Ammonia and urea represent two important chemicals that have contributed to the rapid development of humanity. However, their industrial production requires harsh conditions, consuming excessive energy and resulting in significant greenhouse gas emission. Therefore, there is growing interest in the electrocatalytic synthesis of ammonia and urea as it can be carried out under ambient conditions. Recently, atomic catalysts (ACs) have gained increased attention for their superior catalytic properties, being able to outperform their micro and nano counterparts. This review examines the advantages and disadvantages of ACs and summarises the advancement of ACs in the electrocatalytic synthesis of ammonia and urea. The focus is on two types of AC – single-atom catalysts (SACs) and diatom catalysts (DACs). SACs offer various advantages, including the 100% atom utilization that allows for low material mass loading, suppression of competitive reactions such as hydrogen evolution reaction (HER), and alternative reaction pathways allowing for efficient synthesis of ammonia and urea. DACs inherit these advantages, possessing further benefits of synergistic effects between the two catalytic centers at close proximity, particularly matching the NN bond for N2 reduction and boosting C–N coupling for urea synthesis. DACs also possess the ability to break the linear scaling relation of adsorption energy of reactants and intermediates, allowing for tuning of intermediate adsorption energies. Finally, possible future research directions using ACs are proposed.
氨和尿素是促进人类快速发展的两种重要化学品。然而，它们的工业生产需要苛刻的条件，消耗过多能源，并导致大量温室气体排放。因此，人们对氨和尿素的电催化合成越来越感兴趣，因为它可以在环境条件下进行。最近，原子催化剂（AC）因其优越的催化特性而受到越来越多的关注，其性能超过了微型和纳米催化剂。本综述探讨了原子催化剂的优缺点，并总结了原子催化剂在电催化合成氨和尿素方面的进展。重点是两类交流电--单原子催化剂（SAC）和硅藻催化剂（DAC）。单原子催化剂（SAC）具有各种优势，包括 100% 的原子利用率，可实现较低的材料装载量，抑制氢进化反应（HER）等竞争反应，以及可高效合成氨和尿素的替代反应途径。DAC 在继承这些优点的同时，还进一步发挥了两个催化中心之间的协同效应，特别是在还原 N2 时匹配 NN 键，在合成尿素时促进 C-N 耦合。DAC 还能打破反应物和中间产物吸附能的线性比例关系，从而调整中间产物的吸附能。最后，还提出了使用 AC 的未来研究方向。
{"title":"Single and dual-atom catalysts towards electrosynthesis of ammonia and urea: a review","authors":"Wenyu Luo, Jiawei Liu, Yue Hu, Qingyu Yan","doi":"10.1039/d4nr02387k","DOIUrl":"https://doi.org/10.1039/d4nr02387k","url":null,"abstract":"Ammonia and urea represent two important chemicals that have contributed to the rapid development of humanity. However, their industrial production requires harsh conditions, consuming excessive energy and resulting in significant greenhouse gas emission. Therefore, there is growing interest in the electrocatalytic synthesis of ammonia and urea as it can be carried out under ambient conditions. Recently, atomic catalysts (ACs) have gained increased attention for their superior catalytic properties, being able to outperform their micro and nano counterparts. This review examines the advantages and disadvantages of ACs and summarises the advancement of ACs in the electrocatalytic synthesis of ammonia and urea. The focus is on two types of AC – single-atom catalysts (SACs) and diatom catalysts (DACs). SACs offer various advantages, including the 100% atom utilization that allows for low material mass loading, suppression of competitive reactions such as hydrogen evolution reaction (HER), and alternative reaction pathways allowing for efficient synthesis of ammonia and urea. DACs inherit these advantages, possessing further benefits of synergistic effects between the two catalytic centers at close proximity, particularly matching the N<img alt=\"[triple bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e002.gif\"/>N bond for N<small><sub>2</sub></small> reduction and boosting C–N coupling for urea synthesis. DACs also possess the ability to break the linear scaling relation of adsorption energy of reactants and intermediates, allowing for tuning of intermediate adsorption energies. Finally, possible future research directions using ACs are proposed.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486307","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}
Cécile Huez, David Guerin, Florence Volatron, Anna Proust, Dominique Vuillaume
We study the low-frequency noise, i.e. flicker noise, also referred to as 1/f noise, in 2D networks of molecularly functionalized gold nanoparticles (NMN: nanoparticle-molecule network). We examine the noise behaviors of the NMN hosting alkyl chains (octanethiol), fatty acid oleic acids (oleylamine), redox molecule switches (polyoxometalate derivatives) or photo-isomerizable molecules (azobenzene derivatives) and we compare their 1/f noise behaviors. These noise metrics are used to evaluate which molecules are the best candidates to build in-materio reservoir computing molecular devices based on NMNs.
