Victor ALCOLEA Alcolea-Rodriguez, Ivana Fenoglio, Magda Blosi, Marina Serantoni, Felice Simeone, Ilaria Zanoni, Anna Costa, Raquel Portela, Miguel Bañares
In chemico tests are important tools that complement in silico, in vitro and in vivo approaches to predict the toxicological impact of nanomaterials (NMs). Here, we apply a recently proposed in chemico methodology, based on the evaluation of the number, nature and properties of reactive surface sites of NMs, to a series of magentite-, hydroxyapatite- and silver-based hybrid nanobiomaterials (NBMs). The properties of the NBMs were examined using methanol chemisorption followed by temperature-programmed surface reaction (MeOH-TPSR), dithiothreitol (DTT) oxidation, cyclic voltammetry in biologically relevant media, and electronic paramagnetic resonance (EPR) spectroscopy in a series of relevant media as spin trap. The resulting data were critically compared and correlated with the available in vitro data on the NBMs’ hazard. Our findings reveal significant differences in the oxidative potential of these hybrid NBMs. Iron (Fe) doping in hydroxyapatite (HA) introduced new redox-active surface sites, leading to increased oxidative reactivity via ROS-independent mechanisms, as evidenced by higher DTT depletion and Fenton-like activity compared HA. Conversely, titanium (Ti) doping modified HA's surface by introducing acidic active sites, reducing its oxidative capacity. Coating Fe₃O₄ with poly(ethylene glycol)-poly(lactic-co-glycolic) acid (PEG-PLGA) enhanced oxidative reactivity without ROS generation, suggesting a surface-driven process. In contrast, hydroxyethyl cellulose (HEC) coating significantly reduced the high reactivity of uncoated silver (Ag). This study underscores the importance of determining the NBMs’ reactive profile for safe biomedical use, highlighting how specific coatings and dopants can transform oxidative surface properties.
{"title":"In Chemico Categorization of Magnetite-, Hydroxyapatite-, and Ag-Derived Hybrid Nanobiomaterials Based on the Surface Oxidative Reactivity: Implications of Doping and Coating","authors":"Victor ALCOLEA Alcolea-Rodriguez, Ivana Fenoglio, Magda Blosi, Marina Serantoni, Felice Simeone, Ilaria Zanoni, Anna Costa, Raquel Portela, Miguel Bañares","doi":"10.1039/d5nr00709g","DOIUrl":"https://doi.org/10.1039/d5nr00709g","url":null,"abstract":"In chemico tests are important tools that complement in silico, in vitro and in vivo approaches to predict the toxicological impact of nanomaterials (NMs). Here, we apply a recently proposed in chemico methodology, based on the evaluation of the number, nature and properties of reactive surface sites of NMs, to a series of magentite-, hydroxyapatite- and silver-based hybrid nanobiomaterials (NBMs). The properties of the NBMs were examined using methanol chemisorption followed by temperature-programmed surface reaction (MeOH-TPSR), dithiothreitol (DTT) oxidation, cyclic voltammetry in biologically relevant media, and electronic paramagnetic resonance (EPR) spectroscopy in a series of relevant media as spin trap. The resulting data were critically compared and correlated with the available in vitro data on the NBMs’ hazard. Our findings reveal significant differences in the oxidative potential of these hybrid NBMs. Iron (Fe) doping in hydroxyapatite (HA) introduced new redox-active surface sites, leading to increased oxidative reactivity via ROS-independent mechanisms, as evidenced by higher DTT depletion and Fenton-like activity compared HA. Conversely, titanium (Ti) doping modified HA's surface by introducing acidic active sites, reducing its oxidative capacity. Coating Fe₃O₄ with poly(ethylene glycol)-poly(lactic-co-glycolic) acid (PEG-PLGA) enhanced oxidative reactivity without ROS generation, suggesting a surface-driven process. In contrast, hydroxyethyl cellulose (HEC) coating significantly reduced the high reactivity of uncoated silver (Ag). This study underscores the importance of determining the NBMs’ reactive profile for safe biomedical use, highlighting how specific coatings and dopants can transform oxidative surface properties.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"75 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827278","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}
Li Liu, Haodong Xie, Xiang Ni, Xue Yang, Yan Liu, Yufang Ma, Feixiang Yuan, Shuo Tao, Lei Wang, Hongjun Zhu
Fractal crystals are a class of fascinating crystals in this world, typically captured in dense crystal phases like snowflakes, graphene, and metal alloys. Nevertheless, such crystal analogues are quite rare in framework crystal phases, and their structural origins remain an intriguing enigma. In this work, we successfully constructed a series of fractal TON zeolites via a rare twinning mode, thereby revealing their structural origins. The continuous rotational electron diffraction technique solved its unique crystallographic structure. The fractal boundary exhibited coherence along the {021} facets and left the periodic dangling silanol defects. As evidenced by spatial element reconstruction and structural analysis, we found that the TON fractal was triggered by organic cations anchoring heteroatoms at the framework T3 site. Such fractal dimensions of TON can be effectively tailored by adjusting the heteroatom concentration in the synthetic system. The Pt-loaded fractal TON zeolite bifunctional catalyst demonstrated remarkable performance in the hydroisomerization of n-hexadecane with a maximum isomer yield of 84.4%, which is 28.9% higher than that of the Pt/rod-like TON catalyst, attributed to the more accessible active sites of the fractal architecture. Unravelling the twinning structure and its origin of zeotype catalysts would afford novel insights for the development of promising advanced heterogeneous catalysts.
