Reagan X. Hooper, Benjamin I. Poulter, Jesper Schwarz, Mariam Barakat, Kristjan Kunnus, Kacie J Nelson, Aleksandra Ilic, Clara García-Mateos, Rajdip Chowdhury, Jens Uhlig, Kenneth Wärnmark, Elena Jakubikova, Amy Cordones, Kelly Gaffney
Lifetimes of photoexcited charge transfer (CT) states in transition metal chromophores are influenced by low-lying ligand field (LF) excited states, especially for 3d metal complexes. To manipulate interactions between LF and CT states, it is important to be able to control LF excited state energies using tunable synthetic variables. In this report, we use Fe 2p3d L3-edge resonant inelastic X-ray scattering (RIXS) to measure LF excited state energies of three homoleptic iron chromophores coordinated by strong-field N-heterocyclic carbenes (NHCs). We investigate the effect of oxidation state and ligand scaffold on LF energies and covalency parameters. A cyclometalated bis(NHC) ligand affords both high LF excited state energies (and thus high 10Dq) as well as high metal-ligand covalency compared to other iron complexes with very strong-field ligands. However, for the set of complexes investigated, we do not observe meaningful correlation between the LF excited state energies and the CT excited state lifetimes. These results illustrate that targeting long-lived CT excited states necessitates control of multiple molecular excited state properties, with destabilization of the LF excited state energies proving necessary, but insufficient, to control the CT excited state lifetime in Fe carbene complexes.
{"title":"Highly-Destabilized Ligand Field Excited States of Iron Carbene Complexes and Their Relation to Charge Transfer State Lifetimes","authors":"Reagan X. Hooper, Benjamin I. Poulter, Jesper Schwarz, Mariam Barakat, Kristjan Kunnus, Kacie J Nelson, Aleksandra Ilic, Clara García-Mateos, Rajdip Chowdhury, Jens Uhlig, Kenneth Wärnmark, Elena Jakubikova, Amy Cordones, Kelly Gaffney","doi":"10.1039/d5sc07843a","DOIUrl":"https://doi.org/10.1039/d5sc07843a","url":null,"abstract":"Lifetimes of photoexcited charge transfer (CT) states in transition metal chromophores are influenced by low-lying ligand field (LF) excited states, especially for 3d metal complexes. To manipulate interactions between LF and CT states, it is important to be able to control LF excited state energies using tunable synthetic variables. In this report, we use Fe 2p3d L<small><sub>3</sub></small><small><sub>-</sub></small>edge resonant inelastic X-ray scattering (RIXS) to measure LF excited state energies of three homoleptic iron chromophores coordinated by strong-field <em>N</em>-heterocyclic carbenes (NHCs). We investigate the effect of oxidation state and ligand scaffold on LF energies and covalency parameters. A cyclometalated bis(NHC) ligand affords both high LF excited state energies (and thus high 10Dq) as well as high metal-ligand covalency compared to other iron complexes with very strong-field ligands. However, for the set of complexes investigated, we do not observe meaningful correlation between the LF excited state energies and the CT excited state lifetimes. These results illustrate that targeting long-lived CT excited states necessitates control of multiple molecular excited state properties, with destabilization of the LF excited state energies proving necessary, but insufficient, to control the CT excited state lifetime in Fe carbene complexes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"49 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962355","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}
Mei Wang, Hao Du, Yong Nian, Guanshui Ma, Jinfang Zhang, Xiaoguang Wang, Xiaofeng Li
The development of bifunctional oxygen electrocatalyst is crucial for the commercialization of rechargeable zinc-air batteries (RZABs). This work proposes an innovative strategy of "dealloying-carbon coating-dip pyrolysis" to highly stable anchor a small amount of Pt nanoparticles (0.032 mg cm -2 ) onto carbon-encapsulated nanoporous CoFe2O4 (np-CFO). Benefiting from its nanoporous structure with larger specific surface area and adhered carbon layer with superior electrical conductivity, the sandwich-like Pt/np-CFO@C electrode exhibits a lower OER-ORR potential gap (ΔE) of 0.7 V. Meanwhile, Pt/np-CFO@C based RZAB delivers specific capacity of 781 mA h g -1 , power density of 185 mW cm -2 and cycling life exceeding 1400 hours.FTIR and XAFS results indicate carbon layer could not only play a bridging role between np-CFO and Pt, but also lead to load more zero valence Pt. HAADF image proves that the post-formed oxide layer can protect Pt from inactivation through strong metal-support interaction (SMSI). In-situ Raman and RRDE testing confirm the 4-electron transfer mechanism of ORR on Pt/np-CFO@C. DFT calculations verify that Pt/CFO@C has metallic property, symmetric d-band centers and the lowest energy barrier for ORR/OER. In-situ XRD reveals that the size of Pt nanoparticles could get smaller in the early stage of discharge, which is beneficial to expose more active sites and show gradually improving performance. This work lays the groundwork for the future development of cost-effective RZABs.
