Zakaria Ziani, Caterina Bellatreccia, Filippo Piero Battaglia, Giacomo Morselli, Alessandro Gradone, Paola Ceroni, Marco Villa
Azobenzene derivatives have long been studied for their photochromic behaviour. One of the greatest challenges in this field is the quantitative (E) to (Z) photoconversion triggered by visible light irradiation. In this work, the synthesis and characterization of CuInS2 quantum dots (CIS-QDs) appended with azobenzene units are reported: quantitative (E) → (Z) isomerisation is obtained by visible light (e.g., λex = 533 nm). Interestingly, catalytic amounts of CIS-QDs allow the full photoconversion of ungrafted (E)-azobenzene derivatives into the corresponding (Z)-isomers using visible light. This peculiar behaviour is associated with the direct complexation of the (Z)-isomer on the QD surface.
{"title":"Copper indium sulfide quantum dots enabling quantitative visible light photoisomerisation of (<i>E</i>)-azobenzene chromophores.","authors":"Zakaria Ziani, Caterina Bellatreccia, Filippo Piero Battaglia, Giacomo Morselli, Alessandro Gradone, Paola Ceroni, Marco Villa","doi":"10.1039/d4nr01997k","DOIUrl":"https://doi.org/10.1039/d4nr01997k","url":null,"abstract":"<p><p>Azobenzene derivatives have long been studied for their photochromic behaviour. One of the greatest challenges in this field is the quantitative (<i>E</i>) to (<i>Z</i>) photoconversion triggered by visible light irradiation. In this work, the synthesis and characterization of CuInS<sub>2</sub> quantum dots (CIS-QDs) appended with azobenzene units are reported: quantitative (<i>E</i>) → (<i>Z</i>) isomerisation is obtained by visible light (<i>e.g.</i>, <i>λ</i><sub>ex</sub> = 533 nm). Interestingly, catalytic amounts of CIS-QDs allow the full photoconversion of ungrafted (<i>E</i>)-azobenzene derivatives into the corresponding (<i>Z</i>)-isomers using visible light. This peculiar behaviour is associated with the direct complexation of the (<i>Z</i>)-isomer on the QD surface.</p>","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141441827","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}
Anran Wang, Xingguang Wu, Siwen Zhao, Zheng Han, Yi Shi, Giulio Cerullo, Fengqiu Wang
Van der Waals heterostructures based on transition metal dichalcogenides (TMDs) have emerged as excellent candidates for next-generation optoelectronics and valleytronics, due to their fascinating physical properties. The understanding and active control of the relaxation dynamics of heterostructures play a crucial role in device design and optimization. Here, we investigate the back-gate modulation of exciton dynamics in a WS2/WSe2 heterostructure by combining time-resolved photoluminescence (TRPL) and transient absorption spectroscopy (TAS) at cryogenic temperatures. We find that the non-radiative relaxation lifetimes of photocarriers in heterostructures can be electrically controlled for samples with different twist-angles, whereas such lifetime tuning is not present in standalone monolayers. We attribute such an observation to doping-controlled competition between interlayer and intralayer recombination pathways in high-quality WS2/WSe2 samples. The simultaneous measurement of TRPL and TAS lifetimes within the same sample provides additional insights into the influence of coexisting excitons and background carriers on the photo response, and points to the potential of tailoring light-matter interactions in TMDs heterostructures.
