Transforming CO2 to CO via reverse water-gas shift (RWGS) reaction is widely regarded as a promising technique for improving the efficiency and economics of the CO2 utilization processes. Moreover, it is also considered as a pathway towards e-fuels. Cu-oxide catalysts are widely explored for low-temperature RWGS, nevertheless, they tend to deactivate significantly in applied reaction conditions due to the agglomeration of copper particles at elevated temperatures. Herein, we have synthesized homogeneously distributed Cu metallic nanoparticles supported on Mo2C for RWGS reaction by a unique approach in-situ carburization of metal-organic frameworks (MOFs) comprised of Cu-based MOF i.e., HKUST-1 encapsulating molybdenum-based polyoxometalates. The newly derived Na-Cu-Mo2C nanocomposite catalyst system exhibits excellent catalytic performance with a CO production rate of 3230.0 mmol gcat-1 h-1 with 100 % CO selectivity. Even after 250 h of stability test, the catalyst remained active with more than 80 % of its initial activity.
{"title":"Polyoxometalate-HKUST-1 composite derived nanostructured Na-Cu-Mo2C catalyst for efficient reverse water gas shift reaction","authors":"Gaje rawat, Satyajit Panda, Siddharth Sapan, Pranay Rajendra Chandewar, Jogender Singh, Ankush V. Biradar, Debaprashad Shee, Ankur Bordoloi","doi":"10.1039/d4nr01185f","DOIUrl":"https://doi.org/10.1039/d4nr01185f","url":null,"abstract":"Transforming CO2 to CO via reverse water-gas shift (RWGS) reaction is widely regarded as a promising technique for improving the efficiency and economics of the CO2 utilization processes. Moreover, it is also considered as a pathway towards e-fuels. Cu-oxide catalysts are widely explored for low-temperature RWGS, nevertheless, they tend to deactivate significantly in applied reaction conditions due to the agglomeration of copper particles at elevated temperatures. Herein, we have synthesized homogeneously distributed Cu metallic nanoparticles supported on Mo2C for RWGS reaction by a unique approach in-situ carburization of metal-organic frameworks (MOFs) comprised of Cu-based MOF i.e., HKUST-1 encapsulating molybdenum-based polyoxometalates. The newly derived Na-Cu-Mo2C nanocomposite catalyst system exhibits excellent catalytic performance with a CO production rate of 3230.0 mmol gcat-1 h-1 with 100 % CO selectivity. Even after 250 h of stability test, the catalyst remained active with more than 80 % of its initial activity.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463076","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}
Jingyi Zhao, Kunfeng Zhang, Dezhi Sui, Shuo Wang, Yantong Li, Xueying Tang, Xinrong Liu, Yanzhi Song, Yihui Deng
Tumors have always been a major public health concern worldwide, and the attempts looking for effective treatments have never ceased. Sialic acid is known as a crucial element for tumor development and its receptors are highly expressed on the tumor-associated immune cells, which perform significant roles in establishing immunosuppressive tumor microenvironment and further boosting tumorigenesis, progression, and metastasis. Obviously, it is essential to consider the sophisticated crosstalk among tumors, the immune system, and preparations, and understand the links between pharmaceutics and immunology. Sialic acid-based chemoimmunotherapy enables active targeting drug delivery via mediating the active recognition between sialic acid-modified nano-drug delivery system represented by liposomes and sialic acid-binding receptors on tumor-associated immune cells, which inhibits and utilizes their homing ability to deliver drugs. Such a “Trojan horse” strategy has remarkably improved the shortcomings of traditional passive targeting treatments, unexpectedly promoted tumor shed, and persistently induced robust immunological memory, illuminating the prospective application potential for various tumors. Herein, we review recent advances in sialic acid-based active targeting chemoimmunotherapy promoting tumor shed, summarize the current viewpoints of the tumor shed mechanism, especially the formation of durable immunological memory, and analyze the challenges and opportunities of this attractive approach.