双功能氧电催化剂的开发是实现可充电锌空气电池（RZABs）商业化的关键。本研究提出了一种“脱合金-碳涂层-浸热”的创新策略，将少量铂纳米粒子（0.032 mg cm -2）高稳定地锚定在碳包封的纳米多孔CoFe2O4 （np-CFO）上。得益于其具有较大比表面积的纳米孔结构和具有优异导电性的粘附碳层，三明治状Pt/np-CFO@C电极的OER-ORR电位差（ΔE）较低，为0.7 V。同时，基于Pt/np-CFO@C的RZAB的比容量为781 mA h g -1，功率密度为185 mW cm -2，循环寿命超过1400小时。FTIR和XAFS结果表明，碳层不仅可以在np-CFO和Pt之间起到桥梁作用，而且可以负载更多的零价Pt。HAADF图像证明，后形成的氧化层可以通过强金属-载体相互作用（SMSI）保护Pt免于失活。原位拉曼和RRDE测试证实了ORR在Pt/np-CFO@C上的4电子转移机理。DFT计算验证了Pt/CFO@C具有金属性质、对称的d带中心和ORR/OER的最低能垒。原位XRD分析表明，Pt纳米颗粒在放电初期尺寸变小，有利于暴露更多的活性位点，性能逐渐提高。这项工作为未来开发具有成本效益的rzab奠定了基础。
{"title":"Highly stable linking platinum and porous spinel via carbon bridge engineering towards long-lifespan of rechargeable zinc-air battery","authors":"Mei Wang, Hao Du, Yong Nian, Guanshui Ma, Jinfang Zhang, Xiaoguang Wang, Xiaofeng Li","doi":"10.1039/d5sc09967f","DOIUrl":"https://doi.org/10.1039/d5sc09967f","url":null,"abstract":"The development of bifunctional oxygen electrocatalyst is crucial for the commercialization of rechargeable zinc-air batteries (RZABs). This work proposes an innovative strategy of \"dealloying-carbon coating-dip pyrolysis\" to highly stable anchor a small amount of Pt nanoparticles (0.032 mg cm -2 ) onto carbon-encapsulated nanoporous CoFe2O4 (np-CFO). Benefiting from its nanoporous structure with larger specific surface area and adhered carbon layer with superior electrical conductivity, the sandwich-like Pt/np-CFO@C electrode exhibits a lower OER-ORR potential gap (ΔE) of 0.7 V. Meanwhile, Pt/np-CFO@C based RZAB delivers specific capacity of 781 mA h g -1 , power density of 185 mW cm -2 and cycling life exceeding 1400 hours.FTIR and XAFS results indicate carbon layer could not only play a bridging role between np-CFO and Pt, but also lead to load more zero valence Pt. HAADF image proves that the post-formed oxide layer can protect Pt from inactivation through strong metal-support interaction (SMSI). In-situ Raman and RRDE testing confirm the 4-electron transfer mechanism of ORR on Pt/np-CFO@C. DFT calculations verify that Pt/CFO@C has metallic property, symmetric d-band centers and the lowest energy barrier for ORR/OER. In-situ XRD reveals that the size of Pt nanoparticles could get smaller in the early stage of discharge, which is beneficial to expose more active sites and show gradually improving performance. This work lays the groundwork for the future development of cost-effective RZABs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949952","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}
Lei Tan, Faiza Meharban, Jin Tian, Lingzhi Zhu, Tiantian Su, Xiaotong Wu, Yujie Song, Qiuju Zhang, Jingsan Xu, Chao Lin, Xiaopeng Li, Wei Luo
Proton exchange membrane water electrolysis (PEMWE) is a cornerstone technology for carbon-neutral hydrogen production, yet its scalability is constrained by the intrinsic activity-stability trade-off of oxygen evolution reaction (OER) electrocatalysts. To overcome this challenge, we design a Ru/RuO2 heterostructure by integrating metallic Ru to modulate the d-orbital electron density of RuO2. The metallic Ru domains suppress lattice oxygen migration (LOM) while enhancing electron delocalization. The eg orbital filling shifts the Ru 4d-band center downward, reducing the adsorption strength of reaction intermediates (*OH, *O, *OOH). The optimized Ru/RuO2 electrocatalyst achieves a overpotential of 181 mV at 10 mA cm-2 in 0.5 M H2SO4 and maintains stable performance for 260 hours with minimal degradation rate (0.065 mV h-1). In PEMWE device, it lowers the cell voltage from 1.88 V (RuO2) to 1.68 V (Ru/RuO2) at 1 A cm-2, exhibiting negligible performance loss over 120 hours. This work introduces a dopant-free electronic engineering strategy that advances the design of stable, high performance pure Ru-based anodic catalysts for energy conversion technologies.