{"title":"Defective plane induced fractal TON zeolites for efficient hydroisomerization of long-chain hydrocarbons","authors":"Li Liu, Haodong Xie, Xiang Ni, Xue Yang, Yan Liu, Yufang Ma, Feixiang Yuan, Shuo Tao, Lei Wang, Hongjun Zhu","doi":"10.1039/d5nr00443h","DOIUrl":"https://doi.org/10.1039/d5nr00443h","url":null,"abstract":"Fractal crystals are a class of fascinating crystals in this world, typically captured in dense crystal phases like snowflakes, graphene, and metal alloys. Nevertheless, such crystal analogues are quite rare in framework crystal phases, and their structural origins remain an intriguing enigma. In this work, we successfully constructed a series of fractal <strong>TON</strong> zeolites <em>via</em> a rare twinning mode, thereby revealing their structural origins. The continuous rotational electron diffraction technique solved its unique crystallographic structure. The fractal boundary exhibited coherence along the {021} facets and left the periodic dangling silanol defects. As evidenced by spatial element reconstruction and structural analysis, we found that the <strong>TON</strong> fractal was triggered by organic cations anchoring heteroatoms at the framework T3 site. Such fractal dimensions of <strong>TON</strong> can be effectively tailored by adjusting the heteroatom concentration in the synthetic system. The Pt-loaded fractal <strong>TON</strong> zeolite bifunctional catalyst demonstrated remarkable performance in the hydroisomerization of <em>n</em>-hexadecane with a maximum isomer yield of 84.4%, which is 28.9% higher than that of the Pt/rod-like <strong>TON</strong> catalyst, attributed to the more accessible active sites of the fractal architecture. Unravelling the twinning structure and its origin of zeotype catalysts would afford novel insights for the development of promising advanced heterogeneous catalysts.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"239 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827280","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}
Breast cancer is a leading cause of mortality among women globally, with the human epidermal growth factor receptor-2 (HER-2) serving as a vital biomarker for its diagnosis and management. In this study, an electrochemical aptasensor was developed using V2CTx MXene for the sensitive and selective quantification of HER-2. The sensor's electrochemical performance was evaluated through cyclic voltammetry (CV) and square wave voltammetry (SWV) that demonstrated a wide linear detection range of 1 ng mL−1 to 100 μg mL−1. The aptasensor achieved an exceptional detection limit of 0.36 ng mL−1 and a quantification limit of 1.96 ng mL−1 under optimized conditions. Furthermore, the sensor displayed excellent selectivity for HER-2 against other biomarkers and retained stability for 40 days, making it suitable for prolonged use. The high electrochemical response was attributed to the exceptional surface-to-volume ratio and conductivity of the V2CTx MXene, enabling efficient aptamer immobilization and signal enhancement. These findings highlight the potential of the developed aptasensor as a non-invasive, reliable, and cost-effective platform for early HER-2 detection, paving the way for improved breast cancer diagnosis and monitoring.
