Pub Date : 2026-03-17DOI: 10.1021/acs.chemmater.5c02500
Yanis Souid, Patrick Soudan, Sylvain Franger, Bernard Lestriez, Nathalie Herlin-Boime, Philippe Poizot, Philippe Moreau, Sophie Le Caër
Operando synchrotron techniques provide unique insights into the internal processes of lithium-ion batteries, but radiation-induced effects can alter cell behavior and compromise data interpretation. To better understand these phenomena, we developed an operando cell specifically designed for controlled irradiation studies, replicating synchrotron-like conditions, but at the laboratory scale. The electrolyte was selectively irradiated with an electron beam at doses of 5 and 10 kGy, and the resulting impacts on the electrochemical performance of a silicon-based electrode, gas evolution, and solid electrolyte interphase (SEI) composition were investigated. Irradiation led to immediate and dose-dependent degradation of cycling performance, with the 10 kGy-irradiated cells failing within four cycles. Gas analysis revealed increased formation of H2, CO2, CO, and CH4, the latter two gases being not produced in the nonirradiated cells, as well as the generation of specific compounds such as C2H6 and CH3CHO, absent in nonirradiated cells. While most gases showed dose-dependent production, H2 remained relatively insensitive to irradiation levels, likely due to residual water content. After irradiation followed by cycling of the cell, microscopic and electrochemical impedance spectroscopy analyses indicated significant modifications of the electrode surface and SEI morphology, with the formation of porous or inhomogeneous layers that promote further electrolyte degradation and gas release. These findings underscore the importance of accounting for beam-induced effects in operando studies, with a focus on the effect of the irradiation of the electrolyte, and provide a framework for understanding radiation-accelerated aging mechanisms in lithium-ion batteries.
{"title":"Laboratory Electron Irradiation Operando Cell for Probing Synchrotron Beam Damage Mechanisms in Lithium-Ion Battery Electrolytes","authors":"Yanis Souid, Patrick Soudan, Sylvain Franger, Bernard Lestriez, Nathalie Herlin-Boime, Philippe Poizot, Philippe Moreau, Sophie Le Caër","doi":"10.1021/acs.chemmater.5c02500","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02500","url":null,"abstract":"<i>Operando</i> synchrotron techniques provide unique insights into the internal processes of lithium-ion batteries, but radiation-induced effects can alter cell behavior and compromise data interpretation. To better understand these phenomena, we developed an <i>operando</i> cell specifically designed for controlled irradiation studies, replicating synchrotron-like conditions, but at the laboratory scale. The electrolyte was selectively irradiated with an electron beam at doses of 5 and 10 kGy, and the resulting impacts on the electrochemical performance of a silicon-based electrode, gas evolution, and solid electrolyte interphase (SEI) composition were investigated. Irradiation led to immediate and dose-dependent degradation of cycling performance, with the 10 kGy-irradiated cells failing within four cycles. Gas analysis revealed increased formation of H<sub>2</sub>, CO<sub>2</sub>, CO, and CH<sub>4</sub>, the latter two gases being not produced in the nonirradiated cells, as well as the generation of specific compounds such as C<sub>2</sub>H<sub>6</sub> and CH<sub>3</sub>CHO, absent in nonirradiated cells. While most gases showed dose-dependent production, H<sub>2</sub> remained relatively insensitive to irradiation levels, likely due to residual water content. After irradiation followed by cycling of the cell, microscopic and electrochemical impedance spectroscopy analyses indicated significant modifications of the electrode surface and SEI morphology, with the formation of porous or inhomogeneous layers that promote further electrolyte degradation and gas release. These findings underscore the importance of accounting for beam-induced effects in <i>operando</i> studies, with a focus on the effect of the irradiation of the electrolyte, and provide a framework for understanding radiation-accelerated aging mechanisms in lithium-ion batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"17 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471670","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}
Hexaferrite nanoplatelets exhibit size-dependent structural variations influencing their magnetic properties. Here, we synthesized Mn-substituted barium ferrite nanoplatelets via hydrothermal methods, achieving up to ∼27% Fe substitution. Advanced STEM and Raman analyses revealed depletion of Fe(2b) trigonal lattice sites and associated oxygen vacancies, forming a β-alumina-type ferrite structure─representing the first pure Ba2+ β-ferrite analogue. First-principles modeling confirmed the thermodynamic stabilization of this defected structure at higher Mn/Fe ratios. Mn substitution reduced nanoplatelet size and suppressed magnetic properties, which were restored upon annealing at 800 °C, reverting to the M-type hexaferrite structure with expected magnetic behavior. These findings elucidate nanoscale structural adaptations induced by chemical substitution and offer insights into tailoring the magnetic properties of barium ferrite nanoplatelets through controlled synthesis and post-treatment.