质子交换膜电解（PEMWE）是碳中性制氢的基础技术，但其可扩展性受到析氧反应（OER）电催化剂固有活性与稳定性权衡的限制。为了克服这一挑战，我们设计了Ru/RuO2异质结构，通过整合金属Ru来调节RuO2的d轨道电子密度。金属Ru畴抑制晶格氧迁移（LOM），增强电子离域。eg轨道填充使Ru 4d带中心下移，降低了反应中间体（*OH, *O, *OOH）的吸附强度。优化后的Ru/RuO2电催化剂在0.5 M H2SO4中，在10 mA cm-2条件下的过电位达到181 mV，并以最小的降解率（0.065 mV h-1）保持了260小时的稳定性能。在PEMWE器件中，它在1 A cm-2时将电池电压从1.88 V （RuO2）降低到1.68 V (Ru/RuO2)，在120小时内表现出可以忽略不计的性能损失。这项工作介绍了一种无掺杂的电子工程策略，该策略推进了用于能量转换技术的稳定、高性能纯钌基阳极催化剂的设计。
{"title":"Dopant-Free Stabilization of Ruthenium Oxide via Metallic Ru-Induced d-Orbital Modulation for Acidic Water Electrolysis","authors":"Lei Tan, Faiza Meharban, Jin Tian, Lingzhi Zhu, Tiantian Su, Xiaotong Wu, Yujie Song, Qiuju Zhang, Jingsan Xu, Chao Lin, Xiaopeng Li, Wei Luo","doi":"10.1039/d5sc08602g","DOIUrl":"https://doi.org/10.1039/d5sc08602g","url":null,"abstract":"Proton exchange membrane water electrolysis (PEMWE) is a cornerstone technology for carbon-neutral hydrogen production, yet its scalability is constrained by the intrinsic activity-stability trade-off of oxygen evolution reaction (OER) electrocatalysts. To overcome this challenge, we design a Ru/RuO2 heterostructure by integrating metallic Ru to modulate the d-orbital electron density of RuO2. The metallic Ru domains suppress lattice oxygen migration (LOM) while enhancing electron delocalization. The eg orbital filling shifts the Ru 4d-band center downward, reducing the adsorption strength of reaction intermediates (*OH, *O, *OOH). The optimized Ru/RuO2 electrocatalyst achieves a overpotential of 181 mV at 10 mA cm-2 in 0.5 M H2SO4 and maintains stable performance for 260 hours with minimal degradation rate (0.065 mV h-1). In PEMWE device, it lowers the cell voltage from 1.88 V (RuO2) to 1.68 V (Ru/RuO2) at 1 A cm-2, exhibiting negligible performance loss over 120 hours. This work introduces a dopant-free electronic engineering strategy that advances the design of stable, high performance pure Ru-based anodic catalysts for energy conversion technologies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"144 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949970","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}
Employing noncovalent forces to fabricate self-assembled nanoarchitectures composed of multiple constituents regulates the expression of chirality across hierarchical levels. Here we report a programmed hierarchical chiral assembly through π–hole interactions synchronized with hydrogen bonding. A chiral molecular pincer composed of benzimidazole and cholesteryl moieties capable of forming complementary hydrogen bonds with carboxylic acids, coassembles with achiral organic acids to generate one-dimensional helical superstructures, enhancing the expression of supramolecular chirality and chiroptical activities. The multicomponent coassembly system accommodates structurally diverse acids-including aliphatic, aromatic, and polymeric acids-exhibiting pronounced substrate-dependent induction of supramolecular chirality. Further incorporating fluorinated or chlorinated components introduced π–hole forces that realize modulation of the macroscopic chirality, affording well-defined chiral microarchitectures with tunable topology and chirality. The resulting materials display complex yet highly ordered chiral nanostructures, with the potential for anisotropic growth toward macroscopic scales. This study establishes a modular platform for the high-throughput fabrication of chiroptical materials with tunable supramolecular chirality, offering insights into the rational design of functional soft materials through π–hole interaction driven hierarchical self-assembly.