{"title":"Ultrasensitive electroanalytical sensing platform using aptamer-conjugated V2CTx MXene for the detection of the HER-2 biomarker","authors":"Reema Rawat, Sonam Singh, Souradeep Roy, Samarika Dubey, Tapas Goswami, Ashish Mathur, James McLaughlin","doi":"10.1039/d4nr04503c","DOIUrl":"https://doi.org/10.1039/d4nr04503c","url":null,"abstract":"Breast cancer is a leading cause of mortality among women globally, with the human epidermal growth factor receptor-2 (HER-2) serving as a vital biomarker for its diagnosis and management. In this study, an electrochemical aptasensor was developed using V<small><sub>2</sub></small>CT<small><sub><em>x</em></sub></small> MXene for the sensitive and selective quantification of HER-2. The sensor's electrochemical performance was evaluated through cyclic voltammetry (CV) and square wave voltammetry (SWV) that demonstrated a wide linear detection range of 1 ng mL<small><sup>−1</sup></small> to 100 μg mL<small><sup>−1</sup></small>. The aptasensor achieved an exceptional detection limit of 0.36 ng mL<small><sup>−1</sup></small> and a quantification limit of 1.96 ng mL<small><sup>−1</sup></small> under optimized conditions. Furthermore, the sensor displayed excellent selectivity for HER-2 against other biomarkers and retained stability for 40 days, making it suitable for prolonged use. The high electrochemical response was attributed to the exceptional surface-to-volume ratio and conductivity of the V<small><sub>2</sub></small>CT<small><sub><em>x</em></sub></small> MXene, enabling efficient aptamer immobilization and signal enhancement. These findings highlight the potential of the developed aptasensor as a non-invasive, reliable, and cost-effective platform for early HER-2 detection, paving the way for improved breast cancer diagnosis and monitoring.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"6 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827277","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}
Gowri shonali Natarajamani, Veera Prabu Kannan, M. Sridharan
Achieving high sensitivity and rapid response/recovery times at ambient temperatures remains a significant challenge in gas sensing. Ti3C2Tx MXenes have gained attention for their gas-sensing potential due to their high conductivity and active surface functional groups, but challenges such as limited sensitivity and slow response/recovery persist. In this study, we present an ultrafast, reversible Ti3C2Tx/ZnO hybrid composite sensor for NH₃ detection at room temperature. We evaluated the sensor's performance under both ambient and UV illumination conditions. Under ambient conditions, the Ti3C2Tx/ZnO sensor exhibited a 50-fold enhancement in sensitivity compared to pristine ZnO, with response and recovery times of 49 s and 39 s, respectively, for 10 ppm NH₃. Under UV illumination, optimized Ti3C2Tx/ZnO configurations achieved a sensor response of 88 at 50 ppm NH₃, with ultrafast response and recovery times of 10 s and 13 s, respectively, at 10 ppm NH₃, and a limit of detection (LOD) of 0.1 ppm. These improvements are attributed to charge perturbation at the sensor surface facilitated by the Ti3C2Tx/ZnO interaction and the formation of a Schottky barrier at their interface, accelerating adsorption-desorption kinetics. The sensor also demonstrated excellent selectivity for NH3 and high long-term stability and repeatability, making it highly suitable for environmental monitoring, industrial safety, and medical diagnostics.
