be caused by the presence of diphenylbenzil-based impurities, reiteratively emphasizing the importance of exercising caution whenever a system exhibits unusual properties.
{"title":"'Impurity'-driven Tunable Organic Room Temperature Phosphorescence via Conformational Regulation in Multi Host/Guest Systems","authors":"Arnab Dutta, Utkarsh Singh, Swapan Pati, Uday Maitra","doi":"10.1039/d5sc08129g","DOIUrl":"https://doi.org/10.1039/d5sc08129g","url":null,"abstract":"The presence of trace amounts of impurities can have unprecedented effects on the luminescence features of organic room temperature phosphorescent (ORTP) materials, requiring conscientious investigation. In this study, we have compared the photoluminescence properties of biphenyl-4-carboxylic acid (BCA) and biphenyl-4,4′-dicarboxylic acid (BDCA), synthesized via two distinct synthetic routes-Friedel-Crafts (FC-BCA or FC-BDCA) and cross-coupling (cc-BCA or cc-BDCA) pathways and observed remarkable orange phosphorescence in FC-BCA or FC-BDCA which were absent in cc-BCA or cc-BDCA. Our investigations identified traces (<0.3 mol%) of diphenylbenzil based impurities, formed as byproducts during Friedel-Crafts acylation of biphenyl, responsible for the RTP activation in FC-BCA or FC-BDCA. Bicomponent solids prepared by deliberately doping traces of DPB into various organic matrices ensued tunable RTP color (green to red) with high quantum yield (26.4 %) and lifetime up to 1.6 ms. Comprehensive experimental investigations substantiated with theoretical studies revealed that photoexcited conformational dynamics of guest DPB are responsible for RTP color variation concertedly involving multiple energy transfer channels, e.g., singlet-to-singlet (SSET), triplet-to-triplet (TTET). It presents a novel trace doping strategy for developing RTP materials with tunable optical features by synergistically controlling the ground and excited state geometries of a single guest molecule, which is rarely reported in the literature. Furthermore, by employing a suitable host matrix, we successfully stabilized a linear conformer of guest DPB in the ground state, which is otherwise unstable, resulted in improved quantum yield. Simultaneously, we report an unusual RTP from commercial BDCA, which we suspect to be caused by the presence of diphenylbenzil-based impurities, reiteratively emphasizing the importance of exercising caution whenever a system exhibits unusual properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"34 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955820","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hyun Wook Choi, Deniz Kahraman, Wei-Jia Chen, Lai-Sheng Wang
Understanding the boron-coinage-metal interactions is critical for understanding the nucleation and growth mechanisms of borophene on coinage-metal substrates. Binary metal-boron clusters provide ideal models for obtaining atomic-level information about the metal-boron interactions. Here we report an investigation of the structure and bonding of the AgB8− cluster as a model system to gain insight into the interaction of boron with silver, the most inert substrate to grow borophene. Photoelectron spectroscopy reveals that the spectra of AgB8− resemble those of bare B8−, suggesting extremely weak chemical interactions between Ag and boron. Quantum calculations show that AgB8− (Cs, 1A′) consists of a B8 borozene weakly interacting with a Ag atom on its edge. Chemical bonding analyses find that the Ag atom interacts with the B8 motif primarily through its 5s orbital with little perturbation to the structure and bonding of the B8 borozene. Compared to CuB8− and AuB8−, Ag is found to have the weakest interaction with the B8 motif, consistent with that fact that silver substrates are the most inert for borophene syntheses.
