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2025 Volume 44 Issue 2
2025, 44(2): 100406
doi: 10.1016/j.cjsc.2024.100406
Abstract:
In summary, incorporating vertically aligned structures at the filler-electrolyte interface exhibits excellent interfacial properties and Ion transmission rate. This arrangement effectively avoids particle agglomeration caused by high surface energy ion migration along the vertical direction of ion migration facilitate the uniform deposition of Li+ on the metallic lithium anode. Additionally, the shortened lithium-ion conduction distance and excellent electrolyte/electrode interface contribute to enhance the electrochemical performance of assembled solid-state batteries. By constructing vertically aligned fillers, it not only reduces interfacial impedance, enhances ion diffusion, but also enables preparation of flexible and stable CPEs.
In summary, incorporating vertically aligned structures at the filler-electrolyte interface exhibits excellent interfacial properties and Ion transmission rate. This arrangement effectively avoids particle agglomeration caused by high surface energy ion migration along the vertical direction of ion migration facilitate the uniform deposition of Li+ on the metallic lithium anode. Additionally, the shortened lithium-ion conduction distance and excellent electrolyte/electrode interface contribute to enhance the electrochemical performance of assembled solid-state batteries. By constructing vertically aligned fillers, it not only reduces interfacial impedance, enhances ion diffusion, but also enables preparation of flexible and stable CPEs.
2025, 44(2): 100419
doi: 10.1016/j.cjsc.2024.100419
Abstract:
This research not only helps us deeply understand the Li ion diffusion mechanism in oxide materials, but also provides the new insight in designing the Li superionic conductors within the vast chemical space of fcc-type oxides. It is noted that this design scheme is based on the simultaneous adjustment of the size of diffusion path and the content of Li ions. In fact, previous study has shown that Li ions can still achieve rapid diffusion even under the low Li content (without the synchronized diffusion). Therefore, mastering the coordination between the above two effects holds the key to design Li superionic conductors.
This research not only helps us deeply understand the Li ion diffusion mechanism in oxide materials, but also provides the new insight in designing the Li superionic conductors within the vast chemical space of fcc-type oxides. It is noted that this design scheme is based on the simultaneous adjustment of the size of diffusion path and the content of Li ions. In fact, previous study has shown that Li ions can still achieve rapid diffusion even under the low Li content (without the synchronized diffusion). Therefore, mastering the coordination between the above two effects holds the key to design Li superionic conductors.
2025, 44(2): 100430
doi: 10.1016/j.cjsc.2024.100430
Abstract:
In summary, Liu et al. realized the thermally-induced spin transition with colossal PTE and NTE properties in a cyano-bridged hexanuclear complex. The spin transition as well as the conformational transformation triggered anisotropic alteration of the rhombic {FeIII2FeII2} unit and modifications in intermolecular C–H···π interactions, ultimately resulting in NTE along the b axis. This work demonstrates that merging SCO compounds with a pliable rhombic structure and intermolecular interactions leads to exceptional structural and thermodynamic characteristics. This approach represents a significant strategy in the realm of crystal engineering and thermo-responsive molecular devices.
In summary, Liu et al. realized the thermally-induced spin transition with colossal PTE and NTE properties in a cyano-bridged hexanuclear complex. The spin transition as well as the conformational transformation triggered anisotropic alteration of the rhombic {FeIII2FeII2} unit and modifications in intermolecular C–H···π interactions, ultimately resulting in NTE along the b axis. This work demonstrates that merging SCO compounds with a pliable rhombic structure and intermolecular interactions leads to exceptional structural and thermodynamic characteristics. This approach represents a significant strategy in the realm of crystal engineering and thermo-responsive molecular devices.
2025, 44(2): 100440
doi: 10.1016/j.cjsc.2024.100440
Abstract:
This work underscores the effectiveness of introducing functional heteroatoms at the edges of pores of 2D oxidized graphene for improving CO2/N2 separation. The strong affinity between pyridinic N and CO2, coupled with the 2D nature of pores, enables high selectivity even in dilute CO2 mixtures with a little sacrifice of permeance as compared to graphene membranes without NH3 treatment. These results emphasized the challenges in simultaneously optimizing the gas permeance and selectivity for CO2/N2 separation in future study. The scalability and feasibility of this approach, utilizing gaseous reactants (O3 for oxidation and NH3 for pyridinic-N incorporation), make it an attractive candidate for large-scale carbon capture applications. The impressive CO2/N2 separation performance of pyridinic-N-substituted graphene membrane can be adaptive to multiple carbon sources, including concentrated emissions (from steel and cement plants, coal-fired power stations) and low CO2 concentration (from aluminum production and natural gas processing). The techno-economic analysis of carbon capture indicated the cost of US$ 20 per tonCO2 for concentrated CO2 feed and US$ 76 per tonCO2 for dilute CO2 feed capture. The selective carbon capture technology in this work realized the separation of diluted CO2 to improve the recycling of CO2 so that the emission to atmosphere could be alleviated. This research on screening competitive sorption regimes can be applied to develop high-performance and cost-effective CO2 separation membranes, addressing critical global environmental challenges.