{"title":"Unveiling Superior NH3 Sensing Performance: Ultrafast Response and Enhanced Recovery Kinetics in Ti3C2Tx/ZnO Nano Hybrid Sensors with UV-Induced Schottky Junctions","authors":"Gowri shonali Natarajamani, Veera Prabu Kannan, M. Sridharan","doi":"10.1039/d5nr00484e","DOIUrl":"https://doi.org/10.1039/d5nr00484e","url":null,"abstract":"Achieving high sensitivity and rapid response/recovery times at ambient temperatures remains a significant challenge in gas sensing. Ti3C2Tx MXenes have gained attention for their gas-sensing potential due to their high conductivity and active surface functional groups, but challenges such as limited sensitivity and slow response/recovery persist. In this study, we present an ultrafast, reversible Ti3C2Tx/ZnO hybrid composite sensor for NH₃ detection at room temperature. We evaluated the sensor's performance under both ambient and UV illumination conditions. Under ambient conditions, the Ti3C2Tx/ZnO sensor exhibited a 50-fold enhancement in sensitivity compared to pristine ZnO, with response and recovery times of 49 s and 39 s, respectively, for 10 ppm NH₃. Under UV illumination, optimized Ti3C2Tx/ZnO configurations achieved a sensor response of 88 at 50 ppm NH₃, with ultrafast response and recovery times of 10 s and 13 s, respectively, at 10 ppm NH₃, and a limit of detection (LOD) of 0.1 ppm. These improvements are attributed to charge perturbation at the sensor surface facilitated by the Ti3C2Tx/ZnO interaction and the formation of a Schottky barrier at their interface, accelerating adsorption-desorption kinetics. The sensor also demonstrated excellent selectivity for NH3 and high long-term stability and repeatability, making it highly suitable for environmental monitoring, industrial safety, and medical diagnostics.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"119 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827337","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}
Alexander Simanenko, Jan Škvára, Pankaj kumar Samal, Evanie Franz, Robert Hübsch, Tomas Skala, Nataliya Tsud, Sascha Mehl, Daniel Schauermann, Viktor Johánek, Josef Mysliveček, Olaf Brummel, Yaroslava Lykhach, Joerg Libuda
The stabilities of monometallic Rh and Pd nanoparticles and bimetallic Pd–Rh core–shell nanoparticles supported on Co3O4(111) thin films grown on Ir(100) were investigated with respect to the oxidation state and dissolution in alkaline electrolyte under the conditions relevant for electrochemical ethanol oxidation. Towards this aim, the well-defined model systems were characterized by means of synchrotron radiation photoelectron spectroscopy coupled with an ex situ emersion electrochemical cell (EC-SRPES) and scanning tunneling microscopy (STM). We found that the electronic metal–support interaction (EMSI) has a strong influence on the oxidation state of Rh, resulting in a strong oxidation and anchoring of the oxidized Rh3+ species on the surface of Co3O4(111). Consequently, the EMSI prevents the dissolution of Rh into the electrolyte regardless of the potential range. In contrast, it has no effect on the oxidation state and dissolution of Pd in the potential range of 0.3–1.1 VRHE. However, extending the potential range to 0.3–1.5 VRHE results in a stronger dissolution of Pd due to the reversible oxidation/reduction of Pd, which is enhanced in the presence of the EMSI. Most importantly, the magnitude of the EMSI and, thus, the extent of noble metal oxidation, can be effectively controlled by the nature of the metal/Co3O4(111) interface in the bimetallic Pd–Rh core–shell nanoparticles.
{"title":"Stability of multifunctional Pd‒Rh electrocatalysts supported on Co3O4(111) in alkaline environment: Impact of the electronic metal‒support interaction","authors":"Alexander Simanenko, Jan Škvára, Pankaj kumar Samal, Evanie Franz, Robert Hübsch, Tomas Skala, Nataliya Tsud, Sascha Mehl, Daniel Schauermann, Viktor Johánek, Josef Mysliveček, Olaf Brummel, Yaroslava Lykhach, Joerg Libuda","doi":"10.1039/d5nr00413f","DOIUrl":"https://doi.org/10.1039/d5nr00413f","url":null,"abstract":"The stabilities of monometallic Rh and Pd nanoparticles and bimetallic Pd–Rh core–shell nanoparticles supported on Co<small><sub>3</sub></small>O<small><sub>4</sub></small>(111) thin films grown on Ir(100) were investigated with respect to the oxidation state and dissolution in alkaline electrolyte under the conditions relevant for electrochemical ethanol oxidation. Towards this aim, the well-defined model systems were characterized by means of synchrotron radiation photoelectron spectroscopy coupled with an <em>ex situ</em> emersion electrochemical cell (EC-SRPES) and scanning tunneling microscopy (STM). We found that the electronic metal–support interaction (EMSI) has a strong influence on the oxidation state of Rh, resulting in a strong oxidation and anchoring of the oxidized Rh<small><sup>3+</sup></small> species on the surface of Co<small><sub>3</sub></small>O<small><sub>4</sub></small>(111). Consequently, the EMSI prevents the dissolution of Rh into the electrolyte regardless of the potential range. In contrast, it has no effect on the oxidation state and dissolution of Pd in the potential range of 0.3–1.1 V<small><sub>RHE</sub></small>. However, extending the potential range to 0.3–1.5 V<small><sub>RHE</sub></small> results in a stronger dissolution of Pd due to the reversible oxidation/reduction of Pd, which is enhanced in the presence of the EMSI. Most importantly, the magnitude of the EMSI and, thus, the extent of noble metal oxidation, can be effectively controlled by the nature of the metal/Co<small><sub>3</sub></small>O<small><sub>4</sub></small>(111) interface in the bimetallic Pd–Rh core–shell nanoparticles.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"183 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827279","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}