{"title":"π–hole forces enabled programmable supramolecular chirality based on a chiral benzimidazole pincer","authors":"Weilong Ma, Aiyou Hao, Pengyao Xing","doi":"10.1039/d5sc09567k","DOIUrl":"https://doi.org/10.1039/d5sc09567k","url":null,"abstract":"Employing noncovalent forces to fabricate self-assembled nanoarchitectures composed of multiple constituents regulates the expression of chirality across hierarchical levels. Here we report a programmed hierarchical chiral assembly through π–hole interactions synchronized with hydrogen bonding. A chiral molecular pincer composed of benzimidazole and cholesteryl moieties capable of forming complementary hydrogen bonds with carboxylic acids, coassembles with achiral organic acids to generate one-dimensional helical superstructures, enhancing the expression of supramolecular chirality and chiroptical activities. The multicomponent coassembly system accommodates structurally diverse acids-including aliphatic, aromatic, and polymeric acids-exhibiting pronounced substrate-dependent induction of supramolecular chirality. Further incorporating fluorinated or chlorinated components introduced π–hole forces that realize modulation of the macroscopic chirality, affording well-defined chiral microarchitectures with tunable topology and chirality. The resulting materials display complex yet highly ordered chiral nanostructures, with the potential for anisotropic growth toward macroscopic scales. This study establishes a modular platform for the high-throughput fabrication of chiroptical materials with tunable supramolecular chirality, offering insights into the rational design of functional soft materials through π–hole interaction driven hierarchical self-assembly.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"94 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949954","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}
Joseph Brehm, Richard Lewis, Alan Francis Scott, David John Morgan, Thomas Davies, Nigel Richards, Graham Hutchings
Decreasing our reliance on fossil carbon requires economically viable and scalable pathways to utilize sustainable sources, such as chitin. Current methods for converting chitin to high-value chemicals require treatment with strong acids and/or bases at high temperature, thereby giving complicated product mixtures with substantial, negative environmental impact. Here we present a chemo-enzymatic cascade in which H2O2, generated in situ over Pd-based nanoalloys, is used by a lytic polysaccharide monooxygenase (LPMO) to convert chitin into soluble oligosaccharide fragments. Our approach, which minimizes oxidative damage to the enzyme, eliminates the need for atom-inefficient and energy intensive approaches to chitin depolymerization, potentially achieving substantial environmental and economic savings. The simplicity of this chemo-catalyst/enzyme cascade has significant advantages for accessing chitin as a bio-carbon resource.
