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Chinese Journal of Structural Chemistry
Chinese Journal of Structural Chemistry
主管 : 中国科学院
刊期 : 月刊主编 : 洪茂椿
语种 : 英文主办 : 中国科学院福建物质结构研究所、中国化学会
ISSN : 0254-5861 CN : 35-1112/TQ展开 >The Chinese Journal of Structural Chemistry, founded in 1982 by Prof. Jiaxi Lu, is an international peer-reviewed journal published in English. It publishes original research works about the structure and property of matter, including but not limited to coordination chemistry, organometallic chemistry, catalysis, energy, nanomaterial, theory/computation, structural characterization, pharmacy and life science. Published monthly by Fujian Institute of Research on the Structure of Matter, CAS, in the form of Articles, Communications, Reviews, Perspectives, and News & Views. - 影响因子: 5.9
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1
Recent Advances of Cu-Based Materials for Electrochemical Nitrate Reduction to Ammonia
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Transition Metal Boride-Based Materials for Electrocatalytic Water Splitting
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3
Uncovering the Mechanism for Urea Electrochemical Synthesis by Coupling N2 and CO2 on Mo2C-MXene
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Methods to Make Conductive Covalent Organic Frameworks for Electrocatalytic Applications
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2024, 43(11): 100334
doi: 10.1016/j.cjsc.2024.100334
摘要:
In summary, these two works demonstrate that the solvation structure and the stable SEI layer play a critical role in the electrochemical behavior of AFSMBs. By adjusting the electrolyte salt or solvent, the solvation structure can be effectively regulated and the inorganic-rich, robust SEI with high ionic conductivity can be constructed, in turn achieving the favorable electrochemical performance. The design strategy for refining the electrolyte solvation structure and interfacial chemistry provides valuable insight and stimulates new activity in the future research and development of high-energy batteries for sodium and other rechargeable systems (e.g., rechargeable Li/K batteries).
In summary, these two works demonstrate that the solvation structure and the stable SEI layer play a critical role in the electrochemical behavior of AFSMBs. By adjusting the electrolyte salt or solvent, the solvation structure can be effectively regulated and the inorganic-rich, robust SEI with high ionic conductivity can be constructed, in turn achieving the favorable electrochemical performance. The design strategy for refining the electrolyte solvation structure and interfacial chemistry provides valuable insight and stimulates new activity in the future research and development of high-energy batteries for sodium and other rechargeable systems (e.g., rechargeable Li/K batteries).
2024, 43(11): 100345
doi: 10.1016/j.cjsc.2024.100345
摘要:
In summary, the precise design of new OER catalysts bearing low cost and acid-resistance remains challenging, thus inevitably hindering the rapid development of PEM electrolyzer in the short run. This inspiring work demonstrates the effectiveness of Fe incorporation in reducing the kinetic barrier of acidic OER process by enhancing water adsorption and dissociation via regulating the electrophilicity of surface oxygen, being of great reference value for exploiting economic OER in acidic conditions. However, some key factors that affect catalytic performance, such as hydrogen spillovers, reduction and oxidation properties of catalysts, should be discussed. With respect to the future research, more efforts are worthy to be devoted to finding alternative non-toxic heteroatoms for the design of high-performance satisfactory low-cost catalysts.
In summary, the precise design of new OER catalysts bearing low cost and acid-resistance remains challenging, thus inevitably hindering the rapid development of PEM electrolyzer in the short run. This inspiring work demonstrates the effectiveness of Fe incorporation in reducing the kinetic barrier of acidic OER process by enhancing water adsorption and dissociation via regulating the electrophilicity of surface oxygen, being of great reference value for exploiting economic OER in acidic conditions. However, some key factors that affect catalytic performance, such as hydrogen spillovers, reduction and oxidation properties of catalysts, should be discussed. With respect to the future research, more efforts are worthy to be devoted to finding alternative non-toxic heteroatoms for the design of high-performance satisfactory low-cost catalysts.
2024, 43(11): 100368
doi: 10.1016/j.cjsc.2024.100368
摘要:
In summary, this work presented a compelling study of employing a flexible-robust MOF to achieve highly efficient C3F6/C3F8 separation through a temperature-modulated gating mechanism. Here, they emphasize the important role of temperature-dependent gate-opening adsorption behavior and elucidate the host-guest interactions through a combination of experimental, single-crystal structural, and theoretical computational analyses. This finding provides a valuable idea for harnessing the flexibility of porous adsorbents and distinct host-guest interactions to effectively separate important and challenging industrial gas mixtures.
In summary, this work presented a compelling study of employing a flexible-robust MOF to achieve highly efficient C3F6/C3F8 separation through a temperature-modulated gating mechanism. Here, they emphasize the important role of temperature-dependent gate-opening adsorption behavior and elucidate the host-guest interactions through a combination of experimental, single-crystal structural, and theoretical computational analyses. This finding provides a valuable idea for harnessing the flexibility of porous adsorbents and distinct host-guest interactions to effectively separate important and challenging industrial gas mixtures.
2024, 43(11): 100374
doi: 10.1016/j.cjsc.2024.100374
摘要:
In summary, APMOFs have exhibited great potential for challenging hydrocarbon separations in lab scale by overcoming the trade-off between adsorption capacity and selectivity to a large extent. Nonetheless, several challenges persist for the future deployment of APMOFs in practical industrial separation applications. First, the stability of many APMOFs (eg, SIFSIX-1-Cu) need further improvement; second, the scalability and cost of APMOFs need further consideration; last but not the least, the realistic separation performance under real-word conditions with moisture and more complicated impurities should be evaluated as well.
