This study presents the successful synthesis of highly hierarchical ZnMn2O4 microspheres (HZM) through the self-assembly of nanoparticle arrays. HZM was prepared using a one-step hydrothermal method, without the use of sacrificial agents or templates, at three different hydrothermal times (20, 40, and 72 h). Increasing the hydrothermal time to more than 20 h resulted in the formation of well-defined hierarchically hollow microspheres. Analysis confirmed the proper crystallinity and phase purity of HZM, with regular nanoparticles arranged on their surface in a stacked configuration resembling a hedgehog shape. The photocatalytic characteristics of HZM were assessed through an investigation into the degradation of methylene blue (MB) under visible light. Among the synthesized HZMs, those processed for a duration of 72 h (HZM3) demonstrated an enhanced specific surface area and a reduced recombination rate of photogenerated electron-hole pairs. This improvement has garnered significant attention, resulting in the most effective photocatalytic oxidation of MB (>80 %) achieved within 180 min. The comprehensive evaluation and analysis of the photocatalytic properties of the synthesized hollow microspheres were conducted. The durability and stability of HZM3 in the tricycle indicate that these as-synthesized microspheres can serve as durable photocatalysts for the degradation of organic dye molecules.
{"title":"ZnMn2O4 hierarchical hollow Self-Assembly microspheres Bearing enhanced photocatalytic activity under visible light","authors":"Zivar Azmoodeh , Hossain Milani Moghaddam , Shahruz Nasirian , Alireza Soltani","doi":"10.1016/j.mseb.2025.118194","DOIUrl":"10.1016/j.mseb.2025.118194","url":null,"abstract":"<div><div>This study presents the successful synthesis of highly hierarchical ZnMn<sub>2</sub>O<sub>4</sub> microspheres (HZM) through the self-assembly of nanoparticle arrays. HZM was prepared using a one-step hydrothermal method, without the use of sacrificial agents or templates, at three different hydrothermal times (20, 40, and 72 h). Increasing the hydrothermal time to more than 20 h resulted in the formation of well-defined hierarchically hollow microspheres. Analysis confirmed the proper crystallinity and phase purity of HZM, with regular nanoparticles arranged on their surface in a stacked configuration resembling a hedgehog shape. The photocatalytic characteristics of HZM were assessed through an investigation into the degradation of methylene blue (MB) under visible light. Among the synthesized HZMs, those processed for a duration of 72 h (HZM3) demonstrated an enhanced specific surface area and a reduced recombination rate of photogenerated electron-hole pairs. This improvement has garnered significant attention, resulting in the most effective photocatalytic oxidation of MB (>80 %) achieved within 180 min. The comprehensive evaluation and analysis of the photocatalytic properties of the synthesized hollow microspheres were conducted. The durability and stability of HZM3 in the tricycle indicate that these as-synthesized microspheres can serve as durable photocatalysts for the degradation of organic dye molecules.</div></div>","PeriodicalId":18233,"journal":{"name":"Materials Science and Engineering: B","volume":"317 ","pages":"Article 118194"},"PeriodicalIF":3.9,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Graphitic carbon nitride (g-C3N4), as a fascinating polymeric lamellar semiconductor, has garnered substantial attention in the photocatalytic field benefiting from its non-toxicity, cost-effectiveness, and suitable bandgap. Generally, a thermal polymerization method is utilized to prepare the conventional g-C3N4 by using the various organic precursors. However, the traditional g-C3N4 usually displays low crystallinity and inadequate surface-active centers, leading to the fast recombination of photoinduced charges and poor interfacial reaction efficiency, which can severely restrict its photocatalytic performance. Recently, to overcome these drawbacks, increasing the crystallinity and anchoring metal single atoms emerge as the serviceable strategies to effectively boost the flow and separation of photogenerated charges and provide surface-active centers for improving the photocatalytic activity. Herein, this review outlines the current advancements in various metal-single-atom anchored highly crystalline g-C3N4 (MSA-HCCN) photocatalysts, involving the Cu, Co, Fe, Mg, Mn, Pt, Au, Ni, and others. Initially, the features of highly crystalline g-C3N4 (HCCN) are meticulously presented compared to traditional g-C3N4. Second, the typical characteristics of MSA-HCCN photocatalysts are systematically emphasized. Subsequently, various synthetic methods of MSA-HCCN photocatalysts are presented in detail, containing the calcination method, ion exchange method, and freezing-assisted photodeposition method. After that, the photocatalytic applications of MSA-HCCN are described, encompassing energy photocatalysis (H2 evolution, H2O2 production, etc.), environmental photocatalysis (CO2 reduction, pollutant degradation, etc.), and organic synthesis (CH4 oxidation, alkylaromatic oxidation, etc.). Lastly, the perspectives of MSA-HCCN photocatalysts are described to supply new thoughts for boosting their further development.