{"title":"Mn-Induced Stabilization of a β-Alumina-Type Defect Structure in Barium Hexaferrite Nanoplatelets","authors":"Darko Makovec, Matic Poberžnik, Janvit Teržan, Tomaž Mertelj, Damjan Vengust, Goran Dražić, Darja Lisjak, Sašo Gyergyek","doi":"10.1021/acs.chemmater.6c00103","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c00103","url":null,"abstract":"Hexaferrite nanoplatelets exhibit size-dependent structural variations influencing their magnetic properties. Here, we synthesized Mn-substituted barium ferrite nanoplatelets via hydrothermal methods, achieving up to ∼27% Fe substitution. Advanced STEM and Raman analyses revealed depletion of Fe(2b) trigonal lattice sites and associated oxygen vacancies, forming a β-alumina-type ferrite structure─representing the first pure Ba<sup>2+</sup> β-ferrite analogue. First-principles modeling confirmed the thermodynamic stabilization of this defected structure at higher Mn/Fe ratios. Mn substitution reduced nanoplatelet size and suppressed magnetic properties, which were restored upon annealing at 800 °C, reverting to the M-type hexaferrite structure with expected magnetic behavior. These findings elucidate nanoscale structural adaptations induced by chemical substitution and offer insights into tailoring the magnetic properties of barium ferrite nanoplatelets through controlled synthesis and post-treatment.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"233 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462210","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}
Pub Date : 2026-03-16DOI: 10.1021/acs.chemmater.5c02810
Yangpil Jang, Seung Min Lee, Kangyong Kim, Anir S. Sharbirin, Seongyeop Lim, Sanghwan Park, Jeongyong Kim, Chang Young Lee, Sang Kyu Kwak, Jongnam Park
Low-dimensional Cu(I)-based metal halides have attracted considerable interest because of their low toxicity, stability, and unique self-trapped exciton (STE)-driven luminescence, with blue-emitting Cs5Cu3Cl6I2 demonstrating considerable potential for next-generation optoelectronics. In this article, we present a seed-mediated anisotropic growth method to synthesize one-dimensional (1D) Cs5Cu3Cl6I2 nanorods (NRs) and examine their polarization-dependent optical behaviors. We achieve NRs with aspect ratios (ARs) exceeding 50 by injecting highly reactive Cs5Cu3Cl6I2 seeds into a ligand solution with a skewed acid-to-amine ratio. These NRs exhibit a remarkable degree of polarization of 0.76 when aligned in thin films, demonstrating a significant anisotropic interaction with linearly polarized light. The effects of the ligand concentration and growth temperature on the NR morphology are explored, and density functional theory calculations are used to clarify the underlying anisotropic growth mechanism. The synthesized Cs5Cu3Cl6I2 NRs demonstrate the potential for optoelectronic applications requiring controlled polarization, such as advanced displays and photonic devices.