{"title":"Electrically-tunable non-radiative lifetime in WS2/WSe2 heterostructure","authors":"Anran Wang, Xingguang Wu, Siwen Zhao, Zheng Han, Yi Shi, Giulio Cerullo, Fengqiu Wang","doi":"10.1039/d4nr01982b","DOIUrl":"https://doi.org/10.1039/d4nr01982b","url":null,"abstract":"Van der Waals heterostructures based on transition metal dichalcogenides (TMDs) have emerged as excellent candidates for next-generation optoelectronics and valleytronics, due to their fascinating physical properties. The understanding and active control of the relaxation dynamics of heterostructures play a crucial role in device design and optimization. Here, we investigate the back-gate modulation of exciton dynamics in a WS2/WSe2 heterostructure by combining time-resolved photoluminescence (TRPL) and transient absorption spectroscopy (TAS) at cryogenic temperatures. We find that the non-radiative relaxation lifetimes of photocarriers in heterostructures can be electrically controlled for samples with different twist-angles, whereas such lifetime tuning is not present in standalone monolayers. We attribute such an observation to doping-controlled competition between interlayer and intralayer recombination pathways in high-quality WS2/WSe2 samples. The simultaneous measurement of TRPL and TAS lifetimes within the same sample provides additional insights into the influence of coexisting excitons and background carriers on the photo response, and points to the potential of tailoring light-matter interactions in TMDs heterostructures.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141439793","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}
Electrocatalytic nitrate reduction reaction (NO3RR) is an ideal NH3 synthesis route with ease of operation, high energy efficiency, and low environmental detriment. The electrocatalytic cathodes play a dominant role in NO3RR. Herein, we constructed a carbon fiber paper-supported CuOx nanoarray catalyst (CP/CuOx) by an in situ electrochemical reconstruction method for NO3−-to-NH3 conversion. XRD, in situ Raman, and XPS characterizations unveil the CP/CuOx is a polycrystalline-faceted composite copper nanocatalyst with a valence composition containing Cu0, Cu+ and Cu2+. The CP/CuOx shows more efficient NO3−-to-NH3 conversion than CP/Cu and CP/Cu2O, which indicates the coexistence of various Cu valence states could play a dominant role. The CP/CuOx with suitable Cu2+ content that obtained by adjusting the conductivity during the in situ electrochemical reconstruction process exhibited more than 90% of Faradaic efficiencies for NO3RR in the broad range of -0.3 to -1.0 V vs. RHE, 28.65 mg cm-2 h-1 of peak ammonia yield, and stable NO3RR efficiencies for ten cycles. These findings suggest that the CP/CuOx with suitable copper valence states obtained by fine-tuning the conductivity of the electrochemical reconstruction may provide a competitive cathode catalyst for achieving excellent activity and selectivity of NO3−-to-NH3 conversion.
{"title":"Conductivity-mediated in situ electrochemical reconstruction of CuOx for nitrate reduction to ammonia","authors":"Hao Liang, Yinqiao Zhang, Xiaona Zhang, Zhao Erzhuo, Wendan Xue, Enguang Nie, Jianqiu Chen, Sijin Zuo, Minghua Zhou","doi":"10.1039/d4nr01625d","DOIUrl":"https://doi.org/10.1039/d4nr01625d","url":null,"abstract":"Electrocatalytic nitrate reduction reaction (NO3RR) is an ideal NH3 synthesis route with ease of operation, high energy efficiency, and low environmental detriment. The electrocatalytic cathodes play a dominant role in NO3RR. Herein, we constructed a carbon fiber paper-supported CuOx nanoarray catalyst (CP/CuOx) by an in situ electrochemical reconstruction method for NO3−-to-NH3 conversion. XRD, in situ Raman, and XPS characterizations unveil the CP/CuOx is a polycrystalline-faceted composite copper nanocatalyst with a valence composition containing Cu0, Cu+ and Cu2+. The CP/CuOx shows more efficient NO3−-to-NH3 conversion than CP/Cu and CP/Cu2O, which indicates the coexistence of various Cu valence states could play a dominant role. The CP/CuOx with suitable Cu2+ content that obtained by adjusting the conductivity during the in situ electrochemical reconstruction process exhibited more than 90% of Faradaic efficiencies for NO3RR in the broad range of -0.3 to -1.0 V vs. RHE, 28.65 mg cm-2 h-1 of peak ammonia yield, and stable NO3RR efficiencies for ten cycles. These findings suggest that the CP/CuOx with suitable copper valence states obtained by fine-tuning the conductivity of the electrochemical reconstruction may provide a competitive cathode catalyst for achieving excellent activity and selectivity of NO3−-to-NH3 conversion.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141436137","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}
Peptide nucleic acids (PNAs) are charge-neutral synthetic DNA/RNA analogues. In many aspects of biology and biotechnology, the details of DNA and PNA melting reaction coordinates are crucial, and their associative/dissociative details remain inadequately understood. In the current study, we have attempted to gain insights into comparative melting pathways and binding affinity of iso-sequences of an 18-mer PNA-DNA-PNA triplex and the analogous DNA-DNA-DNA triplex, and DNA-DNA and PNA-DNA duplexes. It is intriguing that while the DNA-DNA-DNA triplex melts in two sequential steps, the PNA-DNA-PNA triplex melts in a single step and the mechanistic aspects for this difference are still not clear. We report an all-atom molecular dynamics simulation of both complexes in the temperature range of 300 to 500 K with 20 K intervals. Based on the trajectory analysis, we provide evidence that the association and dissociation are dictated by the differences in fraying-peeling effects from either terminus to the center in a zipper pattern among the PNA-DNA-PNA triplex and DNA-DNA-DNA triplexes. These are shown to be governed by the different characteristics of H-bonding, RMSD, and Free Energy Landscape (FEL) as analyzed by PCA, leading to the DNA-DNA-DNA triplex exhibiting sequential melting, while the PNA-DNA-PNA triplex shows cooperative melting of the whole fragment in a single-step. The PNA-DNA-PNA triplex base pairs are thermodynamically more stable than the DNA-DNA-DNA triplex, with the binding affinity of PNA-TFO to the PNA : DNA duplex being higher than that of DNA-TFO to the DNA : DNA duplex. The investigation of the association/dissociation of PNA-TFO to the PNA-DNA duplex has relevance and importance in the emerging effective applications of oligonucleotide therapy.