This work underscores the effectiveness of introducing functional heteroatoms at the edges of pores of 2D oxidized graphene for improving CO2/N2 separation. The strong affinity between pyridinic N and CO2, coupled with the 2D nature of pores, enables high selectivity even in dilute CO2 mixtures with a little sacrifice of permeance as compared to graphene membranes without NH3 treatment. These results emphasized the challenges in simultaneously optimizing the gas permeance and selectivity for CO2/N2 separation in future study. The scalability and feasibility of this approach, utilizing gaseous reactants (O3 for oxidation and NH3 for pyridinic-N incorporation), make it an attractive candidate for large-scale carbon capture applications. The impressive CO2/N2 separation performance of pyridinic-N-substituted graphene membrane can be adaptive to multiple carbon sources, including concentrated emissions (from steel and cement plants, coal-fired power stations) and low CO2 concentration (from aluminum production and natural gas processing). The techno-economic analysis of carbon capture indicated the cost of US$ 20 per tonCO2 for concentrated CO2 feed and US$ 76 per tonCO2 for dilute CO2 feed capture. The selective carbon capture technology in this work realized the separation of diluted CO2 to improve the recycling of CO2 so that the emission to atmosphere could be alleviated. This research on screening competitive sorption regimes can be applied to develop high-performance and cost-effective CO2 separation membranes, addressing critical global environmental challenges.
2025, 44(2): 100413
doi: 10.1016/j.cjsc.2024.100413
Abstract:
Given the remarkable tunability and chemical adaptability of polymers, substantial opportunities for advancement in the realm of perovskites are anticipated in the forthcoming years. Through the systematic correlation of polymer structure with PSC performance, by seamlessly oscillating between empirical experiments and theoretical simulations, the journey towards commercializing PSCs will persist in its momentum.
Given the remarkable tunability and chemical adaptability of polymers, substantial opportunities for advancement in the realm of perovskites are anticipated in the forthcoming years. Through the systematic correlation of polymer structure with PSC performance, by seamlessly oscillating between empirical experiments and theoretical simulations, the journey towards commercializing PSCs will persist in its momentum.
2025, 44(2): 100428
doi: 10.1016/j.cjsc.2024.100428
Abstract:
With advancements in printing technology and the ongoing development of materials science, printable MR sensors are emerging as a highly promising field. The broad range of available binders and fillers offers greater design flexibility while enabling customization and personalization. The high-throughput low-cost production of printable MR sensors is vital for meeting the enormous and continuously expanding market demands. Overall, the integration of advanced printing techniques in the fabrication of MR sensors has the potential to revolutionize the field of magnetoelectronics, offering immense benefits for both industry, environment, and human society.
With advancements in printing technology and the ongoing development of materials science, printable MR sensors are emerging as a highly promising field. The broad range of available binders and fillers offers greater design flexibility while enabling customization and personalization. The high-throughput low-cost production of printable MR sensors is vital for meeting the enormous and continuously expanding market demands. Overall, the integration of advanced printing techniques in the fabrication of MR sensors has the potential to revolutionize the field of magnetoelectronics, offering immense benefits for both industry, environment, and human society.
2025, 44(2): 100429
doi: 10.1016/j.cjsc.2024.100429
Abstract:
In conclusion, we collected selected area electron diffraction patterns from different orientations to fit the lattice parameters. The results demonstrate that α-RuI3 adopts the R-3 space group. Density functional theory calculations were employed to discuss the energy advantage of the 3R and 2H phases under various pressures. The 3R phase shows lower energy than 2H under the synthesized pressure. Moreover, the ΔH-P curves imply that the 2H phase will emerge at approximately 11 GPa. Furthermore, the in-situ pressure-dependent resistance measurements reveal the metallic behaviour up to 25.5 GPa. Upon cooling from room temperature, the resistance first slowly increases and then rapidly increases at low pressure. Above 11.9 GPa, the resistance behaviour undergoes a great change–the resistance initially increases fast, then slightly and almost temperature independent. The calculated electronic structure under high pressure shows semi-metallic behaviour, consistent with the experimental observation. Furthermore, the pressure point, where resistance behaviour dramatically changes, is close to the calculated one when P-31c structure emerges, indicating that the resistance changes may be driven by pressure-induced structure transformation. Our work clarifies the detailed structure of α-RuI3 and gives an in-depth investigation of its electrical transport behaviour under high pressure.