{"title":"Low frequency noise in nanoparticle-molecule networks and implications for in-materio reservoir computing.","authors":"Cécile Huez, David Guerin, Florence Volatron, Anna Proust, Dominique Vuillaume","doi":"10.1039/d4nr02428a","DOIUrl":"https://doi.org/10.1039/d4nr02428a","url":null,"abstract":"We study the low-frequency noise, i.e. flicker noise, also referred to as 1/f noise, in 2D networks of molecularly functionalized gold nanoparticles (NMN: nanoparticle-molecule network). We examine the noise behaviors of the NMN hosting alkyl chains (octanethiol), fatty acid oleic acids (oleylamine), redox molecule switches (polyoxometalate derivatives) or photo-isomerizable molecules (azobenzene derivatives) and we compare their 1/f noise behaviors. These noise metrics are used to evaluate which molecules are the best candidates to build in-materio reservoir computing molecular devices based on NMNs.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486682","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}
Pre-lithiation, which is capable of supplying additional active lithium sources to lithium-ion battery, has been widely accepted as one of the most promising approaches to address the issue of active lithium loss during the entire process of initial charging and subsequent cycling. In comparison to anode pre-lithiation, cathode pre-lithiation exhibits a facile operating procedure and good compatibility with the current lithium-ion battery production processes. However, the cathode pre-lithiation additives suffer from high decomposition voltage and low decomposition efficiency. In view of this, a variety of nanocatalysts have been developed in recent years to enhance the decomposition kinetic of cathode pre-lithiation additives. Nevertheless, a comprehensive review of nanocatalysis in cathode pre-lithiation is still lacking. This timely review aims to present the crucial role of nanocatalysis in cathode pre-lithiation and provide an up-to-date overview of this field. After demonstrating the significance of nanocatalyst for cathode pre-lithiation, recent progress in the application of nanocatalysts for high-efficiency cathode pre-lithiation is briefly introduced. Finally, future challenges and directions for the commercialization of cathode pre-lithiation technique in conjunction with nanocatalysts are reviewed. The current review provides important insights into the nanocatalysis as a cutting-edge strategy for favorable cathode pre-lithiation and builds a bridge between academic research and industrial applications of nanocatalytic cathode pre-lithiation for lithium-ion battery with high capacity and good cyclability.
{"title":"Nanocatalysis in Cathode Pre-lithiation for Lithium-ion Battery: Progress and Challenges","authors":"Fujun Niu, Liang Qiu, Huai Chen, Xinyu Chen, Xiangpeng Kong, Qiang Rong, Junqiao Xiong, Yang Guo, Zhijian Cai, Shaohua Shen","doi":"10.1039/d4nr04002c","DOIUrl":"https://doi.org/10.1039/d4nr04002c","url":null,"abstract":"Pre-lithiation, which is capable of supplying additional active lithium sources to lithium-ion battery, has been widely accepted as one of the most promising approaches to address the issue of active lithium loss during the entire process of initial charging and subsequent cycling. In comparison to anode pre-lithiation, cathode pre-lithiation exhibits a facile operating procedure and good compatibility with the current lithium-ion battery production processes. However, the cathode pre-lithiation additives suffer from high decomposition voltage and low decomposition efficiency. In view of this, a variety of nanocatalysts have been developed in recent years to enhance the decomposition kinetic of cathode pre-lithiation additives. Nevertheless, a comprehensive review of nanocatalysis in cathode pre-lithiation is still lacking. This timely review aims to present the crucial role of nanocatalysis in cathode pre-lithiation and provide an up-to-date overview of this field. After demonstrating the significance of nanocatalyst for cathode pre-lithiation, recent progress in the application of nanocatalysts for high-efficiency cathode pre-lithiation is briefly introduced. Finally, future challenges and directions for the commercialization of cathode pre-lithiation technique in conjunction with nanocatalysts are reviewed. The current review provides important insights into the nanocatalysis as a cutting-edge strategy for favorable cathode pre-lithiation and builds a bridge between academic research and industrial applications of nanocatalytic cathode pre-lithiation for lithium-ion battery with high capacity and good cyclability.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452265","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}
Joanna Katarzyna Szymkowiak, Lucas J. Andrew, Wadood Y Hamad, Mark MacLachlan
Chiral nematic mesoporous organosilica (CNMO) films have unique iridescent properties that make them attractive candidates for decorations, sensing and photonics. However, it has proven difficult to control the colour and porosity of CNMO films. Here, we have explored the addition of a range of biodegradable and eco-friendly additives to tune the helical pitch and, hence, the colour of the CNMO materials. It was found that the controlled integration of additives allows for the colour of the materials to be tuned across the visible spectrum, but cannot be used to tune the porosity of the films. This work opens up new prospects for preparation of CNMO materials with adjustable optical properties.
