Chemistry of Materials最新文献

{"title":"Surface Exciton Polariton in Cesium Lead Halide Perovskites","authors":"Jason Hao, Jeffrey Owrutsky, Daniel C. Ratchford, Blake Simpkins, Alexander L. Efros","doi":"10.1021/acs.chemmater.4c03262","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03262","url":null,"abstract":"In this article, we developed a theory describing surface exciton polaritons (SEPs) that accounts for the spatial dispersion of the dielectric constant connected with exciton momentum. Due to strong coupling between light and bulk excitons in the frequency separation, ℏω_LT, between the longitudinal and transverse excitons, the SEP is formed and behaves as partially light and partially matter. The dispersion of the SEP was found through a combined solution of Maxwell’s and Thomas-Hopfield’s equations. The analytical theory describes SEPs at any bulk exciton/vacuum interface and provides its complete dispersion if one knows ℏω_LT, the exciton effective mass, <i>M</i>, and the high-frequency dielectric constant, κ_∞. The presented theory is in excellent agreement with the only numerical modeling of this problem, which was conducted for SEPs at a ZnO/vacuum interface. Calculations show the spatial dispersion of the dielectric constant leads to rather small broadening of the photon-like quasi-particle and suggest using SEPs for long-range coherence transfer. The theory was used to describe SEP dispersion in CsPbCl₃ and CsPbBr₃ perovskites.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"91 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phosphorus Substitution in Li3VO4 Anode: Investigating Polymorphic Stability and Unconventional Redox Potential Modulation","authors":"Keisuke Matsumura*,&nbsp;Patrick Rozier,&nbsp;Taro Matsuura,&nbsp;Etsuro Iwama*,&nbsp;Wako Naoi,&nbsp;Patrice Simon and Katsuhiko Naoi*,&nbsp;","doi":"10.1021/acs.chemmater.5c0012310.1021/acs.chemmater.5c00123","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00123https://doi.org/10.1021/acs.chemmater.5c00123","url":null,"abstract":"<p >This study provides an in-depth investigation into the interplay between crystal polymorphs and phosphorus (P) substitution in wurtzite-type Li₃V_1–<i>x</i>P_<i>x</i>O₄ (LVPO), focusing on how crystal phase and P-substitution effects can be independently optimized to enhance electrochemical properties as anodes in lithium-ion based energy storage systems. Through precise control of the cooling rate after high-temperature synthesis, both β- and γ-phase LVPO can be reproducibly synthesized with identical P content. Powder X-ray diffraction (XRD) and in situ XRD analyses reveal that increasing P content results in a progressive stabilization of the γ-phase, demonstrating the pivotal role of P-substitution in altering the crystal structure. Electrochemical characterizations confirm that both β- and γ-LVPO exhibits smooth, single-phase (solid-solution-type) Li⁺ de/intercalation without undergoing any phase transition, a key feature that differentiates it from nonsubstituted β-Li₃VO₄. Galvanostatic intermittent titration technique (GITT) measurements show that the Li-ion diffusion coefficients follow opposing trends in β- and γ-LVPO as P content increases, providing a clear explanation for the superior rate capabilities observed in γ-LVPO. In addition, the study highlights an intriguing finding: P-substitution lowers the electrochemical redox potential, counteracting the conventional inductive effect typically reported in phosphate-based materials, thus revealing a novel mechanism by which redox behavior is sensitively influenced by local crystal environments. This work significantly advances the fundamental understanding of structure–property relationships in wurtzite-type materials, particularly in relation to how P-substitution and crystal phase transitions can optimize electrode performance. Moreover, the findings emphasize the potential of compositional and crystallographic tuning as a powerful strategy to develop high-rate anode materials with enhanced stability, improved Li⁺ diffusion, and controlled redox behavior, ultimately paving the way for the design of more efficient, stable, and high-rate lithium-ion energy systems.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2325–2338 2325–2338"},"PeriodicalIF":7.