{"title":"Probing the Weak Interaction between Silver and Boron","authors":"Hyun Wook Choi, Deniz Kahraman, Wei-Jia Chen, Lai-Sheng Wang","doi":"10.1039/d5sc08598e","DOIUrl":"https://doi.org/10.1039/d5sc08598e","url":null,"abstract":"Understanding the boron-coinage-metal interactions is critical for understanding the nucleation and growth mechanisms of borophene on coinage-metal substrates. Binary metal-boron clusters provide ideal models for obtaining atomic-level information about the metal-boron interactions. Here we report an investigation of the structure and bonding of the AgB<small><sub>8</sub></small><small><sup>−</sup></small> cluster as a model system to gain insight into the interaction of boron with silver, the most inert substrate to grow borophene. Photoelectron spectroscopy reveals that the spectra of AgB<small><sub>8</sub></small><small><sup>−</sup></small> resemble those of bare B<small><sub>8</sub></small><small><sup>−</sup></small>, suggesting extremely weak chemical interactions between Ag and boron. Quantum calculations show that AgB<small><sub>8</sub></small><small><sup>−</sup></small> (<em>C<small><sub>s</sub></small></em>, <small><sup>1</sup></small>A′) consists of a B<small><sub>8</sub></small> borozene weakly interacting with a Ag atom on its edge. Chemical bonding analyses find that the Ag atom interacts with the B<small><sub>8</sub></small> motif primarily through its 5<em>s</em> orbital with little perturbation to the structure and bonding of the B<small><sub>8</sub></small> borozene. Compared to CuB<small><sub>8</sub></small><small><sup>−</sup></small> and AuB<small><sub>8</sub></small><small><sup>−</sup></small>, Ag is found to have the weakest interaction with the B<small><sub>8</sub></small> motif, consistent with that fact that silver substrates are the most inert for borophene syntheses.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993358","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Garnet-type solid-state electrolytes (SSEs) are promising candidates for next-generation solid-state batteries (SSBs) owing to their high ionic conductivity, robust mechanical strength, and broad electrochemical stability window. However, exposure to ambient air results in the formation of a Li2CO3 passivation layer on the surface, significantly reducing ionic conductivity and deteriorating interfacial wettability, thereby severely impairing the electrochemical performance of SSBs. This review systematically analyzes the formation mechanisms and influencing factors of Li2CO3 contamination on garnet-type SSE surfaces. It summarizes recent strategies for suppressing Li2CO3 formation, including sintering process optimization, elemental doping, and grain boundary/interface engineering. Among these approaches, interfacial treatments have attracted considerable attention owing to their cost-effectiveness and operational efficiency. This review focuses on categorizing diverse treatment strategies for improving electrode/electrolyte interfacial contact, including physical cleaning, chemical treatment and conversion, and the modification with interfacial interlayers—specifically detailing types such as inorganic, organic, and organic-inorganic composite interlayers. Finally, the future prospects of garnet-type SSEs in high-performance SSBs are discussed, pointing out the need for in-depth research into the formation and evolution mechanisms of Li2CO3 and the development of more efficient interface control strategies. This review systematically examines interfacial challenges in garnet-type SSEs, with the ultimate goal of facilitating the development of stable all-solid-state lithium metal batteries and accelerating their commercialization.
{"title":"Mitigation strategies for Li2CO3 contamination in garnet-type solid-state electrolytes: Formation mechanisms and interfacial engineering","authors":"Bin Hao, Qiushi Wang, Fangyuan Zhao, Jialong Wu, Weiheng Chen, Zhong-Jie Jiang, Zhongqing Jiang","doi":"10.1039/d5sc09699e","DOIUrl":"https://doi.org/10.1039/d5sc09699e","url":null,"abstract":"Garnet-type solid-state electrolytes (SSEs) are promising candidates for next-generation solid-state batteries (SSBs) owing to their high ionic conductivity, robust mechanical strength, and broad electrochemical stability window. However, exposure to ambient air results in the formation of a Li2CO3 passivation layer on the surface, significantly reducing ionic conductivity and deteriorating interfacial wettability, thereby severely impairing the electrochemical performance of SSBs. This review systematically analyzes the formation mechanisms and influencing factors of Li2CO3 contamination on garnet-type SSE surfaces. It summarizes recent strategies for suppressing Li2CO3 formation, including sintering process optimization, elemental doping, and grain boundary/interface engineering. Among these approaches, interfacial treatments have attracted considerable attention owing to their cost-effectiveness and operational efficiency. This review focuses on categorizing diverse treatment strategies for improving electrode/electrolyte interfacial contact, including physical cleaning, chemical treatment and conversion, and the modification with interfacial interlayers—specifically detailing types such as inorganic, organic, and organic-inorganic composite interlayers. Finally, the future prospects of garnet-type SSEs in high-performance SSBs are discussed, pointing out the need for in-depth research into the formation and evolution mechanisms of Li2CO3 and the development of more efficient interface control strategies. This review systematically examines interfacial challenges in garnet-type SSEs, with the ultimate goal of facilitating the development of stable all-solid-state lithium metal batteries and accelerating their commercialization.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"34 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968941","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mitochondrial DNA (mtDNA) mutations play critical roles in tumor progression and metabolic reprogramming. Controllable gene editing within tumor cell mitochondria remains a challenge due to the double-membrane barrier and the lack of tumor-selective activation. Herein, we report a dual-responsive CRISPR/Cas delivery platform (UCRP-TPP) that enables spatiotemporally regulated mtDNA editing for targeted tumor therapy. This nanoplatform integrates near infrared light-responsive upconversion nanoparticle (UCNP), an apurinic endonuclease 1 (APE-1)-responsive DNA complex, and a mitochondrial-targeting ligand (TPP), ensuring selective activation and mitochondrial release of Cas9/sgRNA complexes. Upon activation by endogenous APE-1 enzyme and exogenous NIR light, UCRP-TPP induces mtDNA editing by CRISPR/Cas, which leads to mtDNA copy number reduction, mitochondrial membrane depolarization, reactive oxygen species generation, and tumor cell apoptosis. In vivo studies further confirm the robust antitumor efficacy of UCRP-TPP-based nanoplatform. This work presents a versatile and controllable mitochondrial gene-editing strategy.