{"title":"Controlling the Optical Properties of Chiral Nematic Mesoporous Organosilica Films with Bioadditives","authors":"Joanna Katarzyna Szymkowiak, Lucas J. Andrew, Wadood Y Hamad, Mark MacLachlan","doi":"10.1039/d4nr03326d","DOIUrl":"https://doi.org/10.1039/d4nr03326d","url":null,"abstract":"Chiral nematic mesoporous organosilica (CNMO) films have unique iridescent properties that make them attractive candidates for decorations, sensing and photonics. However, it has proven difficult to control the colour and porosity of CNMO films. Here, we have explored the addition of a range of biodegradable and eco-friendly additives to tune the helical pitch and, hence, the colour of the CNMO materials. It was found that the controlled integration of additives allows for the colour of the materials to be tuned across the visible spectrum, but cannot be used to tune the porosity of the films. This work opens up new prospects for preparation of CNMO materials with adjustable optical properties.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486309","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}
Tamara Sloboda, Birgit Kammlander, Elin Berggren, Stefania Riva, Erika Giangrisostomi, Ruslan Ovsyannikov, Håkan Rensmo, Andreas Lindblad, Ute B. Cappel
For directed development of solar cells using nanomaterials such as quantum dots, there is a need to understand the device function in detail. Understanding where photovoltage is generated in a device and where energy losses occur is a key aspect of this, and development of methods which can provide this information is needed. We have previously shown that time-resolved photoelectron spectroscopy of core levels can be used to follow the photovoltage dynamics at a specific interface of a lead sulfide quantum dot solar cell. Here, we use the method's selectivity and sample design to investigate the photovoltage generation in different parts of this solar cell and determine how the different layers (including the absorber layer thickness) contribute to charge separation. We show that all layers contribute to photovoltage generation and that a gold contact deposited on the quantum dots is necessary for full photovoltage generation and slow charge recombination. By combining the information obtained, we are able to experimentally follow the time evolution of the solar cell band structure during the charge separation process. Furthermore, we can identify which specific layers need to be optimized for an overall improvement of quantum dot cells. In the future, this methodology can be applied to other types of devices to provide insights into photovoltage generation mechanisms.