In conclusion, we collected selected area electron diffraction patterns from different orientations to fit the lattice parameters. The results demonstrate that α-RuI3 adopts the R-3 space group. Density functional theory calculations were employed to discuss the energy advantage of the 3R and 2H phases under various pressures. The 3R phase shows lower energy than 2H under the synthesized pressure. Moreover, the ΔH-P curves imply that the 2H phase will emerge at approximately 11 GPa. Furthermore, the in-situ pressure-dependent resistance measurements reveal the metallic behaviour up to 25.5 GPa. Upon cooling from room temperature, the resistance first slowly increases and then rapidly increases at low pressure. Above 11.9 GPa, the resistance behaviour undergoes a great change–the resistance initially increases fast, then slightly and almost temperature independent. The calculated electronic structure under high pressure shows semi-metallic behaviour, consistent with the experimental observation. Furthermore, the pressure point, where resistance behaviour dramatically changes, is close to the calculated one when P-31c structure emerges, indicating that the resistance changes may be driven by pressure-induced structure transformation. Our work clarifies the detailed structure of α-RuI3 and gives an in-depth investigation of its electrical transport behaviour under high pressure.
2025, 44(2): 100460
doi: 10.1016/j.cjsc.2024.100460
Abstract:
Symmetry breaking, a critical phenomenon in both natural and artificial systems, is pivotal in constructing chiral structures from achiral building units. This study focuses on the achiral molecule 8,8',8'',8'''-((pyrazine-2,3,5,6-tetrayltetrakis(benzene-4,1-iyl))tetrakis(oxy))tetrakis (octan-1-ol) (TPP-C8OH), an aggregation-induced emission (AIE) molecule, to explore its symmetry breaking behavior in supramolecular assembly. By analyzing TPP-C8OH in various solvents-both non-chiral and chiral- we found that chiral solvents significantly enhance the molecule’s symmetry breaking and chiroptical properties. Specially, alcohol solvents, particularly dodecyl alcohol, facilitated the formation of helical structures with both left-handed (M) and right-handed (P) helices within single twisted nanoribbons. This observation contrasts with previously reported symmetry breaking phenomena in assembly systems. Chiral solvents induced assemblies with distinct helical orientations, resulting in notable circularly polarized luminescence (CPL) and circular dichroism (CD) signals. This study elucidates the impact of solvent choice on symmetry breaking and chiral assembly, offering insights into the design of advanced chiral materials with tailored self-assembly processes.
Symmetry breaking, a critical phenomenon in both natural and artificial systems, is pivotal in constructing chiral structures from achiral building units. This study focuses on the achiral molecule 8,8',8'',8'''-((pyrazine-2,3,5,6-tetrayltetrakis(benzene-4,1-iyl))tetrakis(oxy))tetrakis (octan-1-ol) (TPP-C8OH), an aggregation-induced emission (AIE) molecule, to explore its symmetry breaking behavior in supramolecular assembly. By analyzing TPP-C8OH in various solvents-both non-chiral and chiral- we found that chiral solvents significantly enhance the molecule’s symmetry breaking and chiroptical properties. Specially, alcohol solvents, particularly dodecyl alcohol, facilitated the formation of helical structures with both left-handed (M) and right-handed (P) helices within single twisted nanoribbons. This observation contrasts with previously reported symmetry breaking phenomena in assembly systems. Chiral solvents induced assemblies with distinct helical orientations, resulting in notable circularly polarized luminescence (CPL) and circular dichroism (CD) signals. This study elucidates the impact of solvent choice on symmetry breaking and chiral assembly, offering insights into the design of advanced chiral materials with tailored self-assembly processes.
2025, 44(2): 100501
doi: 10.1016/j.cjsc.2024.100501
Abstract:
Chemical functionalization of grapheme is a topic of paramount importance to broaden its applications in chemistry, physics, and biological science but remains a great challenge due to its low chemical activity and poor dispersion. Here, we report a strategy for the photosynergetic electrochemical functionalization of graphene (EFG). By using chloride ion (Cl–) as the intercalation anions and co-reactants, the electrogenerated radicals confined in the expanded graphite layers enable efficient radical addition reaction, thus grasping crystalline-perfect EFG. We found that the ultraviolet irradiation and applied voltage have increased the surface/interface concentration of Cl●, thus boosting the functionalization of graphene. Theoretical calculation and experimental results verified the oxygen evolution reaction (OER) on EFG has been improved by regulating the doping of chlorine atoms. In addition, the reduced interlayer distance and the enhanced electrostatic repulsion near the basal plane endow the fabricated EFG-based membrane with high salt retention. This work highlights a method for the in situ functionalization of graphene and the subsequent applications in OER and water desalination.