{"title":"Spatiotemporally Regulated Mitochondrial Genome Editing via Enzyme and NIR-Activated CRISPR/Cas9 nanoplatform","authors":"Fei Yang, Qianqin Ran, Jiahui Chen, Guochen Bao, Yuezhong Xian, Cuiling Zhang","doi":"10.1039/d5sc07976d","DOIUrl":"https://doi.org/10.1039/d5sc07976d","url":null,"abstract":"Mitochondrial DNA (mtDNA) mutations play critical roles in tumor progression and metabolic reprogramming. Controllable gene editing within tumor cell mitochondria remains a challenge due to the double-membrane barrier and the lack of tumor-selective activation. Herein, we report a dual-responsive CRISPR/Cas delivery platform (UCRP-TPP) that enables spatiotemporally regulated mtDNA editing for targeted tumor therapy. This nanoplatform integrates near infrared light-responsive upconversion nanoparticle (UCNP), an apurinic endonuclease 1 (APE-1)-responsive DNA complex, and a mitochondrial-targeting ligand (TPP), ensuring selective activation and mitochondrial release of Cas9/sgRNA complexes. Upon activation by endogenous APE-1 enzyme and exogenous NIR light, UCRP-TPP induces mtDNA editing by CRISPR/Cas, which leads to mtDNA copy number reduction, mitochondrial membrane depolarization, reactive oxygen species generation, and tumor cell apoptosis. In vivo studies further confirm the robust antitumor efficacy of UCRP-TPP-based nanoplatform. This work presents a versatile and controllable mitochondrial gene-editing strategy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"218 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cheng-Zhuo Du, Minqiang Mai, Pei-Han Gao, Yi-Chao Zhao, Xiang-Yu Gao, Dongdong Zhang, Lian Duan, Chunming Cui, Xiao-Ye Wang
Multi-resonance (MR) materials based on 1,4-BN-heteroarenes have attracted extensive attention in recent years for narrowband electroluminescence. Extending the π-conjugation of MR skeletons is a widely adopted strategy to regulate their emission colors, but it inevitably induces structural distortion and undesirable vibronic couplings, thus broadening the emission bandwidth. Herein, we design and synthesize new MR emitters via π-extension of a classic MR backbone (CzBN) and disclose how the twisted structure plays a positive role in reducing emission bandwidth. Specifically, π-extension of CzBN to form a [5]helicene substructure (BN-5H) induces serious vibrations, while further extending the helicene moiety to build a [7]helicene substructure (BN-7H) suppresses undesirable vibrations by locking the conformation. As a consequence, BN-7H achieves a smaller full-width at half-maximum (FWHM) of 28 nm compared with BN-5H (33 nm) in organic lightemitting diodes with longer device lifetime. These results break the traditional cognition of the detrimental effect of highly twisted structure on narrowband emission and offer a new design concept for the future development of narrowband electroluminescence materials.