{"title":"Recent advances in sialic acid-based active targeting chemoimmunotherapy promoting tumor shed: a systematic review","authors":"Jingyi Zhao, Kunfeng Zhang, Dezhi Sui, Shuo Wang, Yantong Li, Xueying Tang, Xinrong Liu, Yanzhi Song, Yihui Deng","doi":"10.1039/d4nr01740d","DOIUrl":"https://doi.org/10.1039/d4nr01740d","url":null,"abstract":"Tumors have always been a major public health concern worldwide, and the attempts looking for effective treatments have never ceased. Sialic acid is known as a crucial element for tumor development and its receptors are highly expressed on the tumor-associated immune cells, which perform significant roles in establishing immunosuppressive tumor microenvironment and further boosting tumorigenesis, progression, and metastasis. Obviously, it is essential to consider the sophisticated crosstalk among tumors, the immune system, and preparations, and understand the links between pharmaceutics and immunology. Sialic acid-based chemoimmunotherapy enables active targeting drug delivery via mediating the active recognition between sialic acid-modified nano-drug delivery system represented by liposomes and sialic acid-binding receptors on tumor-associated immune cells, which inhibits and utilizes their homing ability to deliver drugs. Such a “Trojan horse” strategy has remarkably improved the shortcomings of traditional passive targeting treatments, unexpectedly promoted tumor shed, and persistently induced robust immunological memory, illuminating the prospective application potential for various tumors. Herein, we review recent advances in sialic acid-based active targeting chemoimmunotherapy promoting tumor shed, summarize the current viewpoints of the tumor shed mechanism, especially the formation of durable immunological memory, and analyze the challenges and opportunities of this attractive approach.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462678","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}
Micro/nanomotors (MNMs) are intelligent, efficient and promising micro/nanorobots (MNR) that can respond to external stimuli (e.g., chemical energy, temperature, light, pH, ultrasound, magnetic, biosignals, ions) and perform specific tasks. The MNR can adapt to different external stimuli and transform into various functional forms to match different application scenarios. So far, MNR have found extensive application in targeted therapy, drug delivery, tissue engineering, environmental remediation, and other fields. Despite the promise of MNR, there are few reviews that focus on them. To shed new light on the further development of the field, it is necessary to provide an overview of the current state of development of these MNR. Therefore, this paper reviews the research progress of MNR in terms of propulsion mechanisms, and points out the pros and cons of different stimulus types. Finally, this paper highlights the current challenges faced by MNR and proposes possible solutions to facilitate the practical application of MNR.
{"title":"Propulsion mechanisms of micro/nanorobots: a review","authors":"Tao He, Yonghui Yang, Xue-Bo Chen","doi":"10.1039/d4nr01776e","DOIUrl":"https://doi.org/10.1039/d4nr01776e","url":null,"abstract":"Micro/nanomotors (MNMs) are intelligent, efficient and promising micro/nanorobots (MNR) that can respond to external stimuli (<em>e.g.</em>, chemical energy, temperature, light, pH, ultrasound, magnetic, biosignals, ions) and perform specific tasks. The MNR can adapt to different external stimuli and transform into various functional forms to match different application scenarios. So far, MNR have found extensive application in targeted therapy, drug delivery, tissue engineering, environmental remediation, and other fields. Despite the promise of MNR, there are few reviews that focus on them. To shed new light on the further development of the field, it is necessary to provide an overview of the current state of development of these MNR. Therefore, this paper reviews the research progress of MNR in terms of propulsion mechanisms, and points out the pros and cons of different stimulus types. Finally, this paper highlights the current challenges faced by MNR and proposes possible solutions to facilitate the practical application of MNR.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462401","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}
Yurij V. Kalyuzhnyi, Taras Patsahan, Myroslav Holovko, Peter T. Cummings
Correction for ‘Phase behavior of patchy colloids confined in patchy porous media’ by Yurij V. Kalyuzhnyi et al., Nanoscale, 2024, 16, 4668–4677, https://doi.org/10.1039/D3NR02866F.