{"title":"Seed-Mediated Anisotropic Growth of One-Dimensional Cs5Cu3Cl6I2 Nanorods and Their Polarization-Dependent Optical Response","authors":"Yangpil Jang, Seung Min Lee, Kangyong Kim, Anir S. Sharbirin, Seongyeop Lim, Sanghwan Park, Jeongyong Kim, Chang Young Lee, Sang Kyu Kwak, Jongnam Park","doi":"10.1021/acs.chemmater.5c02810","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02810","url":null,"abstract":"Low-dimensional Cu(I)-based metal halides have attracted considerable interest because of their low toxicity, stability, and unique self-trapped exciton (STE)-driven luminescence, with blue-emitting Cs<sub>5</sub>Cu<sub>3</sub>Cl<sub>6</sub>I<sub>2</sub> demonstrating considerable potential for next-generation optoelectronics. In this article, we present a seed-mediated anisotropic growth method to synthesize one-dimensional (1D) Cs<sub>5</sub>Cu<sub>3</sub>Cl<sub>6</sub>I<sub>2</sub> nanorods (NRs) and examine their polarization-dependent optical behaviors. We achieve NRs with aspect ratios (ARs) exceeding 50 by injecting highly reactive Cs<sub>5</sub>Cu<sub>3</sub>Cl<sub>6</sub>I<sub>2</sub> seeds into a ligand solution with a skewed acid-to-amine ratio. These NRs exhibit a remarkable degree of polarization of 0.76 when aligned in thin films, demonstrating a significant anisotropic interaction with linearly polarized light. The effects of the ligand concentration and growth temperature on the NR morphology are explored, and density functional theory calculations are used to clarify the underlying anisotropic growth mechanism. The synthesized Cs<sub>5</sub>Cu<sub>3</sub>Cl<sub>6</sub>I<sub>2</sub> NRs demonstrate the potential for optoelectronic applications requiring controlled polarization, such as advanced displays and photonic devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"10 5-6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461925","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}
Pub Date : 2026-03-16DOI: 10.1021/acs.chemmater.6c00101
Ya-Ru Kong, Jia-Yi Zhang, Dong-Sheng Shao, Wei Ye, Gang Yang, Qiu Ren, Wei-Hua Ning, Zheng-Fang Tian, Xiao-Ming Ren
Mixed ionic conductors that enable the cooperative transport of multiple charge carriers are essential for advanced solid-state electrochemical devices but remain challenging to realize in crystalline materials. Size-mismatched substitution provides an effective design strategy to promote ionic transport by expanding the lattice and generating an additional interstitial free volume. Guided by this principle, a dual-cation alloying approach is employed to activate coexistence H+/Li+ conduction in a one-dimensional (1D) lead bromide hybrid derived from TBA0.8(H3O)0.2PbBr3 (TBA+ = tetrabutylammonium), a framework intrinsically containing cation vacancies. Partial substitution of Li+ and Mn2+ at the A- and B-sites induces a pronounced size mismatch within the soft hybrid lattice, collectively facilitating ion migration. As a result, the optimized composition (x = 0.134) exhibits a high ionic conductivity of 3.75 × 10–3 S cm–1 at 373 K. This work establishes size-mismatched dual-cation alloying as a general design principle for high-performance mixed ionic conductors in hybrid halides.