{"title":"Dynamics of terminal fraying-peeling and hydrogen bonds dictates the sequential <i>vs</i>. cooperative melting pathways of nanoscale DNA and PNA triplexes.","authors":"Sandip Mandal, Krishna N Ganesh, Prabal K Maiti","doi":"10.1039/d4nr01104j","DOIUrl":"https://doi.org/10.1039/d4nr01104j","url":null,"abstract":"<p><p>Peptide nucleic acids (PNAs) are charge-neutral synthetic DNA/RNA analogues. In many aspects of biology and biotechnology, the details of DNA and PNA melting reaction coordinates are crucial, and their associative/dissociative details remain inadequately understood. In the current study, we have attempted to gain insights into comparative melting pathways and binding affinity of iso-sequences of an 18-mer PNA-DNA-PNA triplex and the analogous DNA-DNA-DNA triplex, and DNA-DNA and PNA-DNA duplexes. It is intriguing that while the DNA-DNA-DNA triplex melts in two sequential steps, the PNA-DNA-PNA triplex melts in a single step and the mechanistic aspects for this difference are still not clear. We report an all-atom molecular dynamics simulation of both complexes in the temperature range of 300 to 500 K with 20 K intervals. Based on the trajectory analysis, we provide evidence that the association and dissociation are dictated by the differences in fraying-peeling effects from either terminus to the center in a zipper pattern among the PNA-DNA-PNA triplex and DNA-DNA-DNA triplexes. These are shown to be governed by the different characteristics of H-bonding, RMSD, and Free Energy Landscape (FEL) as analyzed by PCA, leading to the DNA-DNA-DNA triplex exhibiting sequential melting, while the PNA-DNA-PNA triplex shows cooperative melting of the whole fragment in a single-step. The PNA-DNA-PNA triplex base pairs are thermodynamically more stable than the DNA-DNA-DNA triplex, with the binding affinity of PNA-TFO to the PNA : DNA duplex being higher than that of DNA-TFO to the DNA : DNA duplex. The investigation of the association/dissociation of PNA-TFO to the PNA-DNA duplex has relevance and importance in the emerging effective applications of oligonucleotide therapy.</p>","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430965","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}
Jun Yong Oh, Min-Seok Seu, Ayan Kumar Barui, Haewon Ok, Dohyun Kim, Eunshil Choi, Junmo Seong, Myoung Soo Lah, Ja-Hyoung Ryu
Targeted drug delivery using metal-organic frameworks (MOFs) has shown significant progress. However, the tumor microenvironment (TME) impedes efficient MOF particle transfer into tumor cells. To tackle this issue, we pre-coated nano-sized MOF-808 particles with multifunctional proteins: glutathione S-transferase (GST)-affibody (Afb) and collagenase, aiming to navigate the TME more effectively. The surface of MOF-808 particles is coated with GST-Afb—a fusion protein of GST and human epidermal growth factor receptor 2 (HER2) Afb or epidermal growth factor receptor (EGFR) Afb which has target affinity. We also added collagenase enzymes capable of breaking down collagen in the extracellular matrix (ECM) through supramolecular conjugation, all without chemical modification. By stabilizing these proteins on the surface, GST-Afb mitigate biomolecule absorption, facilitating specific tumor cell targeting. Simultaneously, collagenase degrades the ECM in the TME, enabling deep tissue penetration of MOF particles. Our resulting system, termed collagenase-GST-Afb-MOF-808 (Col-Afb-M808), minimizes undesired interactions between MOF particles and external biological proteins. It not only induces cell death through Afb-mediated cell-specific targeting, but also showcases advanced cellular internalization in 3D multicellular spheroid cancer models, with effective deep tissue penetration. The therapeutic efficacy of Col-Afb-M808 was further assessed via in vivo imaging and evaluation of tumor inhibition following injection of IR-780 loaded Col-Afb-M808 in 4T1tumor-bearing nude mice. This study offers key insights into the regulation of the multifunctional protein-adhesive surface of MOF particles, paving the way for the designing even more effective targeted drug delivery systems with nano-sized MOF particles.
