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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. The journal is published twelve issues a year by Fujian Institute of Research on the Structure of Matter, CAS and is available online:
https://www.sciencedirect.com/journal/chinese-journal-of-structural-chemistry
Contact information：
E-mail: cjsc@fjirsm.ac.cn; Tel: +86-591-63173769
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2024, 43(11): 100334
doi: 10.1016/j.cjsc.2024.100334
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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.