In summary, APMOFs have exhibited great potential for challenging hydrocarbon separations in lab scale by overcoming the trade-off between adsorption capacity and selectivity to a large extent. Nonetheless, several challenges persist for the future deployment of APMOFs in practical industrial separation applications. First, the stability of many APMOFs (eg, SIFSIX-1-Cu) need further improvement; second, the scalability and cost of APMOFs need further consideration; last but not the least, the realistic separation performance under real-word conditions with moisture and more complicated impurities should be evaluated as well.
2024, 43(11): 100375
doi: 10.1016/j.cjsc.2024.100375
摘要:
Utilizing sunlight to split water into H2 and O2 is a highly promising approach in renewable energy production approaches. Recently, significant efforts have been devoted to develop innovative photocatalysts for splitting water. Metal-free two-dimensional (2D) covalent organic frameworks (COFs) are emerging as ideal catalytic platforms for this purpose. However, the rational design of these materials requires appropriate band alignment and active sites capable of catalyzing both hydrogen and oxygen evolution reactions, which depends on the judicious selection of molecular precursors. To address these requirements, first-principles calculations have proven to be an efficient method for designing and screening potential photocatalysts. Here, we provide a concise overview of recent advancements in the development of 2D COFs photocatalysts for overall water splitting (OWS), examining it from a theoretical perspective. This includes outlining the design principles, exploring the data-driven discovery of potential candidates using a COFs database, and applying machine learning techniques to predict the electronic structure of COFs based on the molecular orbitals of their precursors. Furthermore, we discuss the accuracy of current computational methods and address future challenges and potential of 2D COFs in practical applications for OWS.
Utilizing sunlight to split water into H2 and O2 is a highly promising approach in renewable energy production approaches. Recently, significant efforts have been devoted to develop innovative photocatalysts for splitting water. Metal-free two-dimensional (2D) covalent organic frameworks (COFs) are emerging as ideal catalytic platforms for this purpose. However, the rational design of these materials requires appropriate band alignment and active sites capable of catalyzing both hydrogen and oxygen evolution reactions, which depends on the judicious selection of molecular precursors. To address these requirements, first-principles calculations have proven to be an efficient method for designing and screening potential photocatalysts. Here, we provide a concise overview of recent advancements in the development of 2D COFs photocatalysts for overall water splitting (OWS), examining it from a theoretical perspective. This includes outlining the design principles, exploring the data-driven discovery of potential candidates using a COFs database, and applying machine learning techniques to predict the electronic structure of COFs based on the molecular orbitals of their precursors. Furthermore, we discuss the accuracy of current computational methods and address future challenges and potential of 2D COFs in practical applications for OWS.
2024, 43(11): 100392
doi: 10.1016/j.cjsc.2024.100392
摘要:
Overall, nanomaterials with HONs hold tremendous potential for revolutionizing various fields, from electronics and photonics to energy and biomedicine. Their precise control over structure-property relationships offers unprecedented opportunities for designing and engineering materials with tailored properties and functionalities. However, realizing this potential requires addressing key challenges related to scalability, environmental impact, and integration. By overcoming these challenges through collaborative research and innovation, we can unlock the full promise of nanomaterials with HONs and utilize them to have a transformative impact on society and the economy.
Overall, nanomaterials with HONs hold tremendous potential for revolutionizing various fields, from electronics and photonics to energy and biomedicine. Their precise control over structure-property relationships offers unprecedented opportunities for designing and engineering materials with tailored properties and functionalities. However, realizing this potential requires addressing key challenges related to scalability, environmental impact, and integration. By overcoming these challenges through collaborative research and innovation, we can unlock the full promise of nanomaterials with HONs and utilize them to have a transformative impact on society and the economy.
2024, 43(11): 100405
doi: 10.1016/j.cjsc.2024.100405
摘要:
Ligand plays a critical role in determining the physicochemical properties and functionalities of metal nanoclusters, as the ligand molecules interact with a significant amount of metal atoms in the core through various binding moieties. Compared with the most commonly employed thiolate molecule, alkynyl ligand represents a new avenue to prepare coinage metal nanoclusters, as it can bind to the metal atoms with either σ bonding or π bonding or both. In this review, we first describe the definition of atomically precise metal nanoclusters and the significance of ligand in metal nanoclusters. Then, the impact and unique advantages of employing alkynyl ligand for fabricating coinage metal nanoclusters are discussed, with focus on the enrichment of interfacial binding structure, the regulation of physicochemical properties, and the improvement of functionalities. Some explicit examples are provided, aiming to elucidate the structure-property-functionality relationship at the atomic level. Finally, a conclusion and introspective outlook regarding designing alkynyl ligand for future regulation the structure/property/functionality of metal nanoclusters is presented.
Ligand plays a critical role in determining the physicochemical properties and functionalities of metal nanoclusters, as the ligand molecules interact with a significant amount of metal atoms in the core through various binding moieties. Compared with the most commonly employed thiolate molecule, alkynyl ligand represents a new avenue to prepare coinage metal nanoclusters, as it can bind to the metal atoms with either σ bonding or π bonding or both. In this review, we first describe the definition of atomically precise metal nanoclusters and the significance of ligand in metal nanoclusters. Then, the impact and unique advantages of employing alkynyl ligand for fabricating coinage metal nanoclusters are discussed, with focus on the enrichment of interfacial binding structure, the regulation of physicochemical properties, and the improvement of functionalities. Some explicit examples are provided, aiming to elucidate the structure-property-functionality relationship at the atomic level. Finally, a conclusion and introspective outlook regarding designing alkynyl ligand for future regulation the structure/property/functionality of metal nanoclusters is presented.