{"title":"Unraveling the Positive Effect of Twisted Helicene Structure on Narrowband Electroluminescence","authors":"Cheng-Zhuo Du, Minqiang Mai, Pei-Han Gao, Yi-Chao Zhao, Xiang-Yu Gao, Dongdong Zhang, Lian Duan, Chunming Cui, Xiao-Ye Wang","doi":"10.1039/d5sc08405a","DOIUrl":"https://doi.org/10.1039/d5sc08405a","url":null,"abstract":"Multi-resonance (MR) materials based on 1,4-BN-heteroarenes have attracted extensive attention in recent years for narrowband electroluminescence. Extending the π-conjugation of MR skeletons is a widely adopted strategy to regulate their emission colors, but it inevitably induces structural distortion and undesirable vibronic couplings, thus broadening the emission bandwidth. Herein, we design and synthesize new MR emitters via π-extension of a classic MR backbone (CzBN) and disclose how the twisted structure plays a positive role in reducing emission bandwidth. Specifically, π-extension of CzBN to form a [5]helicene substructure (BN-5H) induces serious vibrations, while further extending the helicene moiety to build a [7]helicene substructure (BN-7H) suppresses undesirable vibrations by locking the conformation. As a consequence, BN-7H achieves a smaller full-width at half-maximum (FWHM) of 28 nm compared with BN-5H (33 nm) in organic lightemitting diodes with longer device lifetime. These results break the traditional cognition of the detrimental effect of highly twisted structure on narrowband emission and offer a new design concept for the future development of narrowband electroluminescence materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"57 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962356","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Gaopeng Ren, Austin Mroz, Frederik Philippi, Tom Welton, Kim E. Jelfs
Ionic liquids (ILs) are salts set apart by their low melting points and can act as highly tuneable solvents with broad application potential, for example as catalysts, in batteries, and for drug delivery. The potential chemical space of ILs is vast, with only a very small region having been explored to date. Machine learning offers a promising approach to advance into this vast space of unexplored ILs; however, existing IL databases contain limited ion diversity, constraining the performance of generative models. To address this, we introduce conditional variational autoencoders (CVAEs) and a novel ion scoring method as a conditioning factor. The ion score prioritises ions with a higher likelihood of forming low-melting-point ILs. Our CVAEs effectively generate novel and diverse cations and anions. Furthermore, we constructed a melting point prediction model to identify cation-anion pairs that are likely to yield ILs with low melting points. Visualisation of the generated ILs alongside existing ones reveals that our approach effectively expands the chemical space of ILs with novel structures. Molecular dynamics simulations further validate that 13/15 of the generated ILs possess desirable low melting points (<373 K). The associated code is available at github.com/fate1997/ILGen-ion.
{"title":"Expanding the chemical space of ionic liquids using conditional variational autoencoders","authors":"Gaopeng Ren, Austin Mroz, Frederik Philippi, Tom Welton, Kim E. Jelfs","doi":"10.1039/d5sc08673f","DOIUrl":"https://doi.org/10.1039/d5sc08673f","url":null,"abstract":"Ionic liquids (ILs) are salts set apart by their low melting points and can act as highly tuneable solvents with broad application potential, for example as catalysts, in batteries, and for drug delivery. The potential chemical space of ILs is vast, with only a very small region having been explored to date. Machine learning offers a promising approach to advance into this vast space of unexplored ILs; however, existing IL databases contain limited ion diversity, constraining the performance of generative models. To address this, we introduce conditional variational autoencoders (CVAEs) and a novel ion scoring method as a conditioning factor. The ion score prioritises ions with a higher likelihood of forming low-melting-point ILs. Our CVAEs effectively generate novel and diverse cations and anions. Furthermore, we constructed a melting point prediction model to identify cation-anion pairs that are likely to yield ILs with low melting points. Visualisation of the generated ILs alongside existing ones reveals that our approach effectively expands the chemical space of ILs with novel structures. Molecular dynamics simulations further validate that 13/15 of the generated ILs possess desirable low melting points (<373 K). The associated code is available at github.com/fate1997/ILGen-ion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"96 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949953","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mengjie Li, Hang Liu, Hai Xu, Zehui Fan, Yuansheng Liu, Jixing Yang, Wei Zhu, Qinghao Chen, Yunhua Xu
Organic batteries hold significant promise for large-scale applications due to their environmental friendliness and cost-effectiveness, but they face challenges such as active material dissolution and sluggish reaction kinetics, particularly at low temperatures. Here, we employ gel polymer electrolytes (GPEs) with an ultra-low concentration of 0.1 M to tackle these issues. The diluted GPEs effectively suppress the dissolution and migration of organic species, reduce electrolyte decomposition by forming a polymer-dominated solid-electrolyte interphase, lower the Li⁺ de-solvation barrier, and enhance Li-ion diffusion under low-temperature conditions. The diluted GPEs demonstrate exceptional cycling stability and rate capability of organic batteries, achieving a cycle life of 1200 cycles at 2 C and a high specific capacity of 101 mAh g−1 at an ultra-high 10 C rate at −50 °C. Moreover, even at a high mass loading of 8 mg cm−2, the battery exhibits excellent cycling performance, retaining 90.0% of its capacity after 500 cycles. Our findings significantly expand the applicability of organic batteries to extremely cryogenic environments while also reducing costs.