{"title":"Chemo-enzymatic One-Pot Depolymerization of β-Chitin","authors":"Joseph Brehm, Richard Lewis, Alan Francis Scott, David John Morgan, Thomas Davies, Nigel Richards, Graham Hutchings","doi":"10.1039/d5sc07429k","DOIUrl":"https://doi.org/10.1039/d5sc07429k","url":null,"abstract":"Decreasing our reliance on fossil carbon requires economically viable and scalable pathways to utilize sustainable sources, such as chitin. Current methods for converting chitin to high-value chemicals require treatment with strong acids and/or bases at high temperature, thereby giving complicated product mixtures with substantial, negative environmental impact. Here we present a chemo-enzymatic cascade in which H2O2, generated in situ over Pd-based nanoalloys, is used by a lytic polysaccharide monooxygenase (LPMO) to convert chitin into soluble oligosaccharide fragments. Our approach, which minimizes oxidative damage to the enzyme, eliminates the need for atom-inefficient and energy intensive approaches to chitin depolymerization, potentially achieving substantial environmental and economic savings. The simplicity of this chemo-catalyst/enzyme cascade has significant advantages for accessing chitin as a bio-carbon resource.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955824","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}
Antiaromatic π-electron systems provide unique electronic features arising from the cyclic conjugation of 4n π-electrons, yet synthetic access to strongly antiaromatic heteroarene-fused scaffolds remains limited. Here we report a general and scalable synthetic route to benzothiophene-fused pentalenes via the first thiophene analogue of Brand’s bicyclo[3.3.0]octadiene-1,4-dione intermediate. The pre-installation of the bicyclic five-membered-ring core at an early stage of synthesis enables efficient annulation of benzothiophene moieties and late-stage diversification at the 1,4-positions through the 1,2-addition of organometallic nucleophiles, followed by optimized dehydration. This strategy affords a series of benzothiophene-fused pentalenes bearing diverse aryl, heteroaryl, and alkynyl substituents in practical yields, with isolation by simple filtration. The benzothiophene-fused pentalenes thus obtained exhibit strong antiaromatic character that correlates with electronic effects, consistent with the topological charge stabilization rule. This work establishes a versatile platform for probing substituent-dependent antiaromaticity and for designing functional materials based on strongly antiaromatic π-systems.