2024, 43(11): 100412
doi: 10.1016/j.cjsc.2024.100412
摘要:
Ketene and its derivatives, including surface acetate and acylium ion, are pivotal intermediates in zeolite catalysis, facilitating the conversion of C1 molecules into various chemicals. Understanding the formation, transformation, and function of ketene in zeolite catalysis is fundamental for comprehending and enhancing numerous chemical processes. Recent research advances have contributed significantly to a deeper molecular-level comprehension of how ketene affects the catalytic efficacy of zeolites, thereby playing a crucial role in the advancement of more efficient and selective catalytic processes. This minireview aims to provide an overview of ketene chemistry in zeolite catalysis, delineate the reaction network involving ketene, elucidate the role of ketene in zeolite-catalyzed reactions, and summarize the methods for characterizing ketene in zeolite environments.
Ketene and its derivatives, including surface acetate and acylium ion, are pivotal intermediates in zeolite catalysis, facilitating the conversion of C1 molecules into various chemicals. Understanding the formation, transformation, and function of ketene in zeolite catalysis is fundamental for comprehending and enhancing numerous chemical processes. Recent research advances have contributed significantly to a deeper molecular-level comprehension of how ketene affects the catalytic efficacy of zeolites, thereby playing a crucial role in the advancement of more efficient and selective catalytic processes. This minireview aims to provide an overview of ketene chemistry in zeolite catalysis, delineate the reaction network involving ketene, elucidate the role of ketene in zeolite-catalyzed reactions, and summarize the methods for characterizing ketene in zeolite environments.
2024, 43(11): 100415
doi: 10.1016/j.cjsc.2024.100415
摘要:
The electrocatalytic CO2 reduction reaction (CO2RR) represents an effective way to address energy crises and environmental issues by converting CO2 into valuable chemicals. Single-atom catalysts (SACs) can achieve excellent catalytic activity in CO2RR. However, the study of CO2RR on SACs still poses significant challenges, especially in terms of controlling the selectivity towards the deep product such as CH4 and CH3OH. Herein, we employ density functional theory (DFT) calculations to investigate the CO2RR on the Cu single-atom catalysts supported on N-doped graphene (Cu-N/C) and explore the role of N dopants on the CO2RR performance. The results predict that, compared to Cu SACs supported on N-doped defective graphene with double vacancy (Cu-N/C-DV), Cu SACs supported on N-doped defective graphene with single vacancy (Cu-N/C-SV) can effectively convert CO2 into the deeply reduced C1 products, including CH4 and CH3OH. The results further indicate that Cu-N/C-SV has a stronger interaction with *CO, which is conducive to the deep reduction of *CO. Increasing the coordination number of N atoms or the proximity of the doping site to Cu active site can effectively enhance the stability of the catalyst and promote the adsorption of *CO on Cu-N/C-SV. However, this also increases the free energy of the formation of *CHO intermediate. The results indicate that CuC3-Nm, which contains an N atom in the second coordination shell (meta-position) of Cu SACs, has the best electrocatalytic performance of CO2RR in terms of both selectivity and catalytic activity. These results not only contribute to an in-depth understanding of the reaction mechanism of CO2RR on SACs but also provide insights into the design of SACs for efficient CO2RR.
The electrocatalytic CO2 reduction reaction (CO2RR) represents an effective way to address energy crises and environmental issues by converting CO2 into valuable chemicals. Single-atom catalysts (SACs) can achieve excellent catalytic activity in CO2RR. However, the study of CO2RR on SACs still poses significant challenges, especially in terms of controlling the selectivity towards the deep product such as CH4 and CH3OH. Herein, we employ density functional theory (DFT) calculations to investigate the CO2RR on the Cu single-atom catalysts supported on N-doped graphene (Cu-N/C) and explore the role of N dopants on the CO2RR performance. The results predict that, compared to Cu SACs supported on N-doped defective graphene with double vacancy (Cu-N/C-DV), Cu SACs supported on N-doped defective graphene with single vacancy (Cu-N/C-SV) can effectively convert CO2 into the deeply reduced C1 products, including CH4 and CH3OH. The results further indicate that Cu-N/C-SV has a stronger interaction with *CO, which is conducive to the deep reduction of *CO. Increasing the coordination number of N atoms or the proximity of the doping site to Cu active site can effectively enhance the stability of the catalyst and promote the adsorption of *CO on Cu-N/C-SV. However, this also increases the free energy of the formation of *CHO intermediate. The results indicate that CuC3-Nm, which contains an N atom in the second coordination shell (meta-position) of Cu SACs, has the best electrocatalytic performance of CO2RR in terms of both selectivity and catalytic activity. These results not only contribute to an in-depth understanding of the reaction mechanism of CO2RR on SACs but also provide insights into the design of SACs for efficient CO2RR.
2024, 43(11): 100416
doi: 10.1016/j.cjsc.2023.100416
摘要:
Graphitic carbon nitride (g-C3N4, CN) is recognized as the most extensively studied organic polymeric photocatalyst for pollution control and energy conversion, due to its facile synthesis and suitable electronic band structure. The aim of the present work is to explore the effect of precursors, such as urea (U, (NH2)2CO), dicyandiamide (D, C2H4N4) and melamine (M, C3H6N6), on the structure and photocatalytic activity of the obtained CN samples, denoted as UCN, DCN and MCN, respectively. The sheet-like UCN sample shows significantly enhanced photoreactivity in both NO oxidation and CO2 reduction compared to the bulk DCN and MCN materials. In addition, UCN demonstrates the ability to suppress the formation of the toxic NO2 intermediate during the photocatalytic oxidation of NO. The enhanced photocatalytic activity of UCN can be attributed to a dual effect: first, its increased specific surface area provides more active sites for the photocatalytic reaction; second, it exhibits a stronger affinity for substrates like NO and CO2, which facilitates charge migration at the interface.