对 Yurij V. Kalyuzhnyi 等人撰写的 "Phase behavior of patchy colloids confined in patchy porous media "的更正，Nanoscale，2024，16，4668-4677，https://doi.org/10.1039/D3NR02866F。
{"title":"Correction: Phase behavior of patchy colloids confined in patchy porous media","authors":"Yurij V. Kalyuzhnyi, Taras Patsahan, Myroslav Holovko, Peter T. Cummings","doi":"10.1039/d4nr90128b","DOIUrl":"https://doi.org/10.1039/d4nr90128b","url":null,"abstract":"Correction for ‘Phase behavior of patchy colloids confined in patchy porous media’ by Yurij V. Kalyuzhnyi <em>et al.</em>, <em>Nanoscale</em>, 2024, <strong>16</strong>, 4668–4677, https://doi.org/10.1039/D3NR02866F.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462400","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}
Chase Rotteger, Carter Jarman, Shaun Sutton, Scott Sayres
The excited state lifetimes of neutral (Al)n clusters up to ~1 nm in diameter in size, where n ≤ 43, are systematically measured with femtosecond time-resolved mass spectrometry. The onset of metallic behavior is identified as a distinct change in the relaxation behavior initiated with single ultraviolet (400 nm) photon excitation. The experimentally measured excited state lifetimes gradually decrease with size for small molecular scale clusters (n < 10) before becoming indistinguishable for larger clusters (n > 9), where the measurements are comparable to electron-lattice relaxation time of bulk Al (~300 fs). Particularly intense, or magic, Aln clusters do not exhibit any significant excited state lifetime behavior. Time-dependent density functional theory quantify the excited state properties and are presented to show that dynamics are strongly tied to the excited state charge carrier distributions and overlap, rather than detailed changes related to changes in the cluster’s electronic and geometric structure. The consistency in excited state lifetimes for clusters larger than n = 9 is attributed to the hybridization of the s- and p- orbitals as well as increasing delocalization. Al3 exhibits unique temporal delay in its transient behavior that is attributed to a transition from triangular ground state to linear structure upon excitation.
利用飞秒时间分辨质谱法系统地测量了直径达 ~1 nm 的中性 (Al)n 簇的激发态寿命，其中 n ≤ 43。在单紫外（400 nm）光子激发下，弛豫行为发生明显变化，从而确定了金属行为的开始。实验测得的激发态寿命随着小分子尺度团簇（n <10）的尺寸逐渐减小，然后在较大的团簇（n >9）中变得难以区分，测量结果与块状铝的电子-晶格弛豫时间（约 300 fs）相当。特别强烈或神奇的 Aln 簇没有表现出任何明显的激发态寿命行为。随时间变化的密度泛函理论对激发态特性进行了量化，结果表明动态与激发态电荷载流子分布和重叠密切相关，而不是与团簇电子和几何结构变化有关的细节变化。对于 n = 9 以上的原子团，激发态寿命的一致性归因于 s 和 p 轨道的杂化以及脱ocalization 的增加。Al3 在其瞬态行为中表现出独特的时间延迟，这归因于激发时从三角形基态向线性结构的过渡。
{"title":"Size Onset of Metallic Behavior in Neutral Aluminum Clusters","authors":"Chase Rotteger, Carter Jarman, Shaun Sutton, Scott Sayres","doi":"10.1039/d4nr02032d","DOIUrl":"https://doi.org/10.1039/d4nr02032d","url":null,"abstract":"The excited state lifetimes of neutral (Al)n clusters up to ~1 nm in diameter in size, where n ≤ 43, are systematically measured with femtosecond time-resolved mass spectrometry. The onset of metallic behavior is identified as a distinct change in the relaxation behavior initiated with single ultraviolet (400 nm) photon excitation. The experimentally measured excited state lifetimes gradually decrease with size for small molecular scale clusters (n < 10) before becoming indistinguishable for larger clusters (n > 9), where the measurements are comparable to electron-lattice relaxation time of bulk Al (~300 fs). Particularly intense, or magic, Aln clusters do not exhibit any significant excited state lifetime behavior. Time-dependent density functional theory quantify the excited state properties and are presented to show that dynamics are strongly tied to the excited state charge carrier distributions and overlap, rather than detailed changes related to changes in the cluster’s electronic and geometric structure. The consistency in excited state lifetimes for clusters larger than n = 9 is attributed to the hybridization of the s- and p- orbitals as well as increasing delocalization. Al3 exhibits unique temporal delay in its transient behavior that is attributed to a transition from triangular ground state to linear structure upon excitation.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461715","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}
Naveed Ur Rahman, Rajwali Khan, Muhammad Faisal Hayat, D. Ghernaout, Alsamani A. M. Salih, Ghulam Abbas Ashraf, Abdus Samad, Muhammad Adil Mahmood, Nasir Rahman, Mohammad Sohail, Shahid Iqbal, Sherzod Shukhratovich Abdullaev, Alamzeb Khan