{"title":"Modular Synthesis of Benzothiophene-Fused Pentalene Reveals Substituent-Dependent Antiaromaticity","authors":"Ryosuke Isogai, Kosuke Yasui, Aiko Fukazawa","doi":"10.1039/d5sc09325b","DOIUrl":"https://doi.org/10.1039/d5sc09325b","url":null,"abstract":"Antiaromatic π-electron systems provide unique electronic features arising from the cyclic conjugation of 4n π-electrons, yet synthetic access to strongly antiaromatic heteroarene-fused scaffolds remains limited. Here we report a general and scalable synthetic route to benzothiophene-fused pentalenes via the first thiophene analogue of Brand’s bicyclo[3.3.0]octadiene-1,4-dione intermediate. The pre-installation of the bicyclic five-membered-ring core at an early stage of synthesis enables efficient annulation of benzothiophene moieties and late-stage diversification at the 1,4-positions through the 1,2-addition of organometallic nucleophiles, followed by optimized dehydration. This strategy affords a series of benzothiophene-fused pentalenes bearing diverse aryl, heteroaryl, and alkynyl substituents in practical yields, with isolation by simple filtration. The benzothiophene-fused pentalenes thus obtained exhibit strong antiaromatic character that correlates with electronic effects, consistent with the topological charge stabilization rule. This work establishes a versatile platform for probing substituent-dependent antiaromaticity and for designing functional materials based on strongly antiaromatic π-systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"282 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955826","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}
All-solid-state lithium batteries (ASSLBs) employing Ni-rich layered oxide cathodes (NRLOs) and sulfide solid-state electrolytes (SSEs) demonstrate high energy density and enhanced safety. However, the impact of stacking pressure on the mechanical failure of NRLOs is not well understood. This study systematically investigates the effect of stacking pressure on the chemo-mechanical degradation of NRLOs in sulfide ASSLBs separately with lithium indium (LiIn) and zero-strain lithium titanate (LTO) as anodes. Through multi-dimensional characterization and electrochemical testing, it is demonstrated that increased stacking pressure compresses interfacial voids and reduces lithium-ion transport resistance, significantly enhancing the performance of sulfide ASSLBs. Nevertheless, excessive stacking pressure induces significant stress concentration during cycling, exacerbating lattice distortion, oxygen release, and the decomposition of the sulfide SSE. These effects contribute to fragmentation of NRLO particles and interlayer cracking of electrodes, ultimately leading to severe capacity fade and increased impedance. The findings provide critical insights for optimizing stacking pressure in durable sulfide ASSLBs.
{"title":"Exploring stacking pressure-induced mechanical failure of a Ni-rich cathode in sulfide solid-state batteries.","authors":"Yiman Feng, Zhixing Wang, Gui Luo, Duo Deng, Wenjie Peng, Wenchao Zhang, Hui Duan, Feixiang Wu, Xing Ou, Junchao Zheng, Jiexi Wang","doi":"10.1039/d5sc09321j","DOIUrl":"10.1039/d5sc09321j","url":null,"abstract":"<p><p>All-solid-state lithium batteries (ASSLBs) employing Ni-rich layered oxide cathodes (NRLOs) and sulfide solid-state electrolytes (SSEs) demonstrate high energy density and enhanced safety. However, the impact of stacking pressure on the mechanical failure of NRLOs is not well understood. This study systematically investigates the effect of stacking pressure on the chemo-mechanical degradation of NRLOs in sulfide ASSLBs separately with lithium indium (LiIn) and zero-strain lithium titanate (LTO) as anodes. Through multi-dimensional characterization and electrochemical testing, it is demonstrated that increased stacking pressure compresses interfacial voids and reduces lithium-ion transport resistance, significantly enhancing the performance of sulfide ASSLBs. Nevertheless, excessive stacking pressure induces significant stress concentration during cycling, exacerbating lattice distortion, oxygen release, and the decomposition of the sulfide SSE. These effects contribute to fragmentation of NRLO particles and interlayer cracking of electrodes, ultimately leading to severe capacity fade and increased impedance. The findings provide critical insights for optimizing stacking pressure in durable sulfide ASSLBs.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12794287/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145965713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Crystal structure prediction has developed into a valuable tool for anticipating the likely crystalline arrangement that a molecule will adopt, with applications in materials discovery and polymorph screening. Although powerful, crystal structure prediction is usually limited to locating the local minima of the crystal energy surface. We demonstrate how, by mapping the energy barriers between structures, applying the Monte Carlo threshold algorithm provides a richer description of the crystal energy landscape which allows us to rationalize the differences in experimental conditions under which different crystal polymorphs are observed. As a demonstration, we apply the method to three polymorphic polycyclic aromatic hydrocarbons, phenanthrene, pyrene, and perylene.