Graphitic carbon nitride (g-C3N4, CN) is recognized as the most extensively studied organic polymeric photocatalyst for pollution control and energy conversion, due to its facile synthesis and suitable electronic band structure. The aim of the present work is to explore the effect of precursors, such as urea (U, (NH2)2CO), dicyandiamide (D, C2H4N4) and melamine (M, C3H6N6), on the structure and photocatalytic activity of the obtained CN samples, denoted as UCN, DCN and MCN, respectively. The sheet-like UCN sample shows significantly enhanced photoreactivity in both NO oxidation and CO2 reduction compared to the bulk DCN and MCN materials. In addition, UCN demonstrates the ability to suppress the formation of the toxic NO2 intermediate during the photocatalytic oxidation of NO. The enhanced photocatalytic activity of UCN can be attributed to a dual effect: first, its increased specific surface area provides more active sites for the photocatalytic reaction; second, it exhibits a stronger affinity for substrates like NO and CO2, which facilitates charge migration at the interface.
2024, 43(11): 100417
doi: 10.1016/j.cjsc.2024.100417
摘要:
This work presents a significant advancement in the development of highly efficient NIR-emissive materials. By strategically doping gold nanoclusters with copper, the researchers achieved a near-unity PLQY in the NIR region at room temperature. The comprehensive analysis of structural, photophysical, and excited-state dynamics provides valuable insights into the mechanisms driving this enhanced luminescence. The findings highlight the potential of these nanoclusters for applications in biological imaging and optical communication. However, challenges such as ensuring long-term stability, scalable synthesis, and seamless integration into existing technologies must be addressed, while future exploration of other dopants and synthetic strategies could further enhance their optical properties, paving the way for exciting advancements in nanomaterials.
This work presents a significant advancement in the development of highly efficient NIR-emissive materials. By strategically doping gold nanoclusters with copper, the researchers achieved a near-unity PLQY in the NIR region at room temperature. The comprehensive analysis of structural, photophysical, and excited-state dynamics provides valuable insights into the mechanisms driving this enhanced luminescence. The findings highlight the potential of these nanoclusters for applications in biological imaging and optical communication. However, challenges such as ensuring long-term stability, scalable synthesis, and seamless integration into existing technologies must be addressed, while future exploration of other dopants and synthetic strategies could further enhance their optical properties, paving the way for exciting advancements in nanomaterials.
2024, 43(11): 100426
doi: 10.1016/j.cjsc.2024.100426
摘要:
In recent years, organic-inorganic hybrid materials are widely designed and synthesized as switching materials for temperature response. However, due to the change of the molecular arrangement inside the crystal during the solid-solid phase transition, the distortion of the crystal lattice and the great change of lattice parameters are often caused, which would result a poor repeatability and short life. Thus, designing phase change materials with small lattice changes helps to improve product life. In this article, a novel organic-inorganic hybrid material 3HDMAPAPbBr4 (1, 3HDMAPA is 3-(hydroxydimethylammonio)propan-1-aminium) was successfully synthesized and characterized. For 1, organic cations filled in the van der Waals gap are connected by hydrogen bonds with halogens in the two-dimensional inorganic layer, forming a stable sandwich structure. During the solid-solid phase transition driven by temperature, the changes of inorganic skeleton are relatively small, and the disorder movement of organic cations does not affect the existence of hydrogen bonds, maintaining a relatively stable crystal structure. In addition, electrical property, optical property and crystal structures are analysed and discussed in detail in this work. We believe that our work will contribute to the development and application of phase change materials in response materials.
In recent years, organic-inorganic hybrid materials are widely designed and synthesized as switching materials for temperature response. However, due to the change of the molecular arrangement inside the crystal during the solid-solid phase transition, the distortion of the crystal lattice and the great change of lattice parameters are often caused, which would result a poor repeatability and short life. Thus, designing phase change materials with small lattice changes helps to improve product life. In this article, a novel organic-inorganic hybrid material 3HDMAPAPbBr4 (1, 3HDMAPA is 3-(hydroxydimethylammonio)propan-1-aminium) was successfully synthesized and characterized. For 1, organic cations filled in the van der Waals gap are connected by hydrogen bonds with halogens in the two-dimensional inorganic layer, forming a stable sandwich structure. During the solid-solid phase transition driven by temperature, the changes of inorganic skeleton are relatively small, and the disorder movement of organic cations does not affect the existence of hydrogen bonds, maintaining a relatively stable crystal structure. In addition, electrical property, optical property and crystal structures are analysed and discussed in detail in this work. We believe that our work will contribute to the development and application of phase change materials in response materials.
2024, 43(10): 100321
doi: 10.1016/j.cjsc.2024.100321
摘要:
In summary, the integrated conductivity and hydrophilic gradient imprinted gradient zinc anode can effectively inhibit side reactions and regulate zinc deposition behavior, thus achieving long-term cycling under high current/capacity. When multiple materials are composited for use as zinc anode coatings, different structural designs may have a dramatic effect on the electrochemical performance, even though the components are the same. The gradient imprinted design and related analysis method can be applied to other zinc anode coating materials, which will contribute to the design of future AZIBs. Moreover, at high current density/capacity, other metal-anode secondary batteries (e.g., lithium-ion batteries, sodium-ion batteries, aluminum-ion batteries, etc.) almost always suffer from serious dendrite problems, and thereby this work can also provide new research inspiration.
In summary, the integrated conductivity and hydrophilic gradient imprinted gradient zinc anode can effectively inhibit side reactions and regulate zinc deposition behavior, thus achieving long-term cycling under high current/capacity. When multiple materials are composited for use as zinc anode coatings, different structural designs may have a dramatic effect on the electrochemical performance, even though the components are the same. The gradient imprinted design and related analysis method can be applied to other zinc anode coating materials, which will contribute to the design of future AZIBs. Moreover, at high current density/capacity, other metal-anode secondary batteries (e.g., lithium-ion batteries, sodium-ion batteries, aluminum-ion batteries, etc.) almost always suffer from serious dendrite problems, and thereby this work can also provide new research inspiration.