Renée T. M. van Limpt, Cristian A. A. van Helvoirt, Mariadriana Creatore, Marcel A. Verheijen
NiO and Co3O4 are versatile materials studied for a plethora of applications, yet their performance for a specific application relies on the control of their crystallographic texture and corresponding surface facets. Achieving such control can be challenging, often requiring hetero-epitaxial growth on single-crystalline substrates, which are frequently incompatible with the requirements of the application. The combination of NiO and Co3O4 in heterostructures provides potential to control texture due to their similar crystal structures, whilst retaining the possibility to work with more versatile substrates. In this study, atomic layer deposited (ALD) thin films based on cyclopentadienyl precursors and an oxygen plasma are adopted to tailor the crystallographic texture of NiO from 〈100〉 to 〈111〉 using an ALD Co3O4 template layer, and similarly, to modify the Co3O4 texture from 〈111〉 to 〈100〉 on a NiO template. The films are shown to conform to the crystal orientation of the template material, whilst crystallizing directly in their own stable crystal structure with corresponding metal atom coordination. Further investigation includes ALD process parameters for NiO growth: the film texture is found to depend on the choice of co-reactant and the above-highlighted hetero-epitaxial relationship is stronger for plasma-based processes. In conclusion, these results demonstrate an original approach for application-oriented crystallographic engineering in thin films.
{"title":"On the epitaxial growth in ALD Co3O4- and NiO-based bilayers","authors":"Renée T. M. van Limpt, Cristian A. A. van Helvoirt, Mariadriana Creatore, Marcel A. Verheijen","doi":"10.1039/d5nr01212k","DOIUrl":"https://doi.org/10.1039/d5nr01212k","url":null,"abstract":"NiO and Co<small><sub>3</sub></small>O<small><sub>4</sub></small> are versatile materials studied for a plethora of applications, yet their performance for a specific application relies on the control of their crystallographic texture and corresponding surface facets. Achieving such control can be challenging, often requiring hetero-epitaxial growth on single-crystalline substrates, which are frequently incompatible with the requirements of the application. The combination of NiO and Co<small><sub>3</sub></small>O<small><sub>4</sub></small> in heterostructures provides potential to control texture due to their similar crystal structures, whilst retaining the possibility to work with more versatile substrates. In this study, atomic layer deposited (ALD) thin films based on cyclopentadienyl precursors and an oxygen plasma are adopted to tailor the crystallographic texture of NiO from 〈100〉 to 〈111〉 using an ALD Co<small><sub>3</sub></small>O<small><sub>4</sub></small> template layer, and similarly, to modify the Co<small><sub>3</sub></small>O<small><sub>4</sub></small> texture from 〈111〉 to 〈100〉 on a NiO template. The films are shown to conform to the crystal orientation of the template material, whilst crystallizing directly in their own stable crystal structure with corresponding metal atom coordination. Further investigation includes ALD process parameters for NiO growth: the film texture is found to depend on the choice of co-reactant and the above-highlighted hetero-epitaxial relationship is stronger for plasma-based processes. In conclusion, these results demonstrate an original approach for application-oriented crystallographic engineering in thin films.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"39 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827336","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}
Yang Wang, Wenhao Zhu, Xuanheng Chen, Xiantao Yang, Anling Tong, Sheng Yang, Jihuai Wu, Weihai Sun
Electron transport layer (ETL) in the traditional CsPbBr3 perovskite solar cells (PSCs) without hole transport layer (HTL) presents the capability to transport electrons and to block hole transport, which radically affects the photovoltaic performance of PSCs. However, ZnO ETL prepared by classic sol-gel method exhibits obvious drawbacks, such as serious interfacial recombination reaction, inducement of oxygen vacancy (VO) and zinc interstitials (Zni). Herein, we demonstrate that alkali metal chloride (e.g. KCl), serving as the passivating agent for the surface and bulk phase, can promote surface modification and doping in ZnO ETL, respectively. The experimental results show that the interaction between K+ and Zn2+, and the occupation of VO by Cl-, suppress the internal defect states of ZnO films, which enhances the crystal coordination between ZnO and CsPbBr3, and improves the film morphology as well as the quality of the upper perovskite (PVK) films. The experimental PSCs based on the doping approach have achieved the champion power conversion efficiency (PCE) of 9.22%, which ranks the highest PCE of (FTO/ITO)/ZnO /CsPbBr3/Carbon structure. Moreover, the unpackaged devices of the two experimental PSCs still maintain 97.15% and 74.76% of the original PCE after 28 days exposed in the ambient environment, showing the powerful effect of KCl on the regulation of surface and bulk phase defects in the ZnO ETL.