One of its feasible outcomes to low features in the classical von Neumann formulating system is a brain-inspired photonics technology derived from human brain ideas. Optoelectronic neural devices, which are accustomed to imitating the sensory role in the biological synapse by adjusting connection measures, may be used to make a highly reliable neurologically calculating device, wherein nanosized materials and device designs are attracting attention since they provide numerous potential benefits in terms of limited cool contact, rapid transfer fluidity, as well as the capture of photocarriers. In addition, the combination of classic nanosized photodetectors with recently generated digital synapses offers promising results in a variety of practical uses, like data processing and computation. The present progress in constructing improved optoelectronic synaptic devices that rely on nanomaterials for example 0-Dimension (quantum dots), 1-Dimension, and 2-Dimention composites, besides the continuously rising mixed heterostructures, is the focus of this article. Furthermore, the obstacles and hopeful diagnoses in this field of study are explored.
{"title":"Unveiling Cutting-Edge Developments: Architectures and Nanostructured Materials in Optoelectronic Artificial Synapses","authors":"Naveed Ur Rahman, Rajwali Khan, Muhammad Faisal Hayat, D. Ghernaout, Alsamani A. M. Salih, Ghulam Abbas Ashraf, Abdus Samad, Muhammad Adil Mahmood, Nasir Rahman, Mohammad Sohail, Shahid Iqbal, Sherzod Shukhratovich Abdullaev, Alamzeb Khan","doi":"10.1039/d4nr00904e","DOIUrl":"https://doi.org/10.1039/d4nr00904e","url":null,"abstract":"One of its feasible outcomes to low features in the classical von Neumann formulating system is a brain-inspired photonics technology derived from human brain ideas. Optoelectronic neural devices, which are accustomed to imitating the sensory role in the biological synapse by adjusting connection measures, may be used to make a highly reliable neurologically calculating device, wherein nanosized materials and device designs are attracting attention since they provide numerous potential benefits in terms of limited cool contact, rapid transfer fluidity, as well as the capture of photocarriers. In addition, the combination of classic nanosized photodetectors with recently generated digital synapses offers promising results in a variety of practical uses, like data processing and computation. The present progress in constructing improved optoelectronic synaptic devices that rely on nanomaterials for example 0-Dimension (quantum dots), 1-Dimension, and 2-Dimention composites, besides the continuously rising mixed heterostructures, is the focus of this article. Furthermore, the obstacles and hopeful diagnoses in this field of study are explored.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462399","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}
Caicheng Song, Yiwen Guo, Tianwei Wang, Kun Liu, Pin-Yi Zhao, Ying Liu, He Huang, Rongwen Lu, Shufen Zhang
Functional mesoporous carbon nanomaterials with large pores and small particle sizes have broad accessibility, but remain challenging to achieve. This study proposed a dual-template synergistic assembly strategy to facilely synthesize extra-small nitrogen-doped mesoporous carbon nanospheres with large pores in a low-cost manner. Directed by the synergistic effect of the combination of surfactants, sodium oleate (anionic surfactant) and triblock copolymers-P123 (nonionic surfactant) were selected as a template to construct nanomicelles (nanoemulsions), which were co-assembled with melamine-based oligomers to form composite nanomicelles, thus obtaining nitrogen-doped mesoporous polymer nanospheres (NMePS) and then nitrogen-doped mesoporous carbon nanospheres (NMeCS). Based on Schiff base chemistry, the melamine-based oligomers with self-assembly capability were synthesized as precursors, which is different from the conventional synthetic route of melamine-formaldehyde resin. The key parameters involved in the route were investigated comprehensively and correlated with characterization results. Furthermore, the 50 nm-scale particle size and the large mesoporous size of 5.5 nm can facilitate effective mass transport, coupled with its high nitrogen content (15.7 wt. %), contributing to its excellent performance in lithium-ion batteries.