混合离子导体能够实现多种载流子的协同传输，这对于先进的固态电化学器件是必不可少的，但在晶体材料中实现仍然具有挑战性。尺寸不匹配取代提供了一种有效的设计策略，通过扩展晶格和产生额外的间隙自由体积来促进离子传输。在这一原理的指导下，采用双阳离子合金化方法激活由TBA0.8(h30)0.2PbBr3 （TBA+ =四丁基铵）衍生的一维（1D）溴化铅杂化物中的共存H+/Li+导电，该框架本质上包含阳离子空位。Li+和Mn2+在A位和b位的部分取代导致软杂化晶格内明显的尺寸不匹配，共同促进离子迁移。结果表明，优化后的组合物（x = 0.134）在373 K时具有3.75 × 10-3 S cm-1的高离子电导率。本工作建立了尺寸不匹配双阳离子合金化作为混合卤化物中高性能混合离子导体的一般设计原则。
{"title":"Size-Mismatched Dual-Cation Alloying for Coexistence H+/Li+ Conduction in Lead Bromide Hybrids","authors":"Ya-Ru Kong, Jia-Yi Zhang, Dong-Sheng Shao, Wei Ye, Gang Yang, Qiu Ren, Wei-Hua Ning, Zheng-Fang Tian, Xiao-Ming Ren","doi":"10.1021/acs.chemmater.6c00101","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c00101","url":null,"abstract":"Mixed ionic conductors that enable the cooperative transport of multiple charge carriers are essential for advanced solid-state electrochemical devices but remain challenging to realize in crystalline materials. Size-mismatched substitution provides an effective design strategy to promote ionic transport by expanding the lattice and generating an additional interstitial free volume. Guided by this principle, a dual-cation alloying approach is employed to activate coexistence H<sup>+</sup>/Li<sup>+</sup> conduction in a one-dimensional (1D) lead bromide hybrid derived from TBA<sub>0.8</sub>(H<sub>3</sub>O)<sub>0.2</sub>PbBr<sub>3</sub> (TBA<sup>+</sup> = tetrabutylammonium), a framework intrinsically containing cation vacancies. Partial substitution of Li<sup>+</sup> and Mn<sup>2+</sup> at the A- and B-sites induces a pronounced size mismatch within the soft hybrid lattice, collectively facilitating ion migration. As a result, the optimized composition (<i>x</i> = 0.134) exhibits a high ionic conductivity of 3.75 × 10<sup>–3</sup> S cm<sup>–1</sup> at 373 K. This work establishes size-mismatched dual-cation alloying as a general design principle for high-performance mixed ionic conductors in hybrid halides.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"77 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461929","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}
Pub Date : 2026-03-16DOI: 10.1021/acs.chemmater.5c02931
Chun Zeng,Wen Luo,Tianle Yu,Ning Qin,Jianqiu Deng,Zhouguang Lu
Graphite is widely used as an anode material in lithium-ion batteries, yet its fast-charging capability is constrained by sluggish Li+ intercalation kinetics. In contrast, graphite can store AlCl4– anions very fast when being considered as electrode for aluminum-ion batteries. However, the mechanism underlying this behavior remains unclear due to the lack of suitable Operando probes. Here, we combine Operando electron paramagnetic resonance (EPR) and Raman spectroscopy to investigate the intercalation of AlCl4– in graphite. Operando Raman confirms the reversible insertion of AlCl4–, establishing the structural basis for comparison with Li+ systems. Operando EPR reveals distinct electronic signatures: unlike the monotonic increase in signal intensity observed in Li+ intercalation, AlCl4– intercalation produces a nonmonotonic evolution. EPR line-shape analysis shows consistently larger A/B ratios in the aluminum-ion system, indicating higher metallicity, enhanced conductivity, and faster electron exchange. These spin-level fingerprints demonstrate that electronic delocalization and spin–orbit interactions contribute to the intrinsic ultrafast kinetics of AlCl4– anion intercalation. Operando EPR thus provides an important electronic probe to track the charge transportation in graphite during ion intercalation and deintercalation and offers new guidance for the design of high-rate aluminum-ion batteries.