{"title":"Interface-resolved photovoltage generation dynamics and band structure evolution in a PbS quantum dot solar cell","authors":"Tamara Sloboda, Birgit Kammlander, Elin Berggren, Stefania Riva, Erika Giangrisostomi, Ruslan Ovsyannikov, Håkan Rensmo, Andreas Lindblad, Ute B. Cappel","doi":"10.1039/d4nr03428g","DOIUrl":"https://doi.org/10.1039/d4nr03428g","url":null,"abstract":"For directed development of solar cells using nanomaterials such as quantum dots, there is a need to understand the device function in detail. Understanding where photovoltage is generated in a device and where energy losses occur is a key aspect of this, and development of methods which can provide this information is needed. We have previously shown that time-resolved photoelectron spectroscopy of core levels can be used to follow the photovoltage dynamics at a specific interface of a lead sulfide quantum dot solar cell. Here, we use the method's selectivity and sample design to investigate the photovoltage generation in different parts of this solar cell and determine how the different layers (including the absorber layer thickness) contribute to charge separation. We show that all layers contribute to photovoltage generation and that a gold contact deposited on the quantum dots is necessary for full photovoltage generation and slow charge recombination. By combining the information obtained, we are able to experimentally follow the time evolution of the solar cell band structure during the charge separation process. Furthermore, we can identify which specific layers need to be optimized for an overall improvement of quantum dot cells. In the future, this methodology can be applied to other types of devices to provide insights into photovoltage generation mechanisms.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486292","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}
Markus Freiberger, Olga A. Stasyuk, M. Eugenia Pérez-Ojeda, Luis Echegoyen, Miquel Solà, Thomas Drewello
[n]Cycloparaphenylenes ([n]CPPs) are strained macrocycles, comprising only sp2-hybridized carbon atoms. In recent years, [n]CPPs have become of great research interest in the field of supramolecular chemistry since their special structure enables the formation of novel host-guest complexes. In this work, we investigate the gas-phase chemistry of noncovalent complexes of [10 12]CPP with the pristine fullerenes C76/78/84 and the endohedral metallofullerenes (EMFs) Sc3N@D3h-C78, Sc3N@D5h-C80 and M3N@Ih-C80 (M = Sc, Y, Lu, Gd). The [1:1] complexes with [10-12]CPP are detected as radical cations. The stability and charge distributions of these complexes are studied using energy resolved collision-induced dissociation (ER-CID). Our results asses the size complementarity, the influence of fullerene symmetry and size as well as the role of the metal size inside the EMF on the binding affinity and complex stability. Two main trends in complex stability have been found: First, [10-12]CPP form more stable complexes with EMFs than with pristine fullerenes and second, all complexes of EMFs with the C80 skeleton show similar stability despite the different metal clusters encapsulated. Another major finding is the fact that [11]CPP is generally the most suitable host for fullerenes with a C76/78/80/84 skeleton. Considering the charge distributions, we observe the existence of two different fragmentation channels for complexes with EMFs where the radical cation is either located at the CPP or at the EMF: (1) [n]CPP+• + EMF and (2) [n]CPP + EMF+•. This behavior allows a clear distinction of the cage isomers ([11]CPP⊃Sc3N@Ih-C80)+• and ([11]CPP⊃Sc3N@D5h-C80)+• in the MS2 experiment. The experimental results are accompanied by density functional theory (DFT) calculations of ionization potentials (IPs) and fragmentation energies. The computational results fully confirm the measured order of complex stabilities and explain the prevalence of EMF or CPP signals in the spectra by the trend in ionization potentials.
{"title":"Stability of [10-12]cycloparaphenylene complexes with pristine fullerenes C76, 78, 84 and endohedral metallofullerenes M3N@C78, 80","authors":"Markus Freiberger, Olga A. Stasyuk, M. Eugenia Pérez-Ojeda, Luis Echegoyen, Miquel Solà, Thomas Drewello","doi":"10.1039/d4nr02287d","DOIUrl":"https://doi.org/10.1039/d4nr02287d","url":null,"abstract":"[n]Cycloparaphenylenes ([n]CPPs) are strained macrocycles, comprising only sp2-hybridized carbon atoms. In recent years, [n]CPPs have become of great research interest in the field of supramolecular chemistry since their special structure enables the formation of novel host-guest complexes. In this work, we investigate the gas-phase chemistry of noncovalent complexes of [10 12]CPP with the pristine fullerenes C76/78/84 and the endohedral metallofullerenes (EMFs) Sc3N@D3h-C78, Sc3N@D5h-C80 and M3N@Ih-C80 (M = Sc, Y, Lu, Gd). The [1:1] complexes with [10-12]CPP are detected as radical cations. The stability and charge distributions of these complexes are studied using energy resolved collision-induced dissociation (ER-CID). Our results asses the size complementarity, the influence of fullerene symmetry and size as well as the role of the metal size inside the EMF on the binding affinity and complex stability. Two main trends in complex stability have been found: First, [10-12]CPP form more stable complexes with EMFs than with pristine fullerenes and second, all complexes of EMFs with the C80 skeleton show similar stability despite the different metal clusters encapsulated. Another major finding is the fact that [11]CPP is generally the most suitable host for fullerenes with a C76/78/80/84 skeleton. Considering the charge distributions, we observe the existence of two different fragmentation channels for complexes with EMFs where the radical cation is either located at the CPP or at the EMF: (1) [n]CPP+• + EMF and (2) [n]CPP + EMF+•. This behavior allows a clear distinction of the cage isomers ([11]CPP⊃Sc3N@Ih-C80)+• and ([11]CPP⊃Sc3N@D5h-C80)+• in the MS2 experiment. The experimental results are accompanied by density functional theory (DFT) calculations of ionization potentials (IPs) and fragmentation energies. The computational results fully confirm the measured order of complex stabilities and explain the prevalence of EMF or CPP signals in the spectra by the trend in ionization potentials.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487025","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}