{"title":"Metal-single-atom anchored highly crystalline graphitic carbon nitride in photocatalysis","authors":"Binbin Zhao, Jiachao Xu, Feng Chen, Xuefei Wang, Huogen Yu","doi":"10.1016/j.jmst.2024.12.084","DOIUrl":"https://doi.org/10.1016/j.jmst.2024.12.084","url":null,"abstract":"Graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>), as a fascinating polymeric lamellar semiconductor, has garnered substantial attention in the photocatalytic field benefiting from its non-toxicity, cost-effectiveness, and suitable bandgap. Generally, a thermal polymerization method is utilized to prepare the conventional g-C<sub>3</sub>N<sub>4</sub> by using the various organic precursors. However, the traditional g-C<sub>3</sub>N<sub>4</sub> usually displays low crystallinity and inadequate surface-active centers, leading to the fast recombination of photoinduced charges and poor interfacial reaction efficiency, which can severely restrict its photocatalytic performance. Recently, to overcome these drawbacks, increasing the crystallinity and anchoring metal single atoms emerge as the serviceable strategies to effectively boost the flow and separation of photogenerated charges and provide surface-active centers for improving the photocatalytic activity. Herein, this review outlines the current advancements in various metal-single-atom anchored highly crystalline g-C<sub>3</sub>N<sub>4</sub> (MSA-HCCN) photocatalysts, involving the Cu, Co, Fe, Mg, Mn, Pt, Au, Ni, and others. Initially, the features of highly crystalline g-C<sub>3</sub>N<sub>4</sub> (HCCN) are meticulously presented compared to traditional g-C<sub>3</sub>N<sub>4</sub>. Second, the typical characteristics of MSA-HCCN photocatalysts are systematically emphasized. Subsequently, various synthetic methods of MSA-HCCN photocatalysts are presented in detail, containing the calcination method, ion exchange method, and freezing-assisted photodeposition method. After that, the photocatalytic applications of MSA-HCCN are described, encompassing energy photocatalysis (H<sub>2</sub> evolution, H<sub>2</sub>O<sub>2</sub> production, etc.), environmental photocatalysis (CO<sub>2</sub> reduction, pollutant degradation, etc.), and organic synthesis (CH<sub>4</sub> oxidation, alkylaromatic oxidation, etc.). Lastly, the perspectives of MSA-HCCN photocatalysts are described to supply new thoughts for boosting their further development.","PeriodicalId":16154,"journal":{"name":"Journal of Materials Science & Technology","volume":"19 1","pages":""},"PeriodicalIF":10.9,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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 : 2025-03-07DOI: 10.1016/j.actamat.2025.120863
Jun Liu, Claire Davis, Shuaichao Yue, Mohsen Aghadavoudi Jolfaei, Jialong Shen, Yongjian Li
This paper presents a finite element microstructure model specifically designed to predict scalar anisotropic magnetic permeability. The model integrates crystallographic texture and grain size considerations within specific microstructures, offering a significant advancement in the analysis of scalar permeability and magnetic anisotropy. The model’s precision and robustness have been validated with two types of steel: commercial-grade grain-oriented electrical steel and industrially recrystallised Interstitial-Free steel. Validation was accomplished through comparative magnetic measurements using a modified rotational single sheet tester under varying magnetic field strengths. Additionally, the model employs a generalised power law approach to account for grain size effects, adapting different power laws as necessary. This aspect of the model has been corroborated with experimental data from the literature.