{"title":"Dual-template synergistic assembly strategy towards extra-small nitrogen-doped mesoporous carbon nanospheres with large-pore","authors":"Caicheng Song, Yiwen Guo, Tianwei Wang, Kun Liu, Pin-Yi Zhao, Ying Liu, He Huang, Rongwen Lu, Shufen Zhang","doi":"10.1039/d4nr01072h","DOIUrl":"https://doi.org/10.1039/d4nr01072h","url":null,"abstract":"Functional mesoporous carbon nanomaterials with large pores and small particle sizes have broad accessibility, but remain challenging to achieve. This study proposed a dual-template synergistic assembly strategy to facilely synthesize extra-small nitrogen-doped mesoporous carbon nanospheres with large pores in a low-cost manner. Directed by the synergistic effect of the combination of surfactants, sodium oleate (anionic surfactant) and triblock copolymers-P123 (nonionic surfactant) were selected as a template to construct nanomicelles (nanoemulsions), which were co-assembled with melamine-based oligomers to form composite nanomicelles, thus obtaining nitrogen-doped mesoporous polymer nanospheres (NMePS) and then nitrogen-doped mesoporous carbon nanospheres (NMeCS). Based on Schiff base chemistry, the melamine-based oligomers with self-assembly capability were synthesized as precursors, which is different from the conventional synthetic route of melamine-formaldehyde resin. The key parameters involved in the route were investigated comprehensively and correlated with characterization results. Furthermore, the 50 nm-scale particle size and the large mesoporous size of 5.5 nm can facilitate effective mass transport, coupled with its high nitrogen content (15.7 wt. %), contributing to its excellent performance in lithium-ion batteries.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461870","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}
Lei Wang, Zequan Ma, Jia Xue, Yilin Dong, Lin-Wei Chen, Yu Gu, Hui Shi
Atomically ordered intermetallic compounds (IMCs) have been extensively studied for exploring catalysts with high activity, selectivity, and longevity. Compared to the random alloys, IMCs presented more pronounced geometric and electronic effect with desirable catalytic performance. The well-defined structure makes the IMCs ideal model catalysts for revealing the catalytic mechanism. This review focuses specially on the elemental composition, electron transfer, and structure/phase evolution under high temperature treatment conditions. Providing direct evidence for the migration and rearrangement of metal atoms combined with electron microscope. We then present the outstanding applications of IMCs in growing single-walled nano tubes, hydrogenation/dehydrogenation reaction, and electrocatalysis from the perspective of electronic, geometric, strain, and bifunctional effect of the ordered IMCs. Finally, the current obstacles associated with the use of in situ techniques are proposed, as well as future research possibilities.
{"title":"Structure evolution and specific effect for catalysis of atomically ordered intermetallic compounds","authors":"Lei Wang, Zequan Ma, Jia Xue, Yilin Dong, Lin-Wei Chen, Yu Gu, Hui Shi","doi":"10.1039/d4nr01939c","DOIUrl":"https://doi.org/10.1039/d4nr01939c","url":null,"abstract":"Atomically ordered intermetallic compounds (IMCs) have been extensively studied for exploring catalysts with high activity, selectivity, and longevity. Compared to the random alloys, IMCs presented more pronounced geometric and electronic effect with desirable catalytic performance. The well-defined structure makes the IMCs ideal model catalysts for revealing the catalytic mechanism. This review focuses specially on the elemental composition, electron transfer, and structure/phase evolution under high temperature treatment conditions. Providing direct evidence for the migration and rearrangement of metal atoms combined with electron microscope. We then present the outstanding applications of IMCs in growing single-walled nano tubes, hydrogenation/dehydrogenation reaction, and electrocatalysis from the perspective of electronic, geometric, strain, and bifunctional effect of the ordered IMCs. Finally, the current obstacles associated with the use of in situ techniques are proposed, as well as future research possibilities.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461973","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}