2024, 43(10): 100322
doi: 10.1016/j.cjsc.2024.100322
摘要:
This study reports for the first time the synthesis of homogeneous high-order metalla[4]catenane through coordination driven self-assembly strategy, and the complicated topology could be transformed into corresponding organometallic macrocyclic compound accompanied by a decrease in concentration in methanol solution. Besides, the strong interlayer π…π stacking interaction and non-classical hydrogen bonding play a crucial role in the formation and stability of metalla[4]catenane structure, which contributes to a deeper understanding of the driving forces behind the formation of molecular metalla catenanes and also has important theoretical and practical significance for promoting the development of this research system. These findings will further motivate researchers to explore the construction of mechanically interlocked supramolecular topological complexes.
This study reports for the first time the synthesis of homogeneous high-order metalla[4]catenane through coordination driven self-assembly strategy, and the complicated topology could be transformed into corresponding organometallic macrocyclic compound accompanied by a decrease in concentration in methanol solution. Besides, the strong interlayer π…π stacking interaction and non-classical hydrogen bonding play a crucial role in the formation and stability of metalla[4]catenane structure, which contributes to a deeper understanding of the driving forces behind the formation of molecular metalla catenanes and also has important theoretical and practical significance for promoting the development of this research system. These findings will further motivate researchers to explore the construction of mechanically interlocked supramolecular topological complexes.
2024, 43(10): 100325
doi: 10.1016/j.cjsc.2024.100325
摘要:
In summary, the booming development of c-MOFs brings opportunities for the development of new electromagnetic functional materials and devices, and the design and customization of MOF structural units, overall topology modulation, and the construction of three-dimensional structures based on the understanding of electromagnetic properties and energy conversion provide new insights for further investigation of the EMW absorption mechanism and enhancement of dielectric properties. However, conductive MOFs also face challenges such as few available types, poor impedance matching, and narrow absorption bandwidth. Furthermore, in practical potential applications, conductive MOF can also be made into MOF films for stealth coatings for military equipment and EMW protection for civilian use.
In summary, the booming development of c-MOFs brings opportunities for the development of new electromagnetic functional materials and devices, and the design and customization of MOF structural units, overall topology modulation, and the construction of three-dimensional structures based on the understanding of electromagnetic properties and energy conversion provide new insights for further investigation of the EMW absorption mechanism and enhancement of dielectric properties. However, conductive MOFs also face challenges such as few available types, poor impedance matching, and narrow absorption bandwidth. Furthermore, in practical potential applications, conductive MOF can also be made into MOF films for stealth coatings for military equipment and EMW protection for civilian use.
2024, 43(10): 100329
doi: 10.1016/j.cjsc.2024.100329
摘要:
In the future, the nanoconfined water monolayer concept may also work for the aligning assembly of heterostructures of other types of 2D materials. Indeed, the confinement engineering has provided a universal guideline for designing catalysts, membranes and chemical reactions. First, the synergy of chemical and spatial confinement elevated the secondary battery performances by innovative microstructures and properties. Second, the confinement effect may enhance the supercapacitor performances by the load of redox-active nanowires between MXene nanosheets. Third, the Marangoni effect results in the confinement of carbon nanotubes at MXene interfaces, which compose a fast-response humidity sensor. More interesting behaviors could be expected after improving the in-plane alignment of the heterostructures of 2D materials, which may exhibit enhanced magnetic and half-metallic properties as well as enhanced proton and spin-transport performances.
In the future, the nanoconfined water monolayer concept may also work for the aligning assembly of heterostructures of other types of 2D materials. Indeed, the confinement engineering has provided a universal guideline for designing catalysts, membranes and chemical reactions. First, the synergy of chemical and spatial confinement elevated the secondary battery performances by innovative microstructures and properties. Second, the confinement effect may enhance the supercapacitor performances by the load of redox-active nanowires between MXene nanosheets. Third, the Marangoni effect results in the confinement of carbon nanotubes at MXene interfaces, which compose a fast-response humidity sensor. More interesting behaviors could be expected after improving the in-plane alignment of the heterostructures of 2D materials, which may exhibit enhanced magnetic and half-metallic properties as well as enhanced proton and spin-transport performances.
2024, 43(10): 100330
doi: 10.1016/j.cjsc.2024.100330
摘要:
In conclusion, Xiong et al. developed a HEA/SrTiO3 catalyst for efficient photothermal methane dry reforming. This work proposes a unique carbon exchange mechanism based on in-depth spectroscopic techniques, providing a new perspective on overcoming stability and selectivity issues in the DRM process. The work would be expected to inspire the development of efficient DRM catalysts under mild conditions.
In conclusion, Xiong et al. developed a HEA/SrTiO3 catalyst for efficient photothermal methane dry reforming. This work proposes a unique carbon exchange mechanism based on in-depth spectroscopic techniques, providing a new perspective on overcoming stability and selectivity issues in the DRM process. The work would be expected to inspire the development of efficient DRM catalysts under mild conditions.
2024, 43(10): 100331
doi: 10.1016/j.cjsc.2024.100331
摘要:
In summary, this work establishes a correlation between OVs and bound exciton luminescence by single-particle spectroscopy. It confirms that the PL emission of m-BiVO4 originates from the defect state. Additionally, the study achieves visual imaging of the spatial distribution of oxygen defects by PL lifetime imaging maps. Furthermore, single-particle spectroscopy can be used to monitor charge transfer during photocatalysis in situ, indicating that the generation of OVs at specific crystal facets facilitates efficient charge transfer between electrons and reactants. This work provides an imaging technique to accurately monitor the spatial distribution of defects in single-crystal materials, and a method for spatial high-resolution real-time monitoring of multiphase catalytic reactions, aiming to provide an in-depth understanding of the relationship between the structure-activity of materials.