{"title":"Scalar permeability microstructure model considering crystallographic texture and grain size for magnetic evaluation of anisotropy in steel","authors":"Jun Liu, Claire Davis, Shuaichao Yue, Mohsen Aghadavoudi Jolfaei, Jialong Shen, Yongjian Li","doi":"10.1016/j.actamat.2025.120863","DOIUrl":"https://doi.org/10.1016/j.actamat.2025.120863","url":null,"abstract":"This paper presents a finite element microstructure model specifically designed to predict scalar anisotropic magnetic permeability. The model integrates crystallographic texture and grain size considerations within specific microstructures, offering a significant advancement in the analysis of scalar permeability and magnetic anisotropy. The model’s precision and robustness have been validated with two types of steel: commercial-grade grain-oriented electrical steel and industrially recrystallised Interstitial-Free steel. Validation was accomplished through comparative magnetic measurements using a modified rotational single sheet tester under varying magnetic field strengths. Additionally, the model employs a generalised power law approach to account for grain size effects, adapting different power laws as necessary. This aspect of the model has been corroborated with experimental data from the literature.","PeriodicalId":238,"journal":{"name":"Acta Materialia","volume":"16 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569583","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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 : 2025-03-07DOI: 10.1016/j.apsusc.2025.162887
Yonghui Du, Shuangshun Cai, Beizheng Xu, Tongxiao Yang, Zeyu Lin, Xingyu Chen, Hong Chen
Constructing heterojunction represents an effective strategy to significantly improve photocatalytic performance of water splitting. In this paper, we successfully design a S-scheme SnS2/BN heterojunction, and investigate their structural stability, electronic property, optical performance and the interfacial charge transfer through the first-principles calculations. The SnS2/BN heterojunction exhibits the characteristic of type II band edge alignment with the direct band gap of 1.58 eV. A built-in electric field is created as a result of charge transfer across the interfaces caused by the difference in work function. Under photoexcitation, the photogenerated electrons migrate along the S-scheme pathway under the influence of the built-in electric field, which dramatically improving the separation of photogenerated carriers. Notably, this result maintains the robust redox potential in the SnS2/BN heterojunction, which can satisfy the criteria for overall water splitting. In addition, we also use the biaxial strain to investigate the optical and electronic characteristics of the SnS2/BN heterojunction. The findings demonstrate that the increased tensile strain induces the band gap of the heterojunction to narrow, improving the light absorption. Therefore, the SnS2/BN heterojunction is a promising S-scheme photocatalyst for overall water splitting.
{"title":"Direct S-scheme SnS2/BN heterojunction: A promising photocatalyst for overall water splitting","authors":"Yonghui Du, Shuangshun Cai, Beizheng Xu, Tongxiao Yang, Zeyu Lin, Xingyu Chen, Hong Chen","doi":"10.1016/j.apsusc.2025.162887","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.162887","url":null,"abstract":"Constructing heterojunction represents an effective strategy to significantly improve photocatalytic performance of water splitting. In this paper, we successfully design a S-scheme SnS<sub>2</sub>/BN heterojunction, and investigate their structural stability, electronic property, optical performance and the interfacial charge transfer through the first-principles calculations. The SnS<sub>2</sub>/BN heterojunction exhibits the characteristic of type II band edge alignment with the direct band gap of 1.58 eV. A built-in electric field is created as a result of charge transfer across the interfaces caused by the difference in work function. Under photoexcitation, the photogenerated electrons migrate along the S-scheme pathway under the influence of the built-in electric field, which dramatically improving the separation of photogenerated carriers. Notably, this result maintains the robust redox potential in the SnS<sub>2</sub>/BN heterojunction, which can satisfy the criteria for overall water splitting. In addition, we also use the biaxial strain to investigate the optical and electronic characteristics of the SnS<sub>2</sub>/BN heterojunction. The findings demonstrate that the increased tensile strain induces the band gap of the heterojunction to narrow, improving the light absorption. Therefore, the SnS<sub>2</sub>/BN heterojunction is a promising S-scheme photocatalyst for overall water splitting.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"13 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569682","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 : 2025-03-07DOI: 10.1016/j.apsusc.2025.162917
E. Chaslin, Q. Simon, A. Borroto, S. Bruyère, S. Migot, M. Himdi, X. Castel
Epitaxial growth of CeO2 thin films onto sapphire single crystals is of great interest for high-quality heterostructures. Here, the growth mechanisms and crystallographic characteristics of CeO2 films, from 5 to 40 nm-thick deposited by rf-sputtering on r-plane sapphire substrates, were explored by X-ray diffraction, atomic-force microscopy and high-resolution transmission electron microscopy. A growth competition between (1 1 1)/(0 0 2) orientations was identified during the early stages of growth. While both orientations coexist within the first nanometers, the (0 0 2)-orientation progressively dominates due to its higher growth rate, while (1 1 1)-oriented domains remain contained close to the substrate surface. Post-annealing was achieved to enhance the crystalline quality of the films, removing (1 1 1)-oriented domains and providing (0 0 2)-single-oriented CeO2 epitaxial layers. Misorientation was linked to strain relaxation induced by periodic dislocations, as revealed by TEM analysis. Additionally, in-plane dislocations are present within the entire film thickness. Both contribute significantly to the local misorientation. This study provides detailed pictures of defects and quantifies their effect on the film crystallographic quality. It offers insights into both fundamental growth mechanisms and practical strategies to facilitate the epitaxial growth of complex oxides onto the surface of CeO2 thin films, thereby paving the way for innovative applications in catalysis, electronics and/or energy applications.