Xiaotian Wei, Chung Nguyen, Patrick David Taylor, Vaishnavi Krishnamurthi, Nitu Syed, Phuong Le, Michelle Jeanette Sapountzis Spencer, Torben Daeneke, Lei Bao
Possessing excellent electronic properties and high chemical stability, semiconducting n-type two-dimensional (2D) tin dioxide (SnO2) nanosheets have recently been featured in sensing and electrocatalysis applications. Derived from non-layered crystal structures, 2D SnO2 has abundant unsaturated dangling bonds existing at the surface, providing interfacial activity. How the surface chemistry alters the electronic properties of 2D SnO2 remains unexplored. In this study, we synthesised ultra-thin 2D SnO2 using a liquid metal (LM) touch printing technique and investigated experimentally and theoretically how the interactions of organic solvents composed of alkyl and hydroxyl groups with the surface of LM-derived SnO2 modulate electronic properties. It was found that alkane solvents can physically absorb onto the SnO2 surface with no impact on the material conductivity. Alcohol-based solvents on the other hand interact with the SnO2 surface via chemical absorptions primarily, in which oxygen atoms of hydroxyl groups in the alcohols can bond with the surface atoms of SnO2. The bond stability is determined by the length and configuration of the hydrocarbon chain in alcohols. As representative long-chain alcohols, 1-octanol and 1-pentanol bind onto the SnO2 surface strongly, lowering the binding energy of Sn4+ and reducing the electron transfer ability of SnO2 nanosheets. Consequently, the electronic properties, i.e. conductivity and electronic mobility of SnO2 nanosheet-based electronic devices are decreased significantly.
半导体 n 型二维二氧化锡（SnO2）纳米片具有优异的电子特性和较高的化学稳定性，最近在传感和电催化应用中大放异彩。二维二氧化锡源于非层状晶体结构，表面存在大量不饱和悬键，具有界面活性。表面化学如何改变二维二氧化锡的电子特性仍有待探索。在这项研究中，我们利用液态金属（LM）触印技术合成了超薄二维二氧化锡，并从实验和理论上研究了由烷基和羟基组成的有机溶剂与 LM 衍生二氧化锡表面的相互作用如何调节电子特性。研究发现，烷基溶剂可以物理吸附到二氧化锡表面，对材料的导电性没有影响。另一方面，醇基溶剂主要通过化学吸收与二氧化锡表面相互作用，其中醇中羟基的氧原子可与二氧化锡的表面原子结合。键的稳定性取决于醇中碳氢链的长度和构型。作为长链醇的代表，1-辛醇和 1-戊醇与二氧化锡表面的结合力很强，从而降低了 Sn4+ 的结合能，降低了二氧化锡纳米片的电子传递能力。因此，基于二氧化锡纳米片的电子器件的电子特性，即电导率和电子迁移率显著降低。
{"title":"Surface Chemistry Altering Electronic Behaviours of Liquid Metal-Derived Tin Oxide Nanosheets","authors":"Xiaotian Wei, Chung Nguyen, Patrick David Taylor, Vaishnavi Krishnamurthi, Nitu Syed, Phuong Le, Michelle Jeanette Sapountzis Spencer, Torben Daeneke, Lei Bao","doi":"10.1039/d4nr01841a","DOIUrl":"https://doi.org/10.1039/d4nr01841a","url":null,"abstract":"Possessing excellent electronic properties and high chemical stability, semiconducting n-type two-dimensional (2D) tin dioxide (SnO<small><sub>2</sub></small>) nanosheets have recently been featured in sensing and electrocatalysis applications. Derived from non-layered crystal structures, 2D SnO<small><sub>2</sub></small> has abundant unsaturated dangling bonds existing at the surface, providing interfacial activity. How the surface chemistry alters the electronic properties of 2D SnO<small><sub>2</sub></small> remains unexplored. In this study, we synthesised ultra-thin 2D SnO<small><sub>2</sub></small> using a liquid metal (LM) touch printing technique and investigated experimentally and theoretically how the interactions of organic solvents composed of alkyl and hydroxyl groups with the surface of LM-derived SnO<small><sub>2</sub></small> modulate electronic properties. It was found that alkane solvents can physically absorb onto the SnO<small><sub>2</sub></small> surface with no impact on the material conductivity. Alcohol-based solvents on the other hand interact with the SnO<small><sub>2</sub></small> surface via chemical absorptions primarily, in which oxygen atoms of hydroxyl groups in the alcohols can bond with the surface atoms of SnO<small><sub>2</sub></small>. The bond stability is determined by the length and configuration of the hydrocarbon chain in alcohols. As representative long-chain alcohols, 1-octanol and 1-pentanol bind onto the SnO<small><sub>2</sub></small> surface strongly, lowering the binding energy of Sn<small><sup>4+</sup></small> and reducing the electron transfer ability of SnO<small><sub>2</sub></small> nanosheets. Consequently, the electronic properties, i.e. conductivity and electronic mobility of SnO<small><sub>2</sub></small> nanosheet-based electronic devices are decreased significantly.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461932","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}