In summary, this work establishes a correlation between OVs and bound exciton luminescence by single-particle spectroscopy. It confirms that the PL emission of m-BiVO4 originates from the defect state. Additionally, the study achieves visual imaging of the spatial distribution of oxygen defects by PL lifetime imaging maps. Furthermore, single-particle spectroscopy can be used to monitor charge transfer during photocatalysis in situ, indicating that the generation of OVs at specific crystal facets facilitates efficient charge transfer between electrons and reactants. This work provides an imaging technique to accurately monitor the spatial distribution of defects in single-crystal materials, and a method for spatial high-resolution real-time monitoring of multiphase catalytic reactions, aiming to provide an in-depth understanding of the relationship between the structure-activity of materials.
2024, 43(10): 100344
doi: 10.1016/j.cjsc.2024.100344
摘要:
In summary, the increasing interest in separating lanthanides and actinides for the purposes of spent nuclear fuel reprocessing has spurred renewed research efforts in this domain recently. Although the higher oxidation states of Am have been recognized for several decades, the development of separation techniques based on the control of Am oxidation state remains less advanced. The key challenge in spent fuel reprocessing lies in achieving complete oxidation and long-term stabilization of high-valence Am under practical conditions. This necessitates addressing the complexities of real-world spent fuel reprocessing scenarios (high acidity and radiation level) and minimizing the generation of secondary waste. In this perspective, we outline the most recent advances in lanthanide and actinide separation following redox-based protocols. High Am/Ln separation factors have been achieved in these works via judicious synergy between proper selection of chemical oxidants and stabilization of Am(V)/Am(VI) via complexation or ion sieving. Ongoing efforts to develop oxidation strategies and separation technologies hold the potential to yield an advanced process suitable for application within the nuclear industry. In addition, separation strategies based on oxidation state control holds promise for addressing the even more challenging task of Am/Cm separation in advanced nuclear fuel cycle.
In summary, the increasing interest in separating lanthanides and actinides for the purposes of spent nuclear fuel reprocessing has spurred renewed research efforts in this domain recently. Although the higher oxidation states of Am have been recognized for several decades, the development of separation techniques based on the control of Am oxidation state remains less advanced. The key challenge in spent fuel reprocessing lies in achieving complete oxidation and long-term stabilization of high-valence Am under practical conditions. This necessitates addressing the complexities of real-world spent fuel reprocessing scenarios (high acidity and radiation level) and minimizing the generation of secondary waste. In this perspective, we outline the most recent advances in lanthanide and actinide separation following redox-based protocols. High Am/Ln separation factors have been achieved in these works via judicious synergy between proper selection of chemical oxidants and stabilization of Am(V)/Am(VI) via complexation or ion sieving. Ongoing efforts to develop oxidation strategies and separation technologies hold the potential to yield an advanced process suitable for application within the nuclear industry. In addition, separation strategies based on oxidation state control holds promise for addressing the even more challenging task of Am/Cm separation in advanced nuclear fuel cycle.
2024, 43(10): 100390
doi: 10.1016/j.cjsc.2024.100390
摘要:
Interface is a necessary channel of carrier permeation in sulfide-based all-solid-state lithium battery (ASSLB). Homogeneous and fast lithium-ion (Li+) interfacial transport of cathode is the overriding premise for high capability of ASSLBs. However, the inherent transport heterogeneity of crystalline materials in cathode and the cathode active material (CAM)/sulfide solid electrolyte (SSE) interfacial issues result in high interfacial impedance, decreasing the Li+ transfer kinetics. In this review, we outline the Li+ transport properties of CAMs and SSEs, followed by a discussion of their interfacial electro-chemo-mechanical issues. Commentary is also provided on the solutions to the multiple-scale interfacial Li+ transport failure. Furthermore, the underlying interdependent mechanisms between electrodes are summarized and overviewed. Finally, we suggest future paths to better comprehend and promote the interfacial Li+ transport in ASSLBs. This review provides an in-depth understanding of cathodal interfacial issues and the proposed improvement strategies will provide guidance for further advancement of high-performance ASSLBs.
Interface is a necessary channel of carrier permeation in sulfide-based all-solid-state lithium battery (ASSLB). Homogeneous and fast lithium-ion (Li+) interfacial transport of cathode is the overriding premise for high capability of ASSLBs. However, the inherent transport heterogeneity of crystalline materials in cathode and the cathode active material (CAM)/sulfide solid electrolyte (SSE) interfacial issues result in high interfacial impedance, decreasing the Li+ transfer kinetics. In this review, we outline the Li+ transport properties of CAMs and SSEs, followed by a discussion of their interfacial electro-chemo-mechanical issues. Commentary is also provided on the solutions to the multiple-scale interfacial Li+ transport failure. Furthermore, the underlying interdependent mechanisms between electrodes are summarized and overviewed. Finally, we suggest future paths to better comprehend and promote the interfacial Li+ transport in ASSLBs. This review provides an in-depth understanding of cathodal interfacial issues and the proposed improvement strategies will provide guidance for further advancement of high-performance ASSLBs.
2024, 43(10): 100393
doi: 10.1016/j.cjsc.2023.100393
摘要:
Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing, information encryption, and microelectronics. We report herein the binary assembly of a blue-emissive iridium complex and a red-emissive ruthenium complex into homogeneously-doped or optically-heterostructured microcrystals with thermo-responsive properties. Depending on the assembly conditions, lateral or longitudinal triblock heterostructures with a microplate shape are obtained, which display distinct emission pattern changes upon heating as a result of the decreased efficiency of energy transfer. In addition, branched heterostructures are prepared by a stepwise assembly. The luminescence polarization of the homogeneously-doped binary crystals and the waveguiding property of the longitudinal triblock heterostructure are further examined. This work evidences the versatility of transition metal complexes in the assembly into various luminescent nano/micro structures with potential applications in thermo-sensing and nanophotonics.
Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing, information encryption, and microelectronics. We report herein the binary assembly of a blue-emissive iridium complex and a red-emissive ruthenium complex into homogeneously-doped or optically-heterostructured microcrystals with thermo-responsive properties. Depending on the assembly conditions, lateral or longitudinal triblock heterostructures with a microplate shape are obtained, which display distinct emission pattern changes upon heating as a result of the decreased efficiency of energy transfer. In addition, branched heterostructures are prepared by a stepwise assembly. The luminescence polarization of the homogeneously-doped binary crystals and the waveguiding property of the longitudinal triblock heterostructure are further examined. This work evidences the versatility of transition metal complexes in the assembly into various luminescent nano/micro structures with potential applications in thermo-sensing and nanophotonics.
2024, 43(10): 100394
doi: 10.1016/j.cjsc.2024.100394
摘要:
The identical molecular size and similar physical properties of carbon dioxide (CO2) and acetylene (C2H2) make their adsorptive separation extremely challenging to achieve with most adsorbents. Reports on the separation of CO2 and C2H2 mixtures by zeolites are even rarer with the mechanism of adsorptive separation requiring further exploration. In this paper, we report that ion modulation of zeolite 5A promotes the difference in kinetic diffusion of CO2 and C2H2, realizing the inverse separation of zeolite from selective adsorption of C2H2 to selective adsorption of CO2. Creating a compact pore space restricting the orientation of gas molecules enables charge recognition. The positive electrostatic potential at the pore openings was utilized to hinder the diffusion of C2H2 between the cages while ensuring the transfer of CO2, increasing their diffusion differences in pore channels and leading to the CO2/C2H2 kinetic selectivity of 31.97. Grand canonical Monte Carlo (GCMC) simulation demonstrates that the CO2 distribution in K-5A-β is significantly higher than that of C2H2. Dynamic breakthrough experiments verify the excellent performance of material in practical CO2/C2H2 separation, for CO2/C2H2 (50/50 and 1/99, V/V) mixtures can be separated in one step, thus directly generating high purity C2H2 (> 99.95%), which provides a promising thought for the zeolite-based separation of CO2 and C2H2.
The identical molecular size and similar physical properties of carbon dioxide (CO2) and acetylene (C2H2) make their adsorptive separation extremely challenging to achieve with most adsorbents. Reports on the separation of CO2 and C2H2 mixtures by zeolites are even rarer with the mechanism of adsorptive separation requiring further exploration. In this paper, we report that ion modulation of zeolite 5A promotes the difference in kinetic diffusion of CO2 and C2H2, realizing the inverse separation of zeolite from selective adsorption of C2H2 to selective adsorption of CO2. Creating a compact pore space restricting the orientation of gas molecules enables charge recognition. The positive electrostatic potential at the pore openings was utilized to hinder the diffusion of C2H2 between the cages while ensuring the transfer of CO2, increasing their diffusion differences in pore channels and leading to the CO2/C2H2 kinetic selectivity of 31.97. Grand canonical Monte Carlo (GCMC) simulation demonstrates that the CO2 distribution in K-5A-β is significantly higher than that of C2H2. Dynamic breakthrough experiments verify the excellent performance of material in practical CO2/C2H2 separation, for CO2/C2H2 (50/50 and 1/99, V/V) mixtures can be separated in one step, thus directly generating high purity C2H2 (> 99.95%), which provides a promising thought for the zeolite-based separation of CO2 and C2H2.
2024, 43(10): 100395
doi: 10.1016/j.cjsc.2024.100395
摘要:
Low-dimensional hybrid lead halides with responsive emissions have attracted considerable attention due to their potential applications in sensing. Herein, a new one-dimensional hybrid lead bromide CyPbBr3 (Cy = cytosine cation) was synthesized to explore its emission evolution in response to temperature and pressure. The compound possesses an edge-sharing 1D double-chain structure and emits warm white light across nearly the entire visible spectrum upon ultraviolet excitation. This emission arises from the self-trapped excitons and its broadband feature is attributed to the strong electron-phonon coupling as revealed by the variable-temperature photoluminescence experiments. Moreover, a 4.5-fold pressure-induced emission enhancement was observed at 2.7 GPa which is caused by the pressure suppressed non-radiative energy loss. Furthermore, in-situ powder X-ray diffraction and Raman experiments reveal the maxima of the emission enhancement is associated with a phase transition at the same pressure. Our work demonstrates that low-dimensional metal halides are a promising class of stimuli-responsive materials which could have potential applications in temperature and pressure sensing.
Low-dimensional hybrid lead halides with responsive emissions have attracted considerable attention due to their potential applications in sensing. Herein, a new one-dimensional hybrid lead bromide CyPbBr3 (Cy = cytosine cation) was synthesized to explore its emission evolution in response to temperature and pressure. The compound possesses an edge-sharing 1D double-chain structure and emits warm white light across nearly the entire visible spectrum upon ultraviolet excitation. This emission arises from the self-trapped excitons and its broadband feature is attributed to the strong electron-phonon coupling as revealed by the variable-temperature photoluminescence experiments. Moreover, a 4.5-fold pressure-induced emission enhancement was observed at 2.7 GPa which is caused by the pressure suppressed non-radiative energy loss. Furthermore, in-situ powder X-ray diffraction and Raman experiments reveal the maxima of the emission enhancement is associated with a phase transition at the same pressure. Our work demonstrates that low-dimensional metal halides are a promising class of stimuli-responsive materials which could have potential applications in temperature and pressure sensing.