{"title":"Spin-Resolved Insights into Fast Al-Ion Intercalation in Graphite via Operando Electron Paramagnetic Resonance Approach in Al Batteries","authors":"Chun Zeng,Wen Luo,Tianle Yu,Ning Qin,Jianqiu Deng,Zhouguang Lu","doi":"10.1021/acs.chemmater.5c02931","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02931","url":null,"abstract":"Graphite is widely used as an anode material in lithium-ion batteries, yet its fast-charging capability is constrained by sluggish Li+ intercalation kinetics. In contrast, graphite can store AlCl4– anions very fast when being considered as electrode for aluminum-ion batteries. However, the mechanism underlying this behavior remains unclear due to the lack of suitable Operando probes. Here, we combine Operando electron paramagnetic resonance (EPR) and Raman spectroscopy to investigate the intercalation of AlCl4– in graphite. Operando Raman confirms the reversible insertion of AlCl4–, establishing the structural basis for comparison with Li+ systems. Operando EPR reveals distinct electronic signatures: unlike the monotonic increase in signal intensity observed in Li+ intercalation, AlCl4– intercalation produces a nonmonotonic evolution. EPR line-shape analysis shows consistently larger A/B ratios in the aluminum-ion system, indicating higher metallicity, enhanced conductivity, and faster electron exchange. These spin-level fingerprints demonstrate that electronic delocalization and spin–orbit interactions contribute to the intrinsic ultrafast kinetics of AlCl4– anion intercalation. Operando EPR thus provides an important electronic probe to track the charge transportation in graphite during ion intercalation and deintercalation and offers new guidance for the design of high-rate aluminum-ion batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462273","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}
Pub Date : 2026-03-16DOI: 10.1021/acs.chemmater.6c00306
Lei Gao, Lexiang Han, Xinyu Xu, Dong Zhang, Ri Peng, Yuxiu Zhong, Xinting Cai, Shuai Yuan
Postsynthetic linker exchange offers a powerful route to functionalize metal–organic frameworks (MOFs), yet its application to robust MOFs is limited by the inertness of high-valent metal–carboxylate bonds. Herein, we report an esterification-assisted linker exchange (EALE) strategy that overcomes this limitation by coupling linker substitution with alcohol-mediated esterification of carboxylate linkers. Using MIL-125(Ti) as a model system, we demonstrate that alcohol solvents (e.g., methanol and ethanol) dramatically enhance the linker exchange rate and ratio compared with conventional solvent-assisted linker exchange in N,N-dimethylformamide. Quantitative NMR analyses reveal that displaced carboxylate linkers undergo preferential esterification, irreversibly removing them from the coordination equilibrium and thereby driving exchange toward high substitution ratios. Control experiments and density functional theory calculations establish that Lewis-acidic metal nodes within the framework catalyze esterification, enabling a cooperative, self-driven process. Importantly, this strategy is generalizable to multiple classes of stable MOFs, including Ti-, Zr-, and Al-based frameworks, and accommodates a wide range of functionalized dicarboxylate linkers. EALE thus provides a general and mechanistically distinct pathway for postsynthetic functionalization of robust MOFs, expanding the scope of linker-exchange chemistry toward highly stable framework materials.
{"title":"Esterification-Assisted Linker Exchange in Robust Metal–Organic Frameworks","authors":"Lei Gao, Lexiang Han, Xinyu Xu, Dong Zhang, Ri Peng, Yuxiu Zhong, Xinting Cai, Shuai Yuan","doi":"10.1021/acs.chemmater.6c00306","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c00306","url":null,"abstract":"Postsynthetic linker exchange offers a powerful route to functionalize metal–organic frameworks (MOFs), yet its application to robust MOFs is limited by the inertness of high-valent metal–carboxylate bonds. Herein, we report an esterification-assisted linker exchange (EALE) strategy that overcomes this limitation by coupling linker substitution with alcohol-mediated esterification of carboxylate linkers. Using MIL-125(Ti) as a model system, we demonstrate that alcohol solvents (e.g., methanol and ethanol) dramatically enhance the linker exchange rate and ratio compared with conventional solvent-assisted linker exchange in <i>N</i>,<i>N</i>-dimethylformamide. Quantitative NMR analyses reveal that displaced carboxylate linkers undergo preferential esterification, irreversibly removing them from the coordination equilibrium and thereby driving exchange toward high substitution ratios. Control experiments and density functional theory calculations establish that Lewis-acidic metal nodes within the framework catalyze esterification, enabling a cooperative, self-driven process. Importantly, this strategy is generalizable to multiple classes of stable MOFs, including Ti-, Zr-, and Al-based frameworks, and accommodates a wide range of functionalized dicarboxylate linkers. EALE thus provides a general and mechanistically distinct pathway for postsynthetic functionalization of robust MOFs, expanding the scope of linker-exchange chemistry toward highly stable framework materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"12 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466048","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}