Liquid crystalline materials have attracted significant attention in chiroptical research due to their ability to form long range ordered helical superstructures. Research focus has been on exploiting the unique properties of liquid crystalline materials to demonstrate highly dissymmetric circularly polarised luminescent (CPL) systems. In this study, we present a thermally driven, facile approach to fabricate CPL-active materials utilizing cholesteryl benzoate (ChB) as the active substrate. ChB, a well-known thermotropic liquid crystal, has been found to manifest intriguing optical characteristics upon subjecting to repeated heating-cooling cycles. Despite the absence of conventional fluorescent moieties, the material exhibited luminescence through aggregation induced clustering triggered emission mechanism. Systematic investigations revealed excitation-dependent CPL for solid ChB films. The excited state chiroptical investigation performed after multiple thermal cycles showed a luminescence anisotropy (glum) of 8 x 10-2, a relatively high value for simple organic molecules. Moreover, upon co-assembly with lanthanide-based upconversion nanophosphors (UCNPs), the hybrid nanosystem demonstrated upconverted circularly polarised luminescence (UC-CPL) with enhanced luminescence dissymmetry. Benefiting from the ability to endow upconversion nanoparticles of various sizes, fabrication of UCNP-ChB hybrid nanocomposites exhibiting multicoloured upconversion CPL was demonstrated. These findings highlight the potential of chiral liquid crystalline materials for diverse applications, including 3D optical displays and anticounterfeiting technologies.
{"title":"Clustering Triggered Emissive Liquid Crystalline Template for Dual Mode Upconverted and Down converted Circularly Polarized Luminescence","authors":"Sreelakshmi Theeyenchery Nalavadath, Sonia Maniappan, Anannya Mandal, Jatish Kumar","doi":"10.1039/d4nr00865k","DOIUrl":"https://doi.org/10.1039/d4nr00865k","url":null,"abstract":"Liquid crystalline materials have attracted significant attention in chiroptical research due to their ability to form long range ordered helical superstructures. Research focus has been on exploiting the unique properties of liquid crystalline materials to demonstrate highly dissymmetric circularly polarised luminescent (CPL) systems. In this study, we present a thermally driven, facile approach to fabricate CPL-active materials utilizing cholesteryl benzoate (ChB) as the active substrate. ChB, a well-known thermotropic liquid crystal, has been found to manifest intriguing optical characteristics upon subjecting to repeated heating-cooling cycles. Despite the absence of conventional fluorescent moieties, the material exhibited luminescence through aggregation induced clustering triggered emission mechanism. Systematic investigations revealed excitation-dependent CPL for solid ChB films. The excited state chiroptical investigation performed after multiple thermal cycles showed a luminescence anisotropy (glum) of 8 x 10-2, a relatively high value for simple organic molecules. Moreover, upon co-assembly with lanthanide-based upconversion nanophosphors (UCNPs), the hybrid nanosystem demonstrated upconverted circularly polarised luminescence (UC-CPL) with enhanced luminescence dissymmetry. Benefiting from the ability to endow upconversion nanoparticles of various sizes, fabrication of UCNP-ChB hybrid nanocomposites exhibiting multicoloured upconversion CPL was demonstrated. These findings highlight the potential of chiral liquid crystalline materials for diverse applications, including 3D optical displays and anticounterfeiting technologies.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461956","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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