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phosphorus Substitution in Li3VO4 Anode: Investigating Polymorphic Stability and Unconventional Redox Potential Modulation","authors":"Keisuke Matsumura, Patrick Rozier, Taro Matsuura, Etsuro Iwama, Wako Naoi, Patrice Simon, Katsuhiko Naoi","doi":"10.1021/acs.chemmater.5c00123","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00123","url":null,"abstract":"This study provides an in-depth investigation into the interplay between crystal polymorphs and phosphorus (P) substitution in wurtzite-type Li₃V_1–<i>x</i>P_<i>x</i>O₄ (LVPO), focusing on how crystal phase and P-substitution effects can be independently optimized to enhance electrochemical properties as anodes in lithium-ion based energy storage systems. Through precise control of the cooling rate after high-temperature synthesis, both β- and γ-phase LVPO can be reproducibly synthesized with identical P content. Powder X-ray diffraction (XRD) and in situ XRD analyses reveal that increasing P content results in a progressive stabilization of the γ-phase, demonstrating the pivotal role of P-substitution in altering the crystal structure. Electrochemical characterizations confirm that both β- and γ-LVPO exhibits smooth, single-phase (solid-solution-type) Li⁺ de/intercalation without undergoing any phase transition, a key feature that differentiates it from nonsubstituted β-Li₃VO₄. Galvanostatic intermittent titration technique (GITT) measurements show that the Li-ion diffusion coefficients follow opposing trends in β- and γ-LVPO as P content increases, providing a clear explanation for the superior rate capabilities observed in γ-LVPO. In addition, the study highlights an intriguing finding: P-substitution lowers the electrochemical redox potential, counteracting the conventional inductive effect typically reported in phosphate-based materials, thus revealing a novel mechanism by which redox behavior is sensitively influenced by local crystal environments. This work significantly advances the fundamental understanding of structure–property relationships in wurtzite-type materials, particularly in relation to how P-substitution and crystal phase transitions can optimize electrode performance. Moreover, the findings emphasize the potential of compositional and crystallographic tuning as a powerful strategy to develop high-rate anode materials with enhanced stability, improved Li⁺ diffusion, and controlled redox behavior, ultimately paving the way for the design of more efficient, stable, and high-rate lithium-ion energy systems.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"3 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570041","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impact of SO2 on NiFe Nanoparticle Exsolution and Dissolution from LaFe0.9Ni0.1O3 Perovskite Oxides","authors":"Musa Najimu, Matthew J. Hurlock, Sahanaz Parvin, Courtney Brea, Neelesh Kumar, Yoon Jin Cho, Yiqing Wu, Guoxiang Hu, Zili Wu, Eranda Nikolla, Jonas Baltrusaitis, Tina M. Nenoff, Israel E. Wachs, Kandis Leslie Gilliard-AbdulAziz","doi":"10.1021/acs.chemmater.4c03439","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03439","url":null,"abstract":"Ni-doped LaFeO₃ perovskite oxide is a promising cathode material for solid oxide electrolysis cells (SOECs) designed for CO₂/H₂O coelectrolysis. The performance of LaFe_0.9Ni_0.1O₃ is being investigated under real-world conditions that include exposure to acid gases, such as SO₂, relevant to SOEC operation. Experiments show that LaFe_0.9Ni_0.1O₃ exsolves NiFe nanoparticles, along with the formation of surface SO₄^2– and SO₃^2– after being exposed to 200 ppm of SO₂. This suggests that the ionic diffusion of Ni³⁺ and Fe³⁺ between the bulk and the surface remains unaffected throughout the exsolution–dissolution–exsolution cycle. Thermochemical water splitting has been employed as a probe reaction to evaluate the catalytic properties of the exsolved NiFe nanoparticles. These nanoparticles demonstrated improved hydrogen production compared to bare perovskite oxide substrates. However, after exposure to SO₂, the formation of Fe-rich NiFe nanoparticles led to poor thermocatalytic performance and rapid deactivation of the perovskite at elevated temperatures. Density functional theory (DFT) analysis