{"title":"A multifunctional protein pre-coated metal-organic framework for targeted delivery with deep tissue penetration","authors":"Jun Yong Oh, Min-Seok Seu, Ayan Kumar Barui, Haewon Ok, Dohyun Kim, Eunshil Choi, Junmo Seong, Myoung Soo Lah, Ja-Hyoung Ryu","doi":"10.1039/d4nr02345e","DOIUrl":"https://doi.org/10.1039/d4nr02345e","url":null,"abstract":"Targeted drug delivery using metal-organic frameworks (MOFs) has shown significant progress. However, the tumor microenvironment (TME) impedes efficient MOF particle transfer into tumor cells. To tackle this issue, we pre-coated nano-sized MOF-808 particles with multifunctional proteins: glutathione S-transferase (GST)-affibody (Afb) and collagenase, aiming to navigate the TME more effectively. The surface of MOF-808 particles is coated with GST-Afb—a fusion protein of GST and human epidermal growth factor receptor 2 (HER2) Afb or epidermal growth factor receptor (EGFR) Afb which has target affinity. We also added collagenase enzymes capable of breaking down collagen in the extracellular matrix (ECM) through supramolecular conjugation, all without chemical modification. By stabilizing these proteins on the surface, GST-Afb mitigate biomolecule absorption, facilitating specific tumor cell targeting. Simultaneously, collagenase degrades the ECM in the TME, enabling deep tissue penetration of MOF particles. Our resulting system, termed collagenase-GST-Afb-MOF-808 (Col-Afb-M808), minimizes undesired interactions between MOF particles and external biological proteins. It not only induces cell death through Afb-mediated cell-specific targeting, but also showcases advanced cellular internalization in 3D multicellular spheroid cancer models, with effective deep tissue penetration. The therapeutic efficacy of Col-Afb-M808 was further assessed via in vivo imaging and evaluation of tumor inhibition following injection of IR-780 loaded Col-Afb-M808 in 4T1tumor-bearing nude mice. This study offers key insights into the regulation of the multifunctional protein-adhesive surface of MOF particles, paving the way for the designing even more effective targeted drug delivery systems with nano-sized MOF particles.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141436123","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}
Salma Habib, Mohammed Talhami, Amani Hassanein, Elsadig Mahdi, Maryam Al-Ejji, Mohammad K. Hassan, Ali Altaee, Probir Das, Alaa AlHawari
Iron oxide magnetic nanoparticles (MNPs) are crucial in various areas due to their unique magnetic properties. However, their practical use is often limited by instability and aggregation in aqueous solutions. This review explores the advanced technique of dendrimer functionalization to enhance MNP stability and expand their application potential. Dendrimers, with their symmetric and highly branched structure, effectively stabilize MNPs and provide tailored functional sites for specific applications. We summarize key synthetic modifications, focusing on the impacts of dendrimer size, surface chemistry, and the balance of chemical (e.g., coordination, anchoring) and physical (e.g., electrostatic, hydrophobic) interactions on nanocomposite properties. Current challenges such as dendrimer toxicity, control over dendrimer distribution on MNPs, and the need for biocompatibility are discussed, alongside potential solutions involving advanced characterization techniques. This review highlights significant opportunities in environmental, biomedical, and water treatment applications, stressing the necessity for ongoing research to fully leverage dendrimer-functionalized MNPs. Insights offered here aim to guide further development and application of these promising nanocomposites.