有机电池由于其环境友好性和成本效益，在大规模应用中具有重要的前景，但它们面临着诸如活性物质溶解和反应动力学缓慢等挑战，特别是在低温下。在这里，我们采用超低浓度的凝胶聚合物电解质（gpe）来解决这些问题。稀释后的gpe有效抑制了有机物质的溶解和迁移，通过形成以聚合物为主的固-电解质界面减少了电解质分解，降低了Li +的脱溶剂势垒，增强了Li离子在低温条件下的扩散。稀释后的gpe表现出优异的循环稳定性和有机电池的倍率能力，在2℃下达到1200次循环寿命，在- 50℃的超高10℃倍率下达到101 mAh g - 1的高比容量。此外，即使在8 mg cm−2的高质量负载下，电池也表现出优异的循环性能，在500次循环后仍保持90.0%的容量。我们的发现大大扩展了有机电池在极低温环境中的适用性，同时也降低了成本。
{"title":"Ultra-Low Concentration Gel Polymer Electrolytes Realize Stable and Low-Temperature Lithium−Organic Batteries","authors":"Mengjie Li, Hang Liu, Hai Xu, Zehui Fan, Yuansheng Liu, Jixing Yang, Wei Zhu, Qinghao Chen, Yunhua Xu","doi":"10.1039/d5sc09108j","DOIUrl":"https://doi.org/10.1039/d5sc09108j","url":null,"abstract":"Organic batteries hold significant promise for large-scale applications due to their environmental friendliness and cost-effectiveness, but they face challenges such as active material dissolution and sluggish reaction kinetics, particularly at low temperatures. Here, we employ gel polymer electrolytes (GPEs) with an ultra-low concentration of 0.1 M to tackle these issues. The diluted GPEs effectively suppress the dissolution and migration of organic species, reduce electrolyte decomposition by forming a polymer-dominated solid-electrolyte interphase, lower the Li⁺ de-solvation barrier, and enhance Li-ion diffusion under low-temperature conditions. The diluted GPEs demonstrate exceptional cycling stability and rate capability of organic batteries, achieving a cycle life of 1200 cycles at 2 C and a high specific capacity of 101 mAh g−1 at an ultra-high 10 C rate at −50 °C. Moreover, even at a high mass loading of 8 mg cm−2, the battery exhibits excellent cycling performance, retaining 90.0% of its capacity after 500 cycles. Our findings significantly expand the applicability of organic batteries to extremely cryogenic environments while also reducing costs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"265 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ahmadreza Nezamzadeh, Shayanta Chowdhury, Gaohe Hu, Nathaniel Dominique, Emmett ED Desroche, Sakiat SH Hossain, Mark D. Aloisio, Michael MF Furlan, Ryan R. K. RRKG Groome, Kayla KB Boire, Alastair McLean, Lasse Jensen, Jon Camden, Cathleen Crudden
ABSTRACT: The effect of wingtip groups on the orientation of N-heterocyclic carbene (NHC)–based self-assembled monolayers (SAMs) on a variety of metal surfaces has received considerable attention. However, the influence of backbone substituents on orientation has received virtually no attention, despite the fact that backbone interactions are critical for upright orientation of thiolate-based SAMs and that backbone functionalization is important for many applications. To address this question, a series of gold nanoparticles (NPs) supported by NHCs featuring symmetrical or asymmetrical long alkyl backbone substituents and ethyl and isopropyl wingtips were synthesized. The gold NPs were characterized using UV-Vis spectroscopy, electron microscopy, mass spectrometry, and surface-enhanced Raman spectroscopy (SERS). Experimental SER spectra were compared to simulated spectra, illustrating that both ethyl and isopropyl NHCs with symmetrical dodecyl long chains in the backbone adopt a primarily vertical configuration on the gold surface. However, the ethyl NHC with a single hexyloxy backbone substituent adopts mainly a flat configuration on the gold NP surface based on combined SERS and scanning tunneling microscopy (STM) results. This is attributed to on-surface interactions between long alkyl chains, which provide an unanticipated source of stability favoring the flat-lying orientation. Lastly, the thermal stability of the NHC-functionalized gold NPs at elevated temperatures was investigated. The dodecyloxy-functionalized NHC AuNPs remain thermally stable for 72 hours at 100°C, representing a significant improvement over state-of-the-art NHC-AuNPs. NHCs containing isopropyl wingtip groups provide NPs with higher levels of stability than diethyl-substituted NHCs, regardless of backbone substituents. Taken together, our results highlight critical synthetic considerations for NHC ligand design, enabling control of ligand orientation and nanomaterial stability by tuning NHC backbone substituents.