was utilized to validate the experimental findings, indicating a significantly negative reaction energy for water splitting over exsolved Fe, as well as stronger binding of SO₂ to Fe than to Ni. Computational analysis further suggests that the presence of surface sulfate promotes the formation of Fe-rich NiFe nanoparticles, aligning with the experimental results. Overall, this study clarifies how SO₂ affects the structure of SOEC perovskite oxide candidate materials. Future engineering efforts should focus on enhancing nanoparticle exsolution and sulfur resistance, which is crucial for improving the hydrogen production capacity of La-based perovskite oxides for electro- and thermocatalytic water splitting in real environments containing acid gases.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"18 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561164","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impact of SO2 on NiFe Nanoparticle Exsolution and Dissolution from LaFe0.9Ni0.1O3 Perovskite Oxides","authors":"Musa Najimu,&nbsp;Matthew J. Hurlock,&nbsp;Sahanaz Parvin,&nbsp;Courtney Brea,&nbsp;Neelesh Kumar,&nbsp;Yoon Jin Cho,&nbsp;Yiqing Wu,&nbsp;Guoxiang Hu,&nbsp;Zili Wu,&nbsp;Eranda Nikolla,&nbsp;Jonas Baltrusaitis,&nbsp;Tina M. Nenoff,&nbsp;Israel E. Wachs and Kandis Leslie Gilliard-AbdulAziz*,&nbsp;","doi":"10.1021/acs.chemmater.4c0343910.1021/acs.chemmater.4c03439","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03439https://doi.org/10.1021/acs.chemmater.4c03439","url":null,"abstract":"<p >Ni-doped LaFeO₃ perovskite oxide is a promising cathode material for solid oxide electrolysis cells (SOECs) designed for CO₂/H₂O coelectrolysis. The performance of LaFe_0.9Ni_0.1O₃ is being investigated under real-world conditions that include exposure to acid gases, such as SO₂, relevant to SOEC operation. Experiments show that LaFe_0.9Ni_0.1O₃ exsolves NiFe nanoparticles, along with the formation of surface SO₄^2– and SO₃^2– after being exposed to 200 ppm of SO₂. This suggests that the ionic diffusion of Ni³⁺ and Fe³⁺ between the bulk and the surface remains unaffected throughout the exsolution–dissolution–exsolution cycle. Thermochemical water splitting has been employed as a probe reaction to evaluate the catalytic properties of the exsolved NiFe nanoparticles. These nanoparticles demonstrated improved hydrogen production compared to bare perovskite oxide substrates. However, after exposure to SO₂, the formation of Fe-rich NiFe nanoparticles led to poor thermocatalytic performance and rapid deactivation of the perovskite at elevated temperatures. Density functional theory (DFT) analysis was utilized to validate the experimental findings, indicating a significantly negative reaction energy for water splitting over exsolved Fe, as well as stronger binding of SO₂ to Fe than to Ni. Computational analysis further suggests that the presence of surface sulfate promotes the formation of Fe-rich NiFe nanoparticles, aligning with the experimental results. Overall, this study clarifies how SO₂ affects the structure of SOEC perovskite oxide candidate materials. Future engineering efforts should focus on enhancing nanoparticle exsolution and sulfur resistance, which is crucial for improving the hydrogen production capacity of La-based perovskite oxides for electro- and thermocatalytic water splitting in real environments containing acid gases.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2268–2280 2268–2280"},"PeriodicalIF":7.2,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678508","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Metal-Free Nanozyme-Hydrogel Enabled by Conductive Polymer Nanofibers for Multimodal Antibacterial Therapy","authors":"Wenya Xu, Ziyi Zhu, Zhen Tan, Ziteng Fan, Shibing Wei, Kaili Yang, Lihui Yuwen, Wen Jing Yang, En-Tang Kang, Lianhui Wang","doi":"10.1021/acs.chemmater.4c02480","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02480","url":null,"abstract":"The nanozyme antibacterial materials have been of great interest due to their broad-spectrum activity and minimal drug resistance. A variety of metal-based nanozymes have been designed as bactericidal agents, whereas their biosafety issues are still serious concerns. Accordingly, the development of metal-free nanozymes and