{"title":"Advances in Functionalization and Conjugation Mechanisms of Dendrimers with Iron Oxide Magnetic Nanoparticles","authors":"Salma Habib, Mohammed Talhami, Amani Hassanein, Elsadig Mahdi, Maryam Al-Ejji, Mohammad K. Hassan, Ali Altaee, Probir Das, Alaa AlHawari","doi":"10.1039/d4nr01376j","DOIUrl":"https://doi.org/10.1039/d4nr01376j","url":null,"abstract":"Iron oxide magnetic nanoparticles (MNPs) are crucial in various areas due to their unique magnetic properties. However, their practical use is often limited by instability and aggregation in aqueous solutions. This review explores the advanced technique of dendrimer functionalization to enhance MNP stability and expand their application potential. Dendrimers, with their symmetric and highly branched structure, effectively stabilize MNPs and provide tailored functional sites for specific applications. We summarize key synthetic modifications, focusing on the impacts of dendrimer size, surface chemistry, and the balance of chemical (e.g., coordination, anchoring) and physical (e.g., electrostatic, hydrophobic) interactions on nanocomposite properties. Current challenges such as dendrimer toxicity, control over dendrimer distribution on MNPs, and the need for biocompatibility are discussed, alongside potential solutions involving advanced characterization techniques. This review highlights significant opportunities in environmental, biomedical, and water treatment applications, stressing the necessity for ongoing research to fully leverage dendrimer-functionalized MNPs. Insights offered here aim to guide further development and application of these promising nanocomposites.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141439871","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}
Marianna Testa, Antonio De Santis, Gemma Maria Tinti, Alessandro Paoloni, Giuseppe Papalino, Giulietto Felici, Zaza Chubinidze, Fabio Matteocci, Matthias Auf der Maur, Silvia Rizzato, Leonardo Lo Presti, Ilenia Viola, Silvio Morganti, Chiara Rovelli
We report the detection of high energy electrons of some hundreds of MeV, crossing a methylammonium lead bromide single crystal device with sensitivity down to single electrons. In the device, the released energy is close to the energy released by minimum-ionizing particles. This is the first demonstration of a perovskite-based device that can be used for tracking and counting minimum-ionizing charged particles. The device reaches the single particle sensitivity with a low bias voltage of 5 V. It also shows a good linearity of the response as a function of the number of electrons in a dynamic range of approximately 10^4.
我们报告了通过甲基溴化铅铵单晶装置探测到的约数百兆电子伏的高能电子，其灵敏度低至单个电子。在该装置中，释放的能量接近于最小电离粒子释放的能量。这是首次展示可用于跟踪和计数最小电离带电粒子的基于包晶的装置。该装置在 5 V 的低偏置电压下就能达到单粒子灵敏度。它还显示出在约 10^4 的动态范围内，响应与电子数的函数具有良好的线性关系。
{"title":"Direct detection of minimum ionizing charged particles in perovskite single crystal detector with single particle sensitivity","authors":"Marianna Testa, Antonio De Santis, Gemma Maria Tinti, Alessandro Paoloni, Giuseppe Papalino, Giulietto Felici, Zaza Chubinidze, Fabio Matteocci, Matthias Auf der Maur, Silvia Rizzato, Leonardo Lo Presti, Ilenia Viola, Silvio Morganti, Chiara Rovelli","doi":"10.1039/d4nr01556h","DOIUrl":"https://doi.org/10.1039/d4nr01556h","url":null,"abstract":"We report the detection of high energy electrons of some hundreds of MeV, crossing a methylammonium lead bromide single crystal device with sensitivity down to single electrons. In the device, the released energy is close to the energy released by minimum-ionizing particles. This is the first demonstration of a perovskite-based device that can be used for tracking and counting minimum-ionizing charged particles. The device reaches the single particle sensitivity with a low bias voltage of 5 V. It also shows a good linearity of the response as a function of the number of electrons in a dynamic range of approximately 10^4.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430408","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}
Amr Elgendy, Athanasios A Papaderakis, Andinet Ejigu, Katharina Helmbrecht, Ben Spencer, Axel Gross, Alex Walton, David J Lewis, Robert Dryfe
The nanoscale form of the Chevrel phase, Mo6S8, is demonstrated to be a highly efficient zinc-free anode in aqueous zinc ion hybrid supercapacitors (ZIHSCs). The unique morphological characteristics of the material when its dimensions approach the nanoscale result in fast zinc intercalation kinetics that surpass the ion transport rate reported for some of the most promising materials, such as TiS2 and TiSe2. In-situ Raman spectroscopy, post-mortem X-ray diffraction, Hard X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations were combined to understand the overall mechanism of the zinc ion (de)intercalation process. The previously unknown formation of the sulfur deficient Zn2.9Mo15S19 (Zn1.6Mo6S7.6) phase is identified, leading to a re-evaluation of the mechanism of the (de)intercalation process. A full cell comprised of an activated carbon (YEC-8A) positive electrode, delivers a cell capacity of 38 mAh/g and an energy density of 43.8 Wh/kg at a specific current density of 0.2 A/g. The excellent cycling stability of the device is demonstrated for up to 8000 cycles at 3 A/g with a coulombic efficiency close to 100%. Post-mortem microscopic studies reveal the absence of dendrite formation at the nanosized Mo6S8 anode, in stark contrast to the state-of-the-art zinc electrode.