Pub Date : 2026-03-16DOI: 10.1021/acs.chemmater.5c02703
Srayee Mandal, Santanu Bhattacharyya
Carbon dots (CDs) have emerged as a recent class of luminescent nanomaterials due to their unique photoluminescence properties and biocompatible nature. Despite extensive studies on their photophysical properties, the photocatalytic activity of CDs, especially the crucial role of heteroatom functionality in governing their optoelectronic properties, has not been explored much. This perspective highlights recent advances in the photocatalytic activity of heteroatom functionalized luminescent CDs especially for green H2 production. Incorporation of heteroatom functionalities (e.g., N, P, B, S, etc.) in CDs can modulate the optoelectronic features of CDs, enhancing visible light absorption and promoting photogenerated charge separation. Furthermore, rational tuning of the heteroatom functionalities improves the catalytically active sites and selective photoinduced free carrier accumulation on CDs’ surface which are essential for photocatalysis. Consequently, a traditional metal cocatalyst can be replaced simply by a heteroatom functionality in CDs which can enable simultaneous oxidative and reductive half-reactions without the need for complex heterojunction architectures, which is the major bottleneck for conventional photocatalytic systems. Overall, the present perspective demonstrates those above-mentioned strategies in detail along with the current challenges and future prospects of CDs as sole photocatalysts especially for photocatalytic green H2 production.
{"title":"Unveiling the Photocatalytic Potential of Heteroatom-Rich Luminescent Carbon Dots for Green H2 Production","authors":"Srayee Mandal, Santanu Bhattacharyya","doi":"10.1021/acs.chemmater.5c02703","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02703","url":null,"abstract":"Carbon dots (CDs) have emerged as a recent class of luminescent nanomaterials due to their unique photoluminescence properties and biocompatible nature. Despite extensive studies on their photophysical properties, the photocatalytic activity of CDs, especially the crucial role of heteroatom functionality in governing their optoelectronic properties, has not been explored much. This perspective highlights recent advances in the photocatalytic activity of heteroatom functionalized luminescent CDs especially for green H<sub>2</sub> production. Incorporation of heteroatom functionalities (<i>e.g.,</i> N, P, B, S, etc.) in CDs can modulate the optoelectronic features of CDs, enhancing visible light absorption and promoting photogenerated charge separation. Furthermore, rational tuning of the heteroatom functionalities improves the catalytically active sites and selective photoinduced free carrier accumulation on CDs’ surface which are essential for photocatalysis. Consequently, a traditional metal cocatalyst can be replaced simply by a heteroatom functionality in CDs which can enable simultaneous oxidative and reductive half-reactions without the need for complex heterojunction architectures, which is the major bottleneck for conventional photocatalytic systems. Overall, the present perspective demonstrates those above-mentioned strategies in detail along with the current challenges and future prospects of CDs as sole photocatalysts especially for photocatalytic green H<sub>2</sub> production.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"273 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466047","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}
Pub Date : 2026-03-16DOI: 10.1021/acs.chemmater.5c02921
Magnus Nørgaard Kløve,Andreas Dueholm Bertelsen,Nikolaos Antonios Iakynthos Nemet,Bo Brummerstedt Iversen
Zirconium dioxide (ZrO2) is widely used as a structural ceramic and in various technological applications, where performance often depends on stabilizing the high-temperature t-ZrO2 phase under ambient conditions. However, green synthesis routes using benign precursors typically yield phase mixtures dominated by the thermodynamically stable m-ZrO2 phase. Here, in situ X-ray scattering is used to investigate the solvothermal synthesis of ZrO2 nanoparticles across different solvents (methanol, ethanol, 2-propanol, ethylene glycol, and water) and temperatures (150–400 °C). The metastable t-ZrO2 phase forms initially as a kinetic phase in all syntheses except water before the transition into the m-ZrO2 phase in a solid-state transformation. The conditions required to isolate a phase-pure t-ZrO2 product are established, demonstrating the in situ solvothermal synthesis as an efficient screening tool. Ex situ continuous-flow solvothermal synthesis is then employed to reproduce the required conditions, enabling the isolation of phase-pure t-ZrO2. Continuous flow solvothermal synthesis is an efficient green method for production of nanoparticles, and the fast heating rate and flexible design provide versatility to reach the short reaction time required in this case.