{"title":"Beyond Wingtips: Backbone Alkylation Affects the Orientation of N-Heterocyclic Carbenes on Gold Nanoparticles","authors":"Ahmadreza Nezamzadeh, Shayanta Chowdhury, Gaohe Hu, Nathaniel Dominique, Emmett ED Desroche, Sakiat SH Hossain, Mark D. Aloisio, Michael MF Furlan, Ryan R. K. RRKG Groome, Kayla KB Boire, Alastair McLean, Lasse Jensen, Jon Camden, Cathleen Crudden","doi":"10.1039/d5sc05986k","DOIUrl":"https://doi.org/10.1039/d5sc05986k","url":null,"abstract":"<strong>ABSTRACT:</strong> The effect of wingtip groups on the orientation of N-heterocyclic carbene (NHC)–based self-assembled monolayers (SAMs) on a variety of metal surfaces has received considerable attention. However, the influence of backbone substituents on orientation has received virtually no attention, despite the fact that backbone interactions are critical for upright orientation of thiolate-based SAMs and that backbone functionalization is important for many applications. To address this question, a series of gold nanoparticles (NPs) supported by NHCs featuring symmetrical or asymmetrical long alkyl backbone substituents and ethyl and isopropyl wingtips were synthesized. The gold NPs were characterized using UV-Vis spectroscopy, electron microscopy, mass spectrometry, and surface-enhanced Raman spectroscopy (SERS). Experimental SER spectra were compared to simulated spectra, illustrating that both ethyl and isopropyl NHCs with symmetrical dodecyl long chains in the backbone adopt a primarily vertical configuration on the gold surface. However, the ethyl NHC with a single hexyloxy backbone substituent adopts mainly a flat configuration on the gold NP surface based on combined SERS and scanning tunneling microscopy (STM) results. This is attributed to on-surface interactions between long alkyl chains, which provide an unanticipated source of stability favoring the flat-lying orientation. Lastly, the thermal stability of the NHC-functionalized gold NPs at elevated temperatures was investigated. The dodecyloxy-functionalized NHC AuNPs remain thermally stable for 72 hours at 100°C, representing a significant improvement over state-of-the-art NHC-AuNPs. NHCs containing isopropyl wingtip groups provide NPs with higher levels of stability than diethyl-substituted NHCs, regardless of backbone substituents. Taken together, our results highlight critical synthetic considerations for NHC ligand design, enabling control of ligand orientation and nanomaterial stability by tuning NHC backbone substituents.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"84 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955825","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Single-atom catalysts (SACs) offer exceptional potential for the oxygen evolution reaction (OER), yet their practical application is hindered by an incomplete understanding of structure–activity relationships at the atomic scale. Traditional descriptors fail to fully explain the adsorption behavior of key oxygen intermediates, creating a fundamental gap in catalyst design. This review addresses this limitation by introducing a “structure–adsorption” framework that clarifies how metal–support interactions (MSIs) can be tuned through coordination engineering, such as spin configuration, axial coordination, and atomic distance. Our analysis demonstrates that optimal OER activity arises from a balance between orbital hybridization and electrostatic effects, providing clear design principles for next-generation SACs aimed at sustainable energy conversion.
{"title":"Designing single-atom catalysts: bridging metal–support interaction and adsorption energy optimization","authors":"Huaizhen Cui, Jiaqi Zhang, Chen Chen","doi":"10.1039/d5sc08100a","DOIUrl":"https://doi.org/10.1039/d5sc08100a","url":null,"abstract":"Single-atom catalysts (SACs) offer exceptional potential for the oxygen evolution reaction (OER), yet their practical application is hindered by an incomplete understanding of structure–activity relationships at the atomic scale. Traditional descriptors fail to fully explain the adsorption behavior of key oxygen intermediates, creating a fundamental gap in catalyst design. This review addresses this limitation by introducing a “structure–adsorption” framework that clarifies how metal–support interactions (MSIs) can be tuned through coordination engineering, such as spin configuration, axial coordination, and atomic distance. Our analysis demonstrates that optimal OER activity arises from a balance between orbital hybridization and electrostatic effects, providing clear design principles for next-generation SACs aimed at sustainable energy conversion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949955","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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