{"title":"Nanosized Chevrel Phases for Dendrite-Free Zinc-Ion Based Energy Storage: Unraveling the Phase Transformations","authors":"Amr Elgendy, Athanasios A Papaderakis, Andinet Ejigu, Katharina Helmbrecht, Ben Spencer, Axel Gross, Alex Walton, David J Lewis, Robert Dryfe","doi":"10.1039/d4nr01238k","DOIUrl":"https://doi.org/10.1039/d4nr01238k","url":null,"abstract":"The nanoscale form of the Chevrel phase, Mo6S8, is demonstrated to be a highly efficient zinc-free anode in aqueous zinc ion hybrid supercapacitors (ZIHSCs). The unique morphological characteristics of the material when its dimensions approach the nanoscale result in fast zinc intercalation kinetics that surpass the ion transport rate reported for some of the most promising materials, such as TiS2 and TiSe2. In-situ Raman spectroscopy, post-mortem X-ray diffraction, Hard X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations were combined to understand the overall mechanism of the zinc ion (de)intercalation process. The previously unknown formation of the sulfur deficient Zn2.9Mo15S19 (Zn1.6Mo6S7.6) phase is identified, leading to a re-evaluation of the mechanism of the (de)intercalation process. A full cell comprised of an activated carbon (YEC-8A) positive electrode, delivers a cell capacity of 38 mAh/g and an energy density of 43.8 Wh/kg at a specific current density of 0.2 A/g. The excellent cycling stability of the device is demonstrated for up to 8000 cycles at 3 A/g with a coulombic efficiency close to 100%. Post-mortem microscopic studies reveal the absence of dendrite formation at the nanosized Mo6S8 anode, in stark contrast to the state-of-the-art zinc electrode.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430413","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}
Jing Zhou, Qianyue Liang, Pu Huang, Jing Xu, Tengfei Niu, Yao Wang, Yuming Dong, Jiawei Zhang
Electrocatalytic reduction of CO2 into multicarbon (C2+) products offers a promising pathway for CO2 utilization. However, achieving high selectivity towards multicarbon alcohols, such as ethanol, remains a challenge. In this work, we present a novel CuO nanoflower catalyst with engineered tip curvature, achieving remarkable selectivity and efficiency in the electroreduction of CO2 to ethanol. This catalyst exhibits an ethanol Faradaic efficiency (FEethanol) of 47% and a formation rate of 325 μmol h-1 cm-2, with an overall C2+ product Faradaic efficiency (FEC2+) reaching ~78%. We attribute this performance to the catalyst's sharp tip, which generates a strong local electric field, thereby accelerating CO2 activation and facilitating C-C coupling for deep CO2 reduction. In situ Raman spectroscopy reveals an increased *OH coverage under operating conditions, where the enhanced *OH adsorption facilitates the stabilization of *CHCOH intermediates through hydrogen bonding interaction, thus improving ethanol selectivity. Our findings demonstrate the pivotal role of local electric fields in altering reaction kinetics for CO2 electroreduction, presenting a new avenue for catalyst design aiming at converting CO2 to ethanol.