{"title":"In Situ X-ray Scattering Guided Polymorphism Control in ZrO2 Nanoparticle Synthesis","authors":"Magnus Nørgaard Kløve,Andreas Dueholm Bertelsen,Nikolaos Antonios Iakynthos Nemet,Bo Brummerstedt Iversen","doi":"10.1021/acs.chemmater.5c02921","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02921","url":null,"abstract":"Zirconium dioxide (ZrO2) is widely used as a structural ceramic and in various technological applications, where performance often depends on stabilizing the high-temperature t-ZrO2 phase under ambient conditions. However, green synthesis routes using benign precursors typically yield phase mixtures dominated by the thermodynamically stable m-ZrO2 phase. Here, in situ X-ray scattering is used to investigate the solvothermal synthesis of ZrO2 nanoparticles across different solvents (methanol, ethanol, 2-propanol, ethylene glycol, and water) and temperatures (150–400 °C). The metastable t-ZrO2 phase forms initially as a kinetic phase in all syntheses except water before the transition into the m-ZrO2 phase in a solid-state transformation. The conditions required to isolate a phase-pure t-ZrO2 product are established, demonstrating the in situ solvothermal synthesis as an efficient screening tool. Ex situ continuous-flow solvothermal synthesis is then employed to reproduce the required conditions, enabling the isolation of phase-pure t-ZrO2. Continuous flow solvothermal synthesis is an efficient green method for production of nanoparticles, and the fast heating rate and flexible design provide versatility to reach the short reaction time required in this case.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"17 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462311","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}
Pub Date : 2026-03-15DOI: 10.1021/acs.chemmater.5c02731
Jordan Ackley,Ariel E. Briggs,Karthik Chinnathambi,Nicholas McKibben,Cadré Francis,Josh Eixenberger,Tony Valayil Varghese,David Estrada
Binary pnictogen chalcogen compounds, primarily bismuth tellurides and selenides, are of great interest due to their applications in emerging quantum devices, as well as thermoelectric generators. The performance of bismuth telluride in these roles depends on its structure at the nanoscale, particularly the size, shape, and crystallinity of its nanocrystalline forms. However, current methods for controlling these features are often slow, inconsistent, or difficult to scale. Here, we demonstrate that through a solvothermal synthesis and hot injection process, precise control over the morphology of bismuth telluride nanoplates is possible with independent tuning of process variables, such as temperature and reaction time. We find that the nanoplate shape and internal porosity vary systematically with synthesis temperature and that the same morphological outcomes can be rapidly achieved at a fixed temperature by adjusting reaction duration. These results reveal that both the temperature and time can independently direct bismuth telluride morphological features, allowing for rapid, tunable synthesis strategies. Our approach offers a scalable framework, not only for bismuth telluride but also for related layered chalcogenides used in energy harvesting and quantum technologies.
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Development of highly efficient nonprecious metal-based oxygen reduction catalysts, capable of operating within a broad pH range, has remained a great challenge in electrocatalysis. Herein, ultramicroporous carbon aerogel-supported iron single-atom catalysts (MPCA/Fe) are synthesized using a chitosan hydrogel precursor, with zinc species acting as a sacrificial template. Structural characterizations reveal that the produced ultramicropores effectively facilitate the anchoring of Fe single atoms within the carbon aerogel. The resulting MPCA/Fe composites exhibit a remarkable activity and stability toward the oxygen reduction reaction, featuring a half-wave potential of +0.93, +0.82, and +0.79 V in alkaline, neutral, and acidic media, respectively. Computational studies based on density functional theory calculations indicate that FeN4 sites embedded within the ultramicropores possess moderate *OH adsorption energy, leading to excellent catalytic performance. As MPCA/Fe also exhibits apparent electrocatalytic activity towards the oxygen evolution reaction, a zinc–air battery is assembled with the MPCA/Fe as the cathode catalyst, which delivers an open-circuit voltage (OCV) of 1.50 V and a peak power density of 240.8 mW cm–2 and excellent durability during 1600 charge–discharge cycles. When MPCA/Fe is assembled into an acid/alkali-mixed zinc–air battery, the device enables an exceptionally high OCV of 2.20 V and a discharge voltage of 2.07 V at a current density of 5 mA cm–2. Results from this study offer an effective strategy for the development of high-performance pH-universal oxygen reduction electrocatalysts.