{"title":"Bulk and Surface Defect Manipulation of the ZnO ETL for All-inorganic CsPbBr3 Perovskite Solar Cells","authors":"Yang Wang, Wenhao Zhu, Xuanheng Chen, Xiantao Yang, Anling Tong, Sheng Yang, Jihuai Wu, Weihai Sun","doi":"10.1039/d5nr00315f","DOIUrl":"https://doi.org/10.1039/d5nr00315f","url":null,"abstract":"Electron transport layer (ETL) in the traditional CsPbBr3 perovskite solar cells (PSCs) without hole transport layer (HTL) presents the capability to transport electrons and to block hole transport, which radically affects the photovoltaic performance of PSCs. However, ZnO ETL prepared by classic sol-gel method exhibits obvious drawbacks, such as serious interfacial recombination reaction, inducement of oxygen vacancy (VO) and zinc interstitials (Zni). Herein, we demonstrate that alkali metal chloride (e.g. KCl), serving as the passivating agent for the surface and bulk phase, can promote surface modification and doping in ZnO ETL, respectively. The experimental results show that the interaction between K+ and Zn2+, and the occupation of VO by Cl-, suppress the internal defect states of ZnO films, which enhances the crystal coordination between ZnO and CsPbBr3, and improves the film morphology as well as the quality of the upper perovskite (PVK) films. The experimental PSCs based on the doping approach have achieved the champion power conversion efficiency (PCE) of 9.22%, which ranks the highest PCE of (FTO/ITO)/ZnO /CsPbBr3/Carbon structure. Moreover, the unpackaged devices of the two experimental PSCs still maintain 97.15% and 74.76% of the original PCE after 28 days exposed in the ambient environment, showing the powerful effect of KCl on the regulation of surface and bulk phase defects in the ZnO ETL.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"14 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822419","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}
As a small alcohol molecule with low oxidation potential, ethylene glycol is also a key monomer in the production of polyethylene terephthalate (PET). The realization of efficient ethylene glycol oxidation can further realize the recycling of waste PET. At present, there have been a lot of researches on catalysts for Ethylene glycol oxidation(EGOR), among which transition metal catalysts (including Fe, Co, Ni and other conventional non-precious metals and Pt, Pb and other precious metals) have a good application prospect in the oxidation reaction of ethylene glycol due to their unique electronic structure. In this work, the synthesis strategies of transition metal catalysts used for electrocatalytic oxidation of EG were summarized and the performance of different types of catalysts in ethylene glycol oxidation was reviewed. Advanced characterization methods were used to understand the oxidation mechanism of EG and to control the EGOR intermediates into target products. Therefore, we need to further explore efficient ethylene glycol oxidation catalysts to achieve efficient reactions.