Chemical functionalization of grapheme is a topic of paramount importance to broaden its applications in chemistry, physics, and biological science but remains a great challenge due to its low chemical activity and poor dispersion. Here, we report a strategy for the photosynergetic electrochemical functionalization of graphene (EFG). By using chloride ion (Cl–) as the intercalation anions and co-reactants, the electrogenerated radicals confined in the expanded graphite layers enable efficient radical addition reaction, thus grasping crystalline-perfect EFG. We found that the ultraviolet irradiation and applied voltage have increased the surface/interface concentration of Cl●, thus boosting the functionalization of graphene. Theoretical calculation and experimental results verified the oxygen evolution reaction (OER) on EFG has been improved by regulating the doping of chlorine atoms. In addition, the reduced interlayer distance and the enhanced electrostatic repulsion near the basal plane endow the fabricated EFG-based membrane with high salt retention. This work highlights a method for the in situ functionalization of graphene and the subsequent applications in OER and water desalination.
2025, 44(2): 100504
doi: 10.1016/j.cjsc.2024.100504
Abstract:
The zero-strain spinel Li4Ti5O12 stands out as a promising anode material for lithium-ion batteries due to its outstanding cycling stability. However, the limited theoretic specific capacity, low Li+ diffusion coefficient and electronic conductivity severely hinder its practical application. In this study, we demonstrate a strategy of introducing abundant oxygen vacancies not only on the surface and but also inside the bulk of Li4Ti5O12 particles via reductive thermal sintering. The oxygen vacancies can significantly enhance the electronic conductivity and lithium-ion diffusion coefficient of Li4Ti5O12, leading to a remarkable improvement in rate performance and a reduction in polarization. Moreover, additional lithium-ion accommodation sites can be created at the defective surface, contributing to a high specific capacity of over 200 mAh g-1.
The zero-strain spinel Li4Ti5O12 stands out as a promising anode material for lithium-ion batteries due to its outstanding cycling stability. However, the limited theoretic specific capacity, low Li+ diffusion coefficient and electronic conductivity severely hinder its practical application. In this study, we demonstrate a strategy of introducing abundant oxygen vacancies not only on the surface and but also inside the bulk of Li4Ti5O12 particles via reductive thermal sintering. The oxygen vacancies can significantly enhance the electronic conductivity and lithium-ion diffusion coefficient of Li4Ti5O12, leading to a remarkable improvement in rate performance and a reduction in polarization. Moreover, additional lithium-ion accommodation sites can be created at the defective surface, contributing to a high specific capacity of over 200 mAh g-1.
2025, 44(2): 100508
doi: 10.1016/j.cjsc.2024.100508
Abstract:
Due to the similar physicochemical properties of acetylene (C2H2) and carbon dioxide (CO2), separating C2H2 from a CO2/C2H2 mixture poses a significant challenge in the petrochemical industry. Herein, we successfully synthesized a novel SiF62- anion pillared cage metal-organic framework ZNU-15 possessing a new crs topological structure for the selective capture of C2H2. As a linear bidentate linker, the fluorinated SiF62- anion partitions the pores into various sized cages. ZNU-15 displays moderate adsorption for C2H2 with a capacity of 36.0 cm3 g-1 at 298 K and 1 bar, which is 2.7 times higher than the CO2 uptake. The IAST selectivity of C2H2/CO2 for ZNU-15 at 298 K and 100 kPa is 10.5, surpassing that of most reported materials. The Qst value for C2H2 and CO2 at zero coverage are 54.0 and 42.8 kJ/mol, respectively. Moreover, breakthrough experimental tests show that ZNU-15 is capable of effectively separating C2H2 from a C2H2/CO2 mixture. Theoretical calculations further indicate that C2H2 is preferentially trapped by the small cage with four cooperative hydrogen bonds.