Tamara Sloboda, Birgit Kammlander, Elin Berggren, Stefania Riva, Erika Giangrisostomi, Ruslan Ovsyannikov, Håkan Rensmo, Andreas Lindblad, Ute B Cappel
For directed development of solar cells using nanomaterials such as quantum dots, there is a need to understand the device function in detail. Understanding where photovoltage is generated in a device and where energy losses occur is a key aspect of this, and development of methods which can provide this information is needed. We have previously shown that time-resolved photoelectron spectroscopy of core levels can be used to follow the photovoltage dynamics at a specific interface of a lead sulfide quantum dot solar cell. Here, we use the method's selectivity and sample design to investigate the photovoltage generation in different parts of this solar cell and determine how the different layers (including the absorber layer thickness) contribute to charge separation. We show that all layers contribute to photovoltage generation and that a gold contact deposited on the quantum dots is necessary for full photovoltage generation and slow charge recombination. By combining the information obtained, we are able to experimentally follow the time evolution of the solar cell band structure during the charge separation process. Furthermore, we can identify which specific layers need to be optimized for an overall improvement of quantum dot cells. In the future, this methodology can be applied to other types of devices to provide insights into photovoltage generation mechanisms.
{"title":"Interface-resolved photovoltage generation dynamics and band structure evolution in a PbS quantum dot solar cell.","authors":"Tamara Sloboda, Birgit Kammlander, Elin Berggren, Stefania Riva, Erika Giangrisostomi, Ruslan Ovsyannikov, Håkan Rensmo, Andreas Lindblad, Ute B Cappel","doi":"10.1039/d4nr03428g","DOIUrl":"https://doi.org/10.1039/d4nr03428g","url":null,"abstract":"<p><p>For directed development of solar cells using nanomaterials such as quantum dots, there is a need to understand the device function in detail. Understanding where photovoltage is generated in a device and where energy losses occur is a key aspect of this, and development of methods which can provide this information is needed. We have previously shown that time-resolved photoelectron spectroscopy of core levels can be used to follow the photovoltage dynamics at a specific interface of a lead sulfide quantum dot solar cell. Here, we use the method's selectivity and sample design to investigate the photovoltage generation in different parts of this solar cell and determine how the different layers (including the absorber layer thickness) contribute to charge separation. We show that all layers contribute to photovoltage generation and that a gold contact deposited on the quantum dots is necessary for full photovoltage generation and slow charge recombination. By combining the information obtained, we are able to experimentally follow the time evolution of the solar cell band structure during the charge separation process. Furthermore, we can identify which specific layers need to be optimized for an overall improvement of quantum dot cells. In the future, this methodology can be applied to other types of devices to provide insights into photovoltage generation mechanisms.</p>","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453655","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}
Anubha Rajput, Pandiyan Sivasakthi, Pralok K. Samanta, Biswarup Chakraborty
Among the reported spinel ferrites, the p-block metal containing SnFe2O4 is scarcely explored, but it is a promising water-splitting electrocatalyst. This study focuses on the reaction kinetics and atomic scale insight of the reaction mechanism of oxygen evolution reaction (OER) catalyzed by SnFe2O4 and analogous Fe3O4. The replacement of FeIIOh sites with SnIIOh in SnFe2O4 improves the catalytic efficiency and various intrinsic parameters affecting the reaction kinetics. The variable temperature OER depicts a low activation energy (Ea) of 28.71 kJ mol-1 on SnFe2O4. Experimentally determined second-order dependence on [OH-] and prominent kinetic isotope effect observed during the deuterium labelling study implies the role of hydroxide ion in the rate-determining step (RDS). Using density functional theory, the reaction mechanism on the (001) surface of the SnFe2O4 and Fe3O4 is modelled. The DFT simulated free energy diagram for the reaction intermediates shows an adsorbate evolution mechanism (AEM) on both the ferrite surface where the formation of *OOH is the RDS on SnFe2O4 while *O formation is the RDS on Fe3O4. Contrary to other spinel ferrites, where individual metal sites act independently, in case of SnFe2O4, a synergy between FeIIIOh and the neighbouring SnIIOh atoms is responsible for stabilizing the OER intermediates, enhancing the catalytic OER activity of SnFe2O4 as compared to the isostructural Fe3O4.