{"title":"From Crystal Structure Prediction to Polymorphic Behaviour: Monte Carlo Threshold Mapping of Crystal Energy Landscapes","authors":"Pedro Juan-Royo, Graeme Matthew Day","doi":"10.1039/d5sc08644b","DOIUrl":"https://doi.org/10.1039/d5sc08644b","url":null,"abstract":"Crystal structure prediction has developed into a valuable tool for anticipating the likely crystalline arrangement that a molecule will adopt, with applications in materials discovery and polymorph screening. Although powerful, crystal structure prediction is usually limited to locating the local minima of the crystal energy surface. We demonstrate how, by mapping the energy barriers between structures, applying the Monte Carlo threshold algorithm provides a richer description of the crystal energy landscape which allows us to rationalize the differences in experimental conditions under which different crystal polymorphs are observed. As a demonstration, we apply the method to three polymorphic polycyclic aromatic hydrocarbons, phenanthrene, pyrene, and perylene.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"45 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949958","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}
Noncentrosymmetric (NCS) structure crystalline materials exhibit a range of high-tech applications, however, the controllable synthesis of NCS materials using achiral molecular building blocks remains a great challenge. Herein, we present a crystal engineering strategy for constructing NCS multifunctional materials. We designed 1,4-diazabicyclo[2.2.2]octane (DABCO) derivative dication, which adopts a chiral conformation, despite lacking chiral carbon atoms. These dications were assembled with tetrahedral [MnX4] 2‾ anions to induce asymmetry into the structure. The high directionality H…X interactions between the anions and cations induce and stabilize NCS ion-pair structures, leading to NCS crystallization. We successfully obtained an NCS hybrid crystal, [H-Pr-DABCO]MnBr4 (where H and Pr represent proton and propyl groups, respectively). This compound crystallizes in a polar space group P21 at room temperature and undergoes a reversible phase transition between two polar phases. This chiral-polar hybrid crystal integrates multiple functionalities, including switchable dielectric behavior, reversible thermochromism, second-order nonlinear optical activity, ferroelectricity, and circularly polarized luminescence.Moreover, the material exhibits a notable spontaneous polarization of 21.5 µC cm ‾2 , close to that of the typical inorganic ferroelectric BaTiO3. This work elucidates a design strategy for constructing multifunctional materials, highlighting their potential for application in advanced devices.
{"title":"Rotational Symmetry Dication Assembling Ferroelectric, Thermochromic and Circularly Polarized Luminescent Multifunctional Manganese(II) Bromide Hybrid","authors":"Jia-Yi Yuan, Yu Xu, Lu Zhai, Shan-Shan Hei, Jianyi Huang, Weihua Ning, Hongling Cai, Xiaoming Ren","doi":"10.1039/d5sc08499g","DOIUrl":"https://doi.org/10.1039/d5sc08499g","url":null,"abstract":"Noncentrosymmetric (NCS) structure crystalline materials exhibit a range of high-tech applications, however, the controllable synthesis of NCS materials using achiral molecular building blocks remains a great challenge. Herein, we present a crystal engineering strategy for constructing NCS multifunctional materials. We designed 1,4-diazabicyclo[2.2.2]octane (DABCO) derivative dication, which adopts a chiral conformation, despite lacking chiral carbon atoms. These dications were assembled with tetrahedral [MnX4] 2‾ anions to induce asymmetry into the structure. The high directionality H…X interactions between the anions and cations induce and stabilize NCS ion-pair structures, leading to NCS crystallization. We successfully obtained an NCS hybrid crystal, [H-Pr-DABCO]MnBr4 (where H and Pr represent proton and propyl groups, respectively). This compound crystallizes in a polar space group P21 at room temperature and undergoes a reversible phase transition between two polar phases. This chiral-polar hybrid crystal integrates multiple functionalities, including switchable dielectric behavior, reversible thermochromism, second-order nonlinear optical activity, ferroelectricity, and circularly polarized luminescence.Moreover, the material exhibits a notable spontaneous polarization of 21.5 µC cm ‾2 , close to that of the typical inorganic ferroelectric BaTiO3. This work elucidates a design strategy for constructing multifunctional materials, highlighting their potential for application in advanced devices.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"34 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949969","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：