Due to the similar physicochemical properties of acetylene (C2H2) and carbon dioxide (CO2), separating C2H2 from a CO2/C2H2 mixture poses a significant challenge in the petrochemical industry. Herein, we successfully synthesized a novel SiF62- anion pillared cage metal-organic framework ZNU-15 possessing a new crs topological structure for the selective capture of C2H2. As a linear bidentate linker, the fluorinated SiF62- anion partitions the pores into various sized cages. ZNU-15 displays moderate adsorption for C2H2 with a capacity of 36.0 cm3 g-1 at 298 K and 1 bar, which is 2.7 times higher than the CO2 uptake. The IAST selectivity of C2H2/CO2 for ZNU-15 at 298 K and 100 kPa is 10.5, surpassing that of most reported materials. The Qst value for C2H2 and CO2 at zero coverage are 54.0 and 42.8 kJ/mol, respectively. Moreover, breakthrough experimental tests show that ZNU-15 is capable of effectively separating C2H2 from a C2H2/CO2 mixture. Theoretical calculations further indicate that C2H2 is preferentially trapped by the small cage with four cooperative hydrogen bonds.
2025, 44(2): 100509
doi: 10.1016/j.cjsc.2024.100509
Abstract:
Bifunctional applications in solid state lighting and optical thermometry are attractive in the optical field. Despite Eu3+ doped phosphors are widely used in white-LEDs, phosphors with high temperature sensitivity remain rare. Herein, NaLnTe2O7:Eu3+ (Ln = Y and Gd) phosphors were synthesized using a rapid microwave-assisted solid-state method to fulfill these applications. Under 395 nm excitation, NaLnTe2O7:Eu3+ exhibit the characteristic 5D0→7FJ (J = 1-4) transitions of Eu3+. Substituting Gd3+ for Y3+ enhances luminescence by approximately 2.42 times. Structural analyses reveal that the improved luminescent properties are attributed to the more distorted and appropriate coordination environment in NaGdTe2O7:Eu3+. Finally, white-LEDs using NaGdTe2O7:Eu3+ as the red-component produce white light with high Ra of 89. Furthermore, the distinct thermal responses of the 5D0→7FJ transitions enable NaLnTe2O7:Eu3+ to function as temperature sensors via fluorescence intensity ratio strategy. NaYTe2O7:Eu3+ possesses the maximum relative/absolute sensitivity of 1.45%/15.93% K-1, whereas NaGdTe2O7:Eu3+ achieves the maximum relative/absolute sensitivity of 1.53%/30.24% K-1. This work highlights the significance of cationic substitution in enhancing luminescent properties for multifunctional applications.
Bifunctional applications in solid state lighting and optical thermometry are attractive in the optical field. Despite Eu3+ doped phosphors are widely used in white-LEDs, phosphors with high temperature sensitivity remain rare. Herein, NaLnTe2O7:Eu3+ (Ln = Y and Gd) phosphors were synthesized using a rapid microwave-assisted solid-state method to fulfill these applications. Under 395 nm excitation, NaLnTe2O7:Eu3+ exhibit the characteristic 5D0→7FJ (J = 1-4) transitions of Eu3+. Substituting Gd3+ for Y3+ enhances luminescence by approximately 2.42 times. Structural analyses reveal that the improved luminescent properties are attributed to the more distorted and appropriate coordination environment in NaGdTe2O7:Eu3+. Finally, white-LEDs using NaGdTe2O7:Eu3+ as the red-component produce white light with high Ra of 89. Furthermore, the distinct thermal responses of the 5D0→7FJ transitions enable NaLnTe2O7:Eu3+ to function as temperature sensors via fluorescence intensity ratio strategy. NaYTe2O7:Eu3+ possesses the maximum relative/absolute sensitivity of 1.45%/15.93% K-1, whereas NaGdTe2O7:Eu3+ achieves the maximum relative/absolute sensitivity of 1.53%/30.24% K-1. This work highlights the significance of cationic substitution in enhancing luminescent properties for multifunctional applications.
2025, 44(2): 100511
doi: 10.1016/j.cjsc.2025.100511
Abstract:
The assembly behaviors of two low-symmetric carboxylic acid molecules (CTTA and BCBDA) containing naphthalene rings on graphite surfaces have been investigated using scanning tunneling microscopy (STM). The transformation of nanostructures induced by the second components (EDA and PEBP-C4) have been also examined. Both CTTA and BCBDA molecules self-assemble at the 1-heptanoic acid (HA)/HOPG interface, forming porous network structures. The dimer represents the most elementary building unit due to the formation of double hydrogen bonds. Moreover, the flipping of the naphthalene ring results in the isomerization of the BCBDA molecule. The introduction of the carboxylic acid derivative EDA disrupt the dimer, which subsequently undergoes a structural conformation to form a novel porous structure. Furthermore, upon the addition of the pyridine derivative PEBP-C4, N–H···