{"title":"Epitaxial cerium oxide films deposited on r-plane sapphire substrates: A comprehensive study of growth mechanisms","authors":"E. Chaslin, Q. Simon, A. Borroto, S. Bruyère, S. Migot, M. Himdi, X. Castel","doi":"10.1016/j.apsusc.2025.162917","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.162917","url":null,"abstract":"Epitaxial growth of CeO2 thin films onto sapphire single crystals is of great interest for high-quality heterostructures. Here, the growth mechanisms and crystallographic characteristics of CeO2 films, from 5 to 40 nm-thick deposited by rf-sputtering on r-plane sapphire substrates, were explored by X-ray diffraction, atomic-force microscopy and high-resolution transmission electron microscopy. A growth competition between (1 1 1)/(0 0 2) orientations was identified during the early stages of growth. While both orientations coexist within the first nanometers, the (0 0 2)-orientation progressively dominates due to its higher growth rate, while (1 1 1)-oriented domains remain contained close to the substrate surface. Post-annealing was achieved to enhance the crystalline quality of the films, removing (1 1 1)-oriented domains and providing (0 0 2)-single-oriented CeO2 epitaxial layers. Misorientation was linked to strain relaxation induced by periodic dislocations, as revealed by TEM analysis. Additionally, in-plane dislocations are present within the entire film thickness. Both contribute significantly to the local misorientation. This study provides detailed pictures of defects and quantifies their effect on the film crystallographic quality. It offers insights into both fundamental growth mechanisms and practical strategies to facilitate the epitaxial growth of complex oxides onto the surface of CeO2 thin films, thereby paving the way for innovative applications in catalysis, electronics and/or energy applications.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"17 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569684","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}
Liming Liu, Shishun Li, Xuyang Wu, Hui You, Guojian Yang, Kun Zhang, Cuimin Sun, Shuang Liu
Adsorbents with super-wettability are deemed as an ideal candidate in treatment of oil spills, however, the recovery of high-viscous crude oil faces the difficulties of low adsorption efficiency and the recycling burden from waste adsorbents. In this study, inspired by the substances transport channel of stem from colocasia gigantea, a photo-thermal and flame-retardant aerogel with super-hydrophobicity/super-oleophilicity exhibits a high-throughout recovery of 548 kg m−2h−1 toward solid-paste crude oil under the solar illumination of 0.1 W cm−2. These properties are attributed to its optimized aperture distribution and vertically aligned bio-channel structure, which can be controlled by adjusting freeze-drying process and feeding ratios of aerogel skeleton between cellulose and chitosan. Significantly, the self-decomposition of as-prepared aerogel is demonstrated after burying it in a soil environment, showing the remarkable natural degradability. Additionally, the aerogel maintains a water rolling angle of 8 ± 1° even after the 100 cycles compression test and the immersion in organic solvent (120 h) and corrosive solution (24 h), demonstrating its good mechanochemical durability. This work endows the aerogel adsorbent with selective super-wettability, degradeability, photo-thermal conversion, and flame-retardancy, which are highly demanded in multi-scenarios oil recovery.