the corresponding hydrogel dressings is of great importance for antibacterial applications. Herein, a classical conductive polymer, polyaniline nanofibers (PANI NF), has been developed as a three-pronged metal-free enzyme-like antibacterial material. They exhibited high oxidase-like and peroxidase-like activities for reactive oxygen species (ROS) production, positively charged surfaces capable of capturing/trapping bacteria to reduce ROS diffusion distance, and unique photothermal ablation effect. By harnessing the intrinsic merits of PANI NF, a PANI/poly(vinyl alcohol) (PANI/PVA) nanocomposite hydrogel, with high stability, soft-tissue adhesion properties, self-healing capability, remoldability, and biocompatibility, has been fabricated as biomedical dressings to promote bacteria-infected wound healing. The studies on antibacterial activities of polyaniline nanofibers shed light on the conductive polymer as promising metal-free enzyme-like antibacterial materials. The prepared PANI/PVA hydrogel provides a stable hydrogel dressing without toxic metal leakage for biomedical applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"24 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538809","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Twist-Induced Dimensional Crossover and Topological Phase Transitions in Bismuthene Quasicrystals","authors":"Sang Wook Han, Won Seok Yun, Gi-Beom Cha, Seungho Seong, Jong Chan Kim, Hu Young Jeong, Chang Won Ahn, Keisuke Fukutani, Roland Stania, Jeongsoo Kang","doi":"10.1021/acs.chemmater.5c00204","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00204","url":null,"abstract":"Twisted bismuthene homojunctions, comprised of a Bi(111) bilayer atop two Bi(110) monolayers, exhibit a distinct growth orientation that is facilitated by self-assembly. Our cross-sectional structural analysis reveals an unexpected growth alignment of Bi(110) layers on transition-metal dichalcogenides, deviating from the anticipated Bi(111) bilayer structure. This self-assembly process, driven by the crystal symmetry interplay, induces a topological phase transition beyond a critical thickness. The dimensional crossover in the Fermi surfaces marks the electronic transition from two-dimensional (2D) Bi(110) to 1D Bi(111) quasicrystals. Additionally, the emergence of the topologically nontrivial band structures, an enhanced 1D carrier density, and a metal–insulator transition through band inversion indicate that the twisted bismuthene quasicrystals are promising candidates for higher-order topological quasicrystalline insulators. These findings pave the way for low-resistance contacts in 2D transistors, advancing the development of next-generation electronic devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Twist-Induced Dimensional Crossover and Topological Phase Transitions in Bismuthene Quasicrystals","authors":"Sang Wook Han*,&nbsp;Won Seok Yun,&nbsp;Gi-Beom Cha,&nbsp;Seungho Seong,&nbsp;Jong Chan Kim,&nbsp;Hu Young Jeong*,&nbsp;Chang Won Ahn,&nbsp;Keisuke Fukutani,&nbsp;Roland Stania and Jeongsoo Kang,&nbsp;","doi":"10.1021/acs.chemmater.5c0020410.1021/acs.chemmater.5c00204","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00204https://doi.org/10.1021/acs.chemmater.5c00204","url":null,"abstract":"<p >Twisted bismuthene homojunctions, comprised of a Bi(111) bilayer atop two Bi(110) monolayers, exhibit a distinct growth orientation that is facilitated by self-assembly. Our cross-sectional structural analysis reveals an unexpected growth alignment of Bi(110) layers on transition-metal dichalcogenides, deviating from the anticipated Bi(111) bilayer structure. This self-assembly process, driven by the crystal symmetry interplay, induces a topological phase transition beyond a critical thickness. The dimensional crossover in the Fermi surfaces marks the electronic transition from two-dimensional (2D) Bi(110) to 1D Bi(111) quasicrystals. Additionally, the emergence of the topologically nontrivial band structures, an enhanced 1D carrier density, and a metal–insulator transition through band inversion indicate that the twisted bismuthene quasicrystals are promising candidates for higher-order topological quasicrystalline insulators. These findings pave the way for low-resistance contacts in 2D transistors, advancing the development of next-generation electronic devices.