{"title":"Efficient CO2 Electroreduction to Ethanol Enabled by Tip-Curvature-Induced Local Electric Fields","authors":"Jing Zhou, Qianyue Liang, Pu Huang, Jing Xu, Tengfei Niu, Yao Wang, Yuming Dong, Jiawei Zhang","doi":"10.1039/d4nr01173b","DOIUrl":"https://doi.org/10.1039/d4nr01173b","url":null,"abstract":"Electrocatalytic reduction of CO2 into multicarbon (C2+) products offers a promising pathway for CO2 utilization. However, achieving high selectivity towards multicarbon alcohols, such as ethanol, remains a challenge. In this work, we present a novel CuO nanoflower catalyst with engineered tip curvature, achieving remarkable selectivity and efficiency in the electroreduction of CO2 to ethanol. This catalyst exhibits an ethanol Faradaic efficiency (FEethanol) of 47% and a formation rate of 325 μmol h-1 cm-2, with an overall C2+ product Faradaic efficiency (FEC2+) reaching ~78%. We attribute this performance to the catalyst's sharp tip, which generates a strong local electric field, thereby accelerating CO2 activation and facilitating C-C coupling for deep CO2 reduction. In situ Raman spectroscopy reveals an increased *OH coverage under operating conditions, where the enhanced *OH adsorption facilitates the stabilization of *CHCOH intermediates through hydrogen bonding interaction, thus improving ethanol selectivity. Our findings demonstrate the pivotal role of local electric fields in altering reaction kinetics for CO2 electroreduction, presenting a new avenue for catalyst design aiming at converting CO2 to ethanol.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430482","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}
Dan Xie, Youyou Deng, Xunlong Ji, Yiyan Zhang, Wentao Zhang, Zijin Hong, Wenjing Liu, Jingjing Du, Zhenli Sun
A novel breakthrough has been achieved in gas detection through the innovative application of Surface-Enhanced Raman Scattering (SERS) to hydrogen (H2) detection for the first time. This study capitalizes on the unique SERS effects of gold nanoparticles coupled with the redox interaction between hydrogen and crystal violet, allowing for the development of a magnetic SERS probe that demonstrated enhanced sensitivity and specificity. This new probe can detect hydrogen concentrations as low as 1% by volume in gaseous environments, offering a substantial improvement over the detection limits of traditional hydrogen alarms. Further, this report comprehensively detailed the synthesis of the FA-CV materials, instrumental analysis, and an in-depth evaluation of the SERS performance of the FA-CV substrate, underlining the outstanding sensitivity, stability, and recyclability of the probe. The introduction of SERS in this novel capacity not only contributes a valuable approach to gas sensing technologies but, additionally, it suggests promising avenues for the application of SERS in environmental monitoring and energy security, thus, illustrating the adaptability and potential impact of this powerful technique.
{"title":"Crystal violet-modified Fe3O4@Au SERS probes: A novel highly sensitive method for H2 detection","authors":"Dan Xie, Youyou Deng, Xunlong Ji, Yiyan Zhang, Wentao Zhang, Zijin Hong, Wenjing Liu, Jingjing Du, Zhenli Sun","doi":"10.1039/d4nr01690d","DOIUrl":"https://doi.org/10.1039/d4nr01690d","url":null,"abstract":"A novel breakthrough has been achieved in gas detection through the innovative application of Surface-Enhanced Raman Scattering (SERS) to hydrogen (H2) detection for the first time. This study capitalizes on the unique SERS effects of gold nanoparticles coupled with the redox interaction between hydrogen and crystal violet, allowing for the development of a magnetic SERS probe that demonstrated enhanced sensitivity and specificity. This new probe can detect hydrogen concentrations as low as 1% by volume in gaseous environments, offering a substantial improvement over the detection limits of traditional hydrogen alarms. Further, this report comprehensively detailed the synthesis of the FA-CV materials, instrumental analysis, and an in-depth evaluation of the SERS performance of the FA-CV substrate, underlining the outstanding sensitivity, stability, and recyclability of the probe. The introduction of SERS in this novel capacity not only contributes a valuable approach to gas sensing technologies but, additionally, it suggests promising avenues for the application of SERS in environmental monitoring and energy security, thus, illustrating the adaptability and potential impact of this powerful technique.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430495","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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