{"title":"A Degradable Photo-Thermal Aerogel with Biomimetic Structure and Selective Wettability for High-Throughput Recovery of Viscous Crude Oil","authors":"Liming Liu, Shishun Li, Xuyang Wu, Hui You, Guojian Yang, Kun Zhang, Cuimin Sun, Shuang Liu","doi":"10.1002/adfm.202425886","DOIUrl":"https://doi.org/10.1002/adfm.202425886","url":null,"abstract":"Adsorbents with super-wettability are deemed as an ideal candidate in treatment of oil spills, however, the recovery of high-viscous crude oil faces the difficulties of low adsorption efficiency and the recycling burden from waste adsorbents. In this study, inspired by the substances transport channel of stem from colocasia gigantea, a photo-thermal and flame-retardant aerogel with super-hydrophobicity/super-oleophilicity exhibits a high-throughout recovery of 548 kg m<sup>−2</sup>h<sup>−1</sup> toward solid-paste crude oil under the solar illumination of 0.1 W cm<sup>−2</sup>. These properties are attributed to its optimized aperture distribution and vertically aligned bio-channel structure, which can be controlled by adjusting freeze-drying process and feeding ratios of aerogel skeleton between cellulose and chitosan. Significantly, the self-decomposition of as-prepared aerogel is demonstrated after burying it in a soil environment, showing the remarkable natural degradability. Additionally, the aerogel maintains a water rolling angle of 8 ± 1° even after the 100 cycles compression test and the immersion in organic solvent (120 h) and corrosive solution (24 h), demonstrating its good mechanochemical durability. This work endows the aerogel adsorbent with selective super-wettability, degradeability, photo-thermal conversion, and flame-retardancy, which are highly demanded in multi-scenarios oil recovery.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"12 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chengcheng Gu, Lei Zhang, Ting Hou, Qianqian Wang, Feng Li, Panpan Gai
Chronic wounds are a common complication of diabetes, causing significant inconvenience, persistent pain, and economic burden to patients. Real-time monitoring of wound status and timely treatment with intelligent dressings is a promising way to treat wound infection and accelerate healing. However, the traditional dressings make it difficult to simultaneously maintain the true state of the wound and meet the dynamic needs of chronic wounds. Herein, a multifunctional self-powered patch (MSPP) featured with antibacterial, hypoglycemic, and electrical stimulation is designed to promote wound healing and real-time monitoring of wound status, in which laser-induced nanozyme electrodes are prepared in situ through laser scanning technology to construct the highly stable nanozyme-based glucose biofuel cells (GBFCs). Enzymatic cascade reaction in GBFCs can use local hyperglycemia of wounds to produce reactive oxygen species with effective antibacterial properties, reduce hyperglycemia while generating stable microcurrent, and further promote diabetes wound healing. In just 10 days, the patch-treated group achieves 100% wound shrinkage. Meanwhile, the pH sensing module in the MSPP can also monitor pH fluctuations in real-time and correct glucose test results, improving the sensing accuracy. In brief, the construction of MSPP provides promising solutions for developing closed-loop biomedical systems that integrate monitoring, diagnosis, and treatment.
{"title":"Laser-Induced Nanozyme Biofuel Cell-Based Self-Powered Patch for Accelerating Diabetic Wound Healing With Real-Time Monitoring","authors":"Chengcheng Gu, Lei Zhang, Ting Hou, Qianqian Wang, Feng Li, Panpan Gai","doi":"10.1002/adfm.202423106","DOIUrl":"https://doi.org/10.1002/adfm.202423106","url":null,"abstract":"Chronic wounds are a common complication of diabetes, causing significant inconvenience, persistent pain, and economic burden to patients. Real-time monitoring of wound status and timely treatment with intelligent dressings is a promising way to treat wound infection and accelerate healing. However, the traditional dressings make it difficult to simultaneously maintain the true state of the wound and meet the dynamic needs of chronic wounds. Herein, a multifunctional self-powered patch (MSPP) featured with antibacterial, hypoglycemic, and electrical stimulation is designed to promote wound healing and real-time monitoring of wound status, in which laser-induced nanozyme electrodes are prepared in situ through laser scanning technology to construct the highly stable nanozyme-based glucose biofuel cells (GBFCs). Enzymatic cascade reaction in GBFCs can use local hyperglycemia of wounds to produce reactive oxygen species with effective antibacterial properties, reduce hyperglycemia while generating stable microcurrent, and further promote diabetes wound healing. In just 10 days, the patch-treated group achieves 100% wound shrinkage. Meanwhile, the pH sensing module in the MSPP can also monitor pH fluctuations in real-time and correct glucose test results, improving the sensing accuracy. In brief, the construction of MSPP provides promising solutions for developing closed-loop biomedical systems that integrate monitoring, diagnosis, and treatment.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"18 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569855","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rechargeable Mg batteries are an energy-storage technology suitable for large-scale applications, but the lack of high-performance cathode materials is currently hindering their development. Conversion-type cathodes break the limits of Mg-intercalation principle, but existing structural design strategies mostly focus on morphology optimization to increase active reaction interfaces. The present study reveals that crystal structure also plays a significant role in the Mg-storage activity of conversion reactions. Two types of CoSe2 with orthorhombic and cubic phases are synthesized from ZIF-67 and comparatively investigated as cathode materials for RMBs. Despite exhibiting similar micromorphology and a lower specific surface area, the orthorhombic phase CoSe2 demonstrates superior Mg-storage capacity, rate performance, lower charge transfer resistance, and higher solid-state Mg2+ diffusion coefficients compared to the cubic phase CoSe2. Mechanism studies reveal that the conversion reaction of orthorhombic CoSe2 is more thorough and reversible, involving the redox of both cations and anions. Further theoretical computations indicate that the higher reaction activity at (010) plane of orthorhombic CoSe2, along with more active sites of Se‒Se bonds, facilitates the conversion Mg-storage reaction via co-redox of the cations and anions. This study underscores the importance of crystal structure in the design of conversion-type RMB cathode materials.