{"title":"Research progress of transition metal catalysts for electrocatalytic Ethylene glycol oxidation","authors":"Hongjing Wu, Xiaoyue Zheng, Jiajia Liu, Yanru Yuan, Yuquan Yang, Chenjing Wang, Li Zhou, Lulu Wang, Binbin Jia, Xiaoyu Fan, Jinlong Zheng","doi":"10.1039/d4nr05000b","DOIUrl":"https://doi.org/10.1039/d4nr05000b","url":null,"abstract":"As a small alcohol molecule with low oxidation potential, ethylene glycol is also a key monomer in the production of polyethylene terephthalate (PET). The realization of efficient ethylene glycol oxidation can further realize the recycling of waste PET. At present, there have been a lot of researches on catalysts for Ethylene glycol oxidation(EGOR), among which transition metal catalysts (including Fe, Co, Ni and other conventional non-precious metals and Pt, Pb and other precious metals) have a good application prospect in the oxidation reaction of ethylene glycol due to their unique electronic structure. In this work, the synthesis strategies of transition metal catalysts used for electrocatalytic oxidation of EG were summarized and the performance of different types of catalysts in ethylene glycol oxidation was reviewed. Advanced characterization methods were used to understand the oxidation mechanism of EG and to control the EGOR intermediates into target products. Therefore, we need to further explore efficient ethylene glycol oxidation catalysts to achieve efficient reactions.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"95 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822422","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}
Carla I. M Santos, Ana Catarina Almeida, Ana L. F. Martins, Ana R. Araújo, Leandro Lourenço, Gil Alberto Batista Gonçalves, Maria da Graça P. M. S. Neves
Since their discovery, carbon dots (CDs) have been extensively studied for their potential in diverse applications owing to their unique properties such as high biocompatibility, excellent water solubility, low toxicity, minimal photobleaching, and exceptional chemical versatility. These characteristics position CDs as promising candidates for overcoming the limitations of various molecular compounds. This review provides a comprehensive analysis of the synergistic effects arising from the integration of CDs and phthalocyanines (Pcs) to form hybrids with distinct photophysical and photochemical properties. This study explores recent advances in the development of Pc@CDs hybrids, focusing on their synthesis, conjugation strategies, and synergistic effects that impact their performance in several areas, including optical sensing, electrocatalysis, photodynamic processes and photocatalysis. Emphasis is given to chemical methods that enable efficient conjugation and the role of reactive oxygen species generation in driving these applications. Additionally, the discussion also addresses key challenges, highlighting innovative solutions, and proposing future research directions to fully harness the potential of Pc@CDs hybrids in diverse scientific and technological breakthroughs.
{"title":"Carbon dots-phthalocyanine hybrids: synergistic effects that boost their multifaceted applications","authors":"Carla I. M Santos, Ana Catarina Almeida, Ana L. F. Martins, Ana R. Araújo, Leandro Lourenço, Gil Alberto Batista Gonçalves, Maria da Graça P. M. S. Neves","doi":"10.1039/d5nr00466g","DOIUrl":"https://doi.org/10.1039/d5nr00466g","url":null,"abstract":"Since their discovery, carbon dots (CDs) have been extensively studied for their potential in diverse applications owing to their unique properties such as high biocompatibility, excellent water solubility, low toxicity, minimal photobleaching, and exceptional chemical versatility. These characteristics position CDs as promising candidates for overcoming the limitations of various molecular compounds. This review provides a comprehensive analysis of the synergistic effects arising from the integration of CDs and phthalocyanines (Pcs) to form hybrids with distinct photophysical and photochemical properties. This study explores recent advances in the development of Pc@CDs hybrids, focusing on their synthesis, conjugation strategies, and synergistic effects that impact their performance in several areas, including optical sensing, electrocatalysis, photodynamic processes and photocatalysis. Emphasis is given to chemical methods that enable efficient conjugation and the role of reactive oxygen species generation in driving these applications. Additionally, the discussion also addresses key challenges, highlighting innovative solutions, and proposing future research directions to fully harness the potential of Pc@CDs hybrids in diverse scientific and technological breakthroughs.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"27 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143824843","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}
Samuel Aldana Delgado, Cara-Lena Nies, Michael Nolan
The miniaturization of electronic devices poses severe challenges for metal interconnect deposition in back end of line processing due to the decreasing volume available in the interconnect via. Cu is currently used as the interconnect metal and requires barrier and liner layers to prevent diffusion into silicon and promote smooth film growth. However, these layers occupy critical space in the already narrow, high-aspect ratio interconnect vias. Designing combined barrier/liner materials is critical tooptimizingavailable interconnect volume. While film morphology can be predicted from first principles calculations, e.g. Density Functional Theory (DFT), modelling deposition to understand the evolution of metal growth and optimize barrier material design and metal deposition is extremely challenging. We present an atomistic kinetic Monte Carlo (kMC) investigation of Cu deposition on Ru-modified TaN as a potential dual-function barrier/line material. Using DFT-calculated activation barriers, we predict Cu morphology on these technologically important substrates at back end of line processing temperatures. We evaluate 2D vs. 3D morphology and film quality by analyzing film roughness, island size, substrate exposure, layer occupation rate, film compactness and the effect of annealing. Our results show Ru-modified TaN with 50% Ru incorporation significantly reduces roughness and islanding, promoting desired 2D growth. Vacuum annealing further promotes smooth Cu films, eliminating vacancy defects on Ru-modified substrates, while TaN promotes further island formation. This demonstrates the potential of Ru-TaN in optimizing Cu deposition for advanced CMOS interconnects and showcases a new, robust approach for atomistic simulation of metal deposition on a range of substrates.