开发能在较宽pH范围内工作的高效非贵金属基氧还原催化剂一直是电催化领域的一大挑战。本文以壳聚糖水凝胶为前驱体，锌作为牺牲模板，合成了超微孔碳气凝胶负载铁单原子催化剂（MPCA/Fe）。结构表征表明，生成的超微孔有效地促进了铁单原子在碳气凝胶中的锚定。制备的MPCA/Fe复合材料在碱性、中性和酸性介质中的半波电位分别为+0.93、+0.82和+0.79 V，表现出良好的氧还原活性和稳定性。基于密度泛函理论计算的计算研究表明，嵌入在超微孔中的FeN4位点具有中等的*OH吸附能，具有优异的催化性能。由于MPCA/Fe对析氧反应也表现出明显的电催化活性，因此以MPCA/Fe作为阴极催化剂组装锌空气电池，其开路电压（OCV）为1.50 V，峰值功率密度为240.8 mW cm-2，在1600次充放电循环中具有优异的耐久性。当MPCA/Fe组装成酸/碱混合锌-空气电池时，该器件在电流密度为5 mA cm-2的情况下可实现2.20 V的超高OCV和2.07 V的放电电压。研究结果为开发高性能的ph -通用氧还原电催化剂提供了有效的策略。
{"title":"Ultramicroporous Carbon Aerogel-Supported Iron Single-Atom Catalysts Toward Efficient pH-Universal Oxygen Reduction and Acidic/Alkaline Zinc–Air Batteries","authors":"Dahai Xu, Haizhong Dai, Jingjing Liu, Jiahui Zhang, Josue Pizano, Shaowei Chen, Ting He","doi":"10.1021/acs.chemmater.5c03104","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03104","url":null,"abstract":"Development of highly efficient nonprecious metal-based oxygen reduction catalysts, capable of operating within a broad pH range, has remained a great challenge in electrocatalysis. Herein, ultramicroporous carbon aerogel-supported iron single-atom catalysts (MPCA/Fe) are synthesized using a chitosan hydrogel precursor, with zinc species acting as a sacrificial template. Structural characterizations reveal that the produced ultramicropores effectively facilitate the anchoring of Fe single atoms within the carbon aerogel. The resulting MPCA/Fe composites exhibit a remarkable activity and stability toward the oxygen reduction reaction, featuring a half-wave potential of +0.93, +0.82, and +0.79 V in alkaline, neutral, and acidic media, respectively. Computational studies based on density functional theory calculations indicate that FeN<sub>4</sub> sites embedded within the ultramicropores possess moderate *OH adsorption energy, leading to excellent catalytic performance. As MPCA/Fe also exhibits apparent electrocatalytic activity towards the oxygen evolution reaction, a zinc–air battery is assembled with the MPCA/Fe as the cathode catalyst, which delivers an open-circuit voltage (OCV) of 1.50 V and a peak power density of 240.8 mW cm<sup>–2</sup> and excellent durability during 1600 charge–discharge cycles. When MPCA/Fe is assembled into an acid/alkali-mixed zinc–air battery, the device enables an exceptionally high OCV of 2.20 V and a discharge voltage of 2.07 V at a current density of 5 mA cm<sup>–2</sup>. Results from this study offer an effective strategy for the development of high-performance pH-universal oxygen reduction electrocatalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147448272","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}
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