{"title":"Favorable Orthorhombic Phase Cobalt Diselenide Cathode for Rechargeable Mg Batteries: Elucidating the Significant Impact of Crystal Structure on Conversion-Type Mg-Storage Reactions","authors":"Hou-an Zhang, Panfei Xiao, Changchun Hu, Donggang Tao, Daohong Zhang, Yuliang Cao, Ting Li, Fei Xu","doi":"10.1002/adfm.202426006","DOIUrl":"https://doi.org/10.1002/adfm.202426006","url":null,"abstract":"Rechargeable Mg batteries are an energy-storage technology suitable for large-scale applications, but the lack of high-performance cathode materials is currently hindering their development. Conversion-type cathodes break the limits of Mg-intercalation principle, but existing structural design strategies mostly focus on morphology optimization to increase active reaction interfaces. The present study reveals that crystal structure also plays a significant role in the Mg-storage activity of conversion reactions. Two types of CoSe<sub>2</sub> with orthorhombic and cubic phases are synthesized from ZIF-67 and comparatively investigated as cathode materials for RMBs. Despite exhibiting similar micromorphology and a lower specific surface area, the orthorhombic phase CoSe<sub>2</sub> demonstrates superior Mg-storage capacity, rate performance, lower charge transfer resistance, and higher solid-state Mg<sup>2+</sup> diffusion coefficients compared to the cubic phase CoSe<sub>2</sub>. Mechanism studies reveal that the conversion reaction of orthorhombic CoSe<sub>2</sub> is more thorough and reversible, involving the redox of both cations and anions. Further theoretical computations indicate that the higher reaction activity at (010) plane of orthorhombic CoSe<sub>2</sub>, along with more active sites of Se‒Se bonds, facilitates the conversion Mg-storage reaction via co-redox of the cations and anions. This study underscores the importance of crystal structure in the design of conversion-type RMB cathode materials.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"87 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Plasmonic “antenna reactor” alloys, consisting of a plasmonic material doped with a catalytically active metal, show great promise for efficient photocatalysis. However, while simple, intuitive, and approximate design principles such as the Sabatier principle have been developed for thermal and electrocatalysis, similar design principles for plasmonic catalysts remain elusive. Here, we develop these simple design principles by using real-time, time-dependent density functional theory to study small molecule activation (CH4, CO2, H2O, and N2) on a number of Cu-based antenna reactors and elucidate trends. We first show that this technique gives results consistent with experimental plasmonic catalysis studies. We then identify promising, previously untested antenna reactors for these molecules. Next, we find that, for a given molecule, bond activation correlates with the size of the charge oscillations between the nanoparticle and molecule as quantified by the standard deviation over the propagation time. Furthermore, the orbital overlap between the dopant and molecule also roughly correlates with the bond activation. For CH4, N2, and H2O, a greater overlap leads to higher activation. For CO2, the trend is reversed because a greater overlap leads to higher chemical activation upon adsorption, which inhibits photoactivation. Hence, the orbital overlap can be used as a computationally efficient and intuitively simple predictor of photoactivation for the initial screening of plasmonic catalysts.