2024, 43(10): 100397
doi: 10.1016/j.cjsc.2024.100397
摘要:
As an emerging class of inorganic hybrid materials, salt-inclusion chalcogenides (SICs) have garnered significant attention in the past decade owing to their distinct host-guest structural characteristics and outstanding performance in the field of optoelectronics. In this study, a novel quaternary SIC [Cs14Cl][Tm71Se110] has been discovered using an appropriate flux method. The structure comprises two distinct parts within the lattice: the host [Tm71Se110]13- framework and the guest [Cs14Cl]13+ polycation. Notably, this structure reveals the presence of mixed-valent Tm2+/Tm3+ and different types of closed cavities for the first time. Additionally, thermal transport performance testing shows that it has ultralow thermal conductivity, ranging from 0.29 to 0.24 W/m·K within the temperature range of 323–673 K, which is one of the lowest reported values among polycrystalline chalcogenides. This research not only advances the coordination chemistry of rare-earth-based compounds but also reaffirms that SIC semiconductors are promising systems for achieving ultralow thermal conductivity.
As an emerging class of inorganic hybrid materials, salt-inclusion chalcogenides (SICs) have garnered significant attention in the past decade owing to their distinct host-guest structural characteristics and outstanding performance in the field of optoelectronics. In this study, a novel quaternary SIC [Cs14Cl][Tm71Se110] has been discovered using an appropriate flux method. The structure comprises two distinct parts within the lattice: the host [Tm71Se110]13- framework and the guest [Cs14Cl]13+ polycation. Notably, this structure reveals the presence of mixed-valent Tm2+/Tm3+ and different types of closed cavities for the first time. Additionally, thermal transport performance testing shows that it has ultralow thermal conductivity, ranging from 0.29 to 0.24 W/m·K within the temperature range of 323–673 K, which is one of the lowest reported values among polycrystalline chalcogenides. This research not only advances the coordination chemistry of rare-earth-based compounds but also reaffirms that SIC semiconductors are promising systems for achieving ultralow thermal conductivity.
2024, 43(10): 100410
doi: 10.1016/j.cjsc.2024.100410
摘要:
Photoluminescence (PL) has been increasingly applied in anticounterfeiting and encryption as counterfeiting becomes more prevalent. However, common luminescent encryption techniques are based on static PL measurements and are easy to counterfeit. In this work, we have developed a thermal vapor deposition (TVD) approach using melem as the unique starting material to synthesize highly homogeneous carbon nitride (CN) thin films featuring unique dynamic PL switching properties. After being irradiated by a white LED, the blue PL intensity of the CN film increases significantly and then fades in darkness, demonstrating excellent recyclability. Experimental results prove that CN films contain cyano groups in the structure, and density functional theory (DFT) calculations indicate that the integration of cyano groups results in traps within the bandgap of CN, suggesting that the dynamic PL switching effect is essentially associated with the fullness of the trap states. We have therefore developed an advanced luminescent device for the secure transmission of encrypted information through controlled illumination. It can be easily read with a portable UV (365 nm) lamp and effectively erased using the white LED, thereby preventing information leakage and showing great potential for many applications.
Photoluminescence (PL) has been increasingly applied in anticounterfeiting and encryption as counterfeiting becomes more prevalent. However, common luminescent encryption techniques are based on static PL measurements and are easy to counterfeit. In this work, we have developed a thermal vapor deposition (TVD) approach using melem as the unique starting material to synthesize highly homogeneous carbon nitride (CN) thin films featuring unique dynamic PL switching properties. After being irradiated by a white LED, the blue PL intensity of the CN film increases significantly and then fades in darkness, demonstrating excellent recyclability. Experimental results prove that CN films contain cyano groups in the structure, and density functional theory (DFT) calculations indicate that the integration of cyano groups results in traps within the bandgap of CN, suggesting that the dynamic PL switching effect is essentially associated with the fullness of the trap states. We have therefore developed an advanced luminescent device for the secure transmission of encrypted information through controlled illumination. It can be easily read with a portable UV (365 nm) lamp and effectively erased using the white LED, thereby preventing information leakage and showing great potential for many applications.
2024, 43(10): 100411
doi: 10.1016/j.cjsc.2024.100411
摘要:
The ligand effects have been extensively investigated in Au and Ag nanoclusters, while corresponding research efforts focusing on Cu nanoclusters remain relatively insufficient. Such a scarcity could primarily be attributed to the inherent instability of Cu nanoclusters relative to their Au/Ag analogues. In this work, we report the controllable preparation and structural determination of a hydride-containing Cu28 nanocluster with a chemical formula of Cu28H10(SPhpOMe)18(DPPOE)3. The combination of Cu28H10(SPhpOMe)18(DPPOE)3 and previously reported Cu28H10(SPhoMe)18(TPP)3 constructs a structure-correlated cluster pair with comparable structures and properties. Accordingly, the ligand effects in directing the geometric structures and physicochemical properties (including optical absorptions and catalytic activities towards the selected hydrogenation) of copper nanoclusters were analyzed. Overall, this work presents a structure-correlated Cu28 pair that enables the atomic-level understanding of ligand effects on the structures and properties of metal nanoclusters.
The ligand effects have been extensively investigated in Au and Ag nanoclusters, while corresponding research efforts focusing on Cu nanoclusters remain relatively insufficient. Such a scarcity could primarily be attributed to the inherent instability of Cu nanoclusters relative to their Au/Ag analogues. In this work, we report the controllable preparation and structural determination of a hydride-containing Cu28 nanocluster with a chemical formula of Cu28H10(SPhpOMe)18(DPPOE)3. The combination of Cu28H10(SPhpOMe)18(DPPOE)3 and previously reported Cu28H10(SPhoMe)18(TPP)3 constructs a structure-correlated cluster pair with comparable structures and properties. Accordingly, the ligand effects in directing the geometric structures and physicochemical properties (including optical absorptions and catalytic activities towards the selected hydrogenation) of copper nanoclusters were analyzed. Overall, this work presents a structure-correlated Cu28 pair that enables the atomic-level understanding of ligand effects on the structures and properties of metal nanoclusters.