电子设备的微型化给后端加工中的金属互连沉积带来了严峻的挑战，因为互连通孔的可用体积越来越小。铜目前用作互连金属，需要阻挡层和衬垫层来防止扩散到硅中，并促进薄膜的顺利生长。然而，这些层占据了本已狭窄的高纵横比互连通孔的关键空间。设计组合式阻挡层/衬垫材料对于优化可用互连体积至关重要。虽然可以通过密度泛函理论（DFT）等第一性原理计算预测薄膜形态，但建立沉积模型以了解金属生长的演变过程并优化阻挡层材料设计和金属沉积却极具挑战性。我们介绍了一项原子动力学蒙特卡洛（kMC）研究，研究铜在作为潜在双功能阻挡层/线材料的 Ru 改性 TaN 上的沉积。利用 DFT 计算的活化势垒，我们预测了铜在这些具有重要技术意义的基底上在生产线后端加工温度下的形态。我们通过分析薄膜粗糙度、岛尺寸、基底暴露、层占用率、薄膜致密性和退火的影响，评估了二维与三维形态和薄膜质量。我们的研究结果表明，掺入 50% Ru 的 Ru 改性 TaN 能显著减少粗糙度和孤岛，促进理想的二维生长。真空退火进一步促进了铜薄膜的平滑，消除了 Ru 改性基底上的空位缺陷，而 TaN 则进一步促进了孤岛的形成。这证明了 Ru-TaN 在优化先进 CMOS 互连的铜沉积方面的潜力，并展示了在一系列基底上进行金属沉积的原子模拟的全新、稳健的方法。
{"title":"Control of Cu morphology on TaN barrier and combined Ru-TaN barrier/liner substrates for nanoscale interconnects from atomistic kinetic Monte Carlo simulations","authors":"Samuel Aldana Delgado, Cara-Lena Nies, Michael Nolan","doi":"10.1039/d4nr04505j","DOIUrl":"https://doi.org/10.1039/d4nr04505j","url":null,"abstract":"The miniaturization of electronic devices poses severe challenges for metal interconnect deposition in back end of line processing due to the decreasing volume available in the interconnect via. Cu is currently used as the interconnect metal and requires barrier and liner layers to prevent diffusion into silicon and promote smooth film growth. However, these layers occupy critical space in the already narrow, high-aspect ratio interconnect vias. Designing combined barrier/liner materials is critical tooptimizingavailable interconnect volume. While film morphology can be predicted from first principles calculations, e.g. Density Functional Theory (DFT), modelling deposition to understand the evolution of metal growth and optimize barrier material design and metal deposition is extremely challenging. We present an atomistic kinetic Monte Carlo (kMC) investigation of Cu deposition on Ru-modified TaN as a potential dual-function barrier/line material. Using DFT-calculated activation barriers, we predict Cu morphology on these technologically important substrates at back end of line processing temperatures. We evaluate 2D vs. 3D morphology and film quality by analyzing film roughness, island size, substrate exposure, layer occupation rate, film compactness and the effect of annealing. Our results show Ru-modified TaN with 50% Ru incorporation significantly reduces roughness and islanding, promoting desired 2D growth. Vacuum annealing further promotes smooth Cu films, eliminating vacancy defects on Ru-modified substrates, while TaN promotes further island formation. This demonstrates the potential of Ru-TaN in optimizing Cu deposition for advanced CMOS interconnects and showcases a new, robust approach for atomistic simulation of metal deposition on a range of substrates.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"14 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819385","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}
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