{"title":"Computational Discovery of Design Principles for Plasmon-Driven Bond Activation on Alloy Antenna Reactors","authors":"Connor J. Herring, Matthew M. Montemore","doi":"10.1021/acsnano.4c13602","DOIUrl":"https://doi.org/10.1021/acsnano.4c13602","url":null,"abstract":"Plasmonic “antenna reactor” alloys, consisting of a plasmonic material doped with a catalytically active metal, show great promise for efficient photocatalysis. However, while simple, intuitive, and approximate design principles such as the Sabatier principle have been developed for thermal and electrocatalysis, similar design principles for plasmonic catalysts remain elusive. Here, we develop these simple design principles by using real-time, time-dependent density functional theory to study small molecule activation (CH<sub>4</sub>, CO<sub>2</sub>, H<sub>2</sub>O, and N<sub>2</sub>) on a number of Cu-based antenna reactors and elucidate trends. We first show that this technique gives results consistent with experimental plasmonic catalysis studies. We then identify promising, previously untested antenna reactors for these molecules. Next, we find that, for a given molecule, bond activation correlates with the size of the charge oscillations between the nanoparticle and molecule as quantified by the standard deviation over the propagation time. Furthermore, the orbital overlap between the dopant and molecule also roughly correlates with the bond activation. For CH<sub>4</sub>, N<sub>2</sub>, and H<sub>2</sub>O, a greater overlap leads to higher activation. For CO<sub>2</sub>, the trend is reversed because a greater overlap leads to higher chemical activation upon adsorption, which inhibits photoactivation. Hence, the orbital overlap can be used as a computationally efficient and intuitively simple predictor of photoactivation for the initial screening of plasmonic catalysts.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"71 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kaihua Liu, Peiyao Lin, Jing Li, Yuanyuan Liu, Meiri Wang, Hongtao Cui, Shasha Yi
Constructing highly efficient bismuth (Bi)-based catalysts to accelerate the sluggish kinetic process of CO2 electroreduction to HCOOH is crucial for promoting its practical application but also highly challenging. Herein, the bismuth cerium oxide catalyst integrated with dual active centers of oxygen vacancy and the heterogeneous interface is fabricated to facilitate the reduction process and enhance the CO2 electroreduction performance. It is revealed that the introduction of dual active centers endows the catalyst with a remarkably enhanced CO2 adsorption capacity and facilitates the transfer of more electrons to *CO2. Furthermore, it even steers the reaction pathway favorably toward HCOOH production. The optimization of CO2 adsorption, activation, and reaction energy barriers expedited the process of CO2 electroreduction to HCOOH. As expected, this catalyst exhibits enhanced catalytic performance with a Faradaic efficiency of 97% for HCOOH even at the current density of 300 mA cm−2. This work highlights the significant synergistic advantages of oxygen vacancies and heterogeneous interfaces in optimizing molecular adsorption, activation, and reaction energy barriers to accelerate the kinetic process.
{"title":"Synergistic Acceleration of CO2 Electroreduction Kinetics by Oxygen Vacancy and Heterogeneous Interface for Efficient HCOOH Production","authors":"Kaihua Liu, Peiyao Lin, Jing Li, Yuanyuan Liu, Meiri Wang, Hongtao Cui, Shasha Yi","doi":"10.1002/adfm.202424357","DOIUrl":"https://doi.org/10.1002/adfm.202424357","url":null,"abstract":"Constructing highly efficient bismuth (Bi)-based catalysts to accelerate the sluggish kinetic process of CO<sub>2</sub> electroreduction to HCOOH is crucial for promoting its practical application but also highly challenging. Herein, the bismuth cerium oxide catalyst integrated with dual active centers of oxygen vacancy and the heterogeneous interface is fabricated to facilitate the reduction process and enhance the CO<sub>2</sub> electroreduction performance. It is revealed that the introduction of dual active centers endows the catalyst with a remarkably enhanced CO<sub>2</sub> adsorption capacity and facilitates the transfer of more electrons to <sup>*</sup>CO<sub>2</sub>. Furthermore, it even steers the reaction pathway favorably toward HCOOH production. The optimization of CO<sub>2</sub> adsorption, activation, and reaction energy barriers expedited the process of CO<sub>2</sub> electroreduction to HCOOH. As expected, this catalyst exhibits enhanced catalytic performance with a Faradaic efficiency of 97% for HCOOH even at the current density of 300 mA cm<sup>−2</sup>. This work highlights the significant synergistic advantages of oxygen vacancies and heterogeneous interfaces in optimizing molecular adsorption, activation, and reaction energy barriers to accelerate the kinetic process.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"49 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569935","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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