{"title":"Recognizing the Reactive Site of SnFe2O4 for the Oxygen Evolution Reaction: Synergistic Effect of SnII and FeIII in Stabilizing Reaction Intermediates","authors":"Anubha Rajput, Pandiyan Sivasakthi, Pralok K. Samanta, Biswarup Chakraborty","doi":"10.1039/d4nr03107e","DOIUrl":"https://doi.org/10.1039/d4nr03107e","url":null,"abstract":"Among the reported spinel ferrites, the p-block metal containing SnFe2O4 is scarcely explored, but it is a promising water-splitting electrocatalyst. This study focuses on the reaction kinetics and atomic scale insight of the reaction mechanism of oxygen evolution reaction (OER) catalyzed by SnFe2O4 and analogous Fe3O4. The replacement of FeIIOh sites with SnIIOh in SnFe2O4 improves the catalytic efficiency and various intrinsic parameters affecting the reaction kinetics. The variable temperature OER depicts a low activation energy (Ea) of 28.71 kJ mol-1 on SnFe2O4. Experimentally determined second-order dependence on [OH-] and prominent kinetic isotope effect observed during the deuterium labelling study implies the role of hydroxide ion in the rate-determining step (RDS). Using density functional theory, the reaction mechanism on the (001) surface of the SnFe2O4 and Fe3O4 is modelled. The DFT simulated free energy diagram for the reaction intermediates shows an adsorbate evolution mechanism (AEM) on both the ferrite surface where the formation of *OOH is the RDS on SnFe2O4 while *O formation is the RDS on Fe3O4. Contrary to other spinel ferrites, where individual metal sites act independently, in case of SnFe2O4, a synergy between FeIIIOh and the neighbouring SnIIOh atoms is responsible for stabilizing the OER intermediates, enhancing the catalytic OER activity of SnFe2O4 as compared to the isostructural Fe3O4.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486290","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}
Xingzhong Chen, Qianqian Tian, Zheng Xiong, Min Wu, Xiao Gong
Flexible wearable sensors can mimic the sensing ability of the skin and transform deformation stimuli into monitorable electrical signals, making them favored in the fields of personalized healthcare, human motion monitoring, and remote monitoring system. However, breathability, softness, comfort, self-cleaning, and stability requirements remain critical challenges because of the proximity to human skin. Here, an innovative piezoresistive physical sensor based on superhydrophobic DTMS/PPy/CNT cotton fabrics (DPC-CFs) was assembled via the dip-coating method. The flexible wearable sensor exhibits self-cleaning capability (high water contact angle of 158.3°), good electric conductivity (45.43 S/m), photo-thermal conversion (surface temperature up to 94.8 °C), rapid response/recovery time (60 ms/50 ms), and excellent stability (> 2400 cycles), which was successfully applied to the dynamic monitoring in a series of human activities such as wrist pulse, voice recognition, and finger bending. Overall, the development of this innovative superhydrophobic piezoresistive physical sensor means an important step forward in the evolution of wearable sensors, offering improved comfort, flexibility, and multi-functionality. The multifunctional flexible wearable sensor can better cover the three-dimensional irregular surface to collect mechanical stimulation signals. It is foreseen that such sensors have broad application prospects in the next generation of biomedical systems, fitness, and human-computer interactive devices.