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2358–2366 2358–2366"},"PeriodicalIF":7.2,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Metal-Free Nanozyme-Hydrogel Enabled by Conductive Polymer Nanofibers for Multimodal Antibacterial Therapy","authors":"Wenya Xu,&nbsp;Ziyi Zhu,&nbsp;Zhen Tan,&nbsp;Ziteng Fan,&nbsp;Shibing Wei,&nbsp;Kaili Yang,&nbsp;Lihui Yuwen,&nbsp;Wen Jing Yang*,&nbsp;En-Tang Kang* and Lianhui Wang*,&nbsp;","doi":"10.1021/acs.chemmater.4c0248010.1021/acs.chemmater.4c02480","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02480https://doi.org/10.1021/acs.chemmater.4c02480","url":null,"abstract":"<p >The nanozyme antibacterial materials have been of great interest due to their broad-spectrum activity and minimal drug resistance. A variety of metal-based nanozymes have been designed as bactericidal agents, whereas their biosafety issues are still serious concerns. Accordingly, the development of metal-free nanozymes and the corresponding hydrogel dressings is of great importance for antibacterial applications. Herein, a classical conductive polymer, polyaniline nanofibers (PANI NF), has been developed as a three-pronged metal-free enzyme-like antibacterial material. They exhibited high oxidase-like and peroxidase-like activities for reactive oxygen species (ROS) production, positively charged surfaces capable of capturing/trapping bacteria to reduce ROS diffusion distance, and unique photothermal ablation effect. By harnessing the intrinsic merits of PANI NF, a PANI/poly(vinyl alcohol) (PANI/PVA) nanocomposite hydrogel, with high stability, soft-tissue adhesion properties, self-healing capability, remoldability, and biocompatibility, has been fabricated as biomedical dressings to promote bacteria-infected wound healing. The studies on antibacterial activities of polyaniline nanofibers shed light on the conductive polymer as promising metal-free enzyme-like antibacterial materials. The prepared PANI/PVA hydrogel provides a stable hydrogel dressing without toxic metal leakage for biomedical applications.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2106–2124 2106–2124"},"PeriodicalIF":7.2,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Confined Palladium Nanocrystals within Covalent Organic Framework-Intercalated MXene Nanoarchitectures toward Highly Efficient Methanol Electrooxidation","authors":"Lan Yue, Quanguo Jiang, Le Ma, Yanan Li, Lu Yang, Jian Zhang, Haiyan He, Huajie Huang","doi":"10.1021/acs.chemmater.4c02659","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02659","url":null,"abstract":"The rational design of high-performance electrocatalysts toward the methanol oxidation reaction plays a noticeable role in the progress of stimulating the industrial development of direct methanol fuel cells. In this study, ultrafine palladium nanocrystals are <i>in situ</i> confined within the hydrazone-linked covalent organic framework (COF-42)-intercalated Ti₃C₂T_<i>x</i> MXene nanoarchitectures (Pd/COF-MX) through a facile and robust stereoconstruction strategy. The existence of hydrangea-shaped COF-42 with abundant N species makes it possible to optimize the coordination environments for Pd nanocrystals to facilitate their size confinement and homogeneous dispersion, while the MXene nanosheets afford strong electronic interactions and contemporaneously reduce the overall charge-transfer resistance of the hybrid catalyst. As a result, the emerging Pd/COF-MX nanoarchitectures demonstrate a preferable catalytic methanol electrooxidation performance with an extensive electrochemically active surface area, superior mass activity, and dependable long-term stability, significantly outperforming the conventional Pd/carbon black, Pd/carbon nanotube, Pd/reduced graphene oxide, and Pd/MXene catalysts. Density functional theory simulation additionally discloses that the functionalization of COF-42 enables a stronger atomic interaction with the Pd component, which induces an obvious left shift of its d-band center and leads to a weaker adsorption ability toward the CO molecule.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"46 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538852","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}