{"title":"Flexible Wearable Piezoresistive Physical Sensor with Photothermal Conversion and Self-Cleaning Functions for Human Motion Monitoring","authors":"Xingzhong Chen, Qianqian Tian, Zheng Xiong, Min Wu, Xiao Gong","doi":"10.1039/d4nr04063e","DOIUrl":"https://doi.org/10.1039/d4nr04063e","url":null,"abstract":"Flexible wearable sensors can mimic the sensing ability of the skin and transform deformation stimuli into monitorable electrical signals, making them favored in the fields of personalized healthcare, human motion monitoring, and remote monitoring system. However, breathability, softness, comfort, self-cleaning, and stability requirements remain critical challenges because of the proximity to human skin. Here, an innovative piezoresistive physical sensor based on superhydrophobic DTMS/PPy/CNT cotton fabrics (DPC-CFs) was assembled via the dip-coating method. The flexible wearable sensor exhibits self-cleaning capability (high water contact angle of 158.3°), good electric conductivity (45.43 S/m), photo-thermal conversion (surface temperature up to 94.8 °C), rapid response/recovery time (60 ms/50 ms), and excellent stability (> 2400 cycles), which was successfully applied to the dynamic monitoring in a series of human activities such as wrist pulse, voice recognition, and finger bending. Overall, the development of this innovative superhydrophobic piezoresistive physical sensor means an important step forward in the evolution of wearable sensors, offering improved comfort, flexibility, and multi-functionality. The multifunctional flexible wearable sensor can better cover the three-dimensional irregular surface to collect mechanical stimulation signals. It is foreseen that such sensors have broad application prospects in the next generation of biomedical systems, fitness, and human-computer interactive devices.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486305","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}
Yue Zhao, Calvin Thenarianto, Cansu Sevencan, Sivamathini Rajappa, Di Shen, Suppanat Puangpathumanond, Xiaomin Yao, Tedrick Thomas Salim Lew
The pressing issue of food security amid climate change necessitates innovative agricultural practices, including advanced plant genetic engineering techniques. Efficient delivery of biomolecules such as DNA, RNA, and proteins into plant cells is essential for targeted crop improvements, yet traditional methods face significant barriers. This review discusses the multifaceted challenges of biomolecule delivery into plant cells, emphasizing the limitations of conventional methods. We explore the promise of nanoparticle-mediated delivery systems as a versatile alternative. By highlighting the diverse design parameters to tune the physical and chemical properties of nanoparticles, we analyze how these factors influence delivery efficacy. Furthermore, we summarize recent advancements in nanoparticle-mediated delivery, showcasing successful examples of DNA, RNA, and protein transport into plant cells. By understanding and optimizing these design parameters, we can enhance the potential of nanoparticle technologies in plant genetic engineering, paving the way for more resilient and productive agriculture.
{"title":"Rational Nanoparticle Design for Efficient Biomolecule Delivery in Plant Genetic Engineering","authors":"Yue Zhao, Calvin Thenarianto, Cansu Sevencan, Sivamathini Rajappa, Di Shen, Suppanat Puangpathumanond, Xiaomin Yao, Tedrick Thomas Salim Lew","doi":"10.1039/d4nr03760j","DOIUrl":"https://doi.org/10.1039/d4nr03760j","url":null,"abstract":"The pressing issue of food security amid climate change necessitates innovative agricultural practices, including advanced plant genetic engineering techniques. Efficient delivery of biomolecules such as DNA, RNA, and proteins into plant cells is essential for targeted crop improvements, yet traditional methods face significant barriers. This review discusses the multifaceted challenges of biomolecule delivery into plant cells, emphasizing the limitations of conventional methods. We explore the promise of nanoparticle-mediated delivery systems as a versatile alternative. By highlighting the diverse design parameters to tune the physical and chemical properties of nanoparticles, we analyze how these factors influence delivery efficacy. Furthermore, we summarize recent advancements in nanoparticle-mediated delivery, showcasing successful examples of DNA, RNA, and protein transport into plant cells. By understanding and optimizing these design parameters, we can enhance the potential of nanoparticle technologies in plant genetic engineering, paving the way for more resilient and productive agriculture.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486302","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}
![[triple bond, length as m-dash]](https://www.rsc.org/images/entities/char_e002.gif)
N bond for N2 reduction and boosting C–N coupling for urea synthesis. DACs also possess the ability to break the linear scaling relation of adsorption energy of reactants and intermediates, allowing for tuning of intermediate adsorption energies. Finally, possible future research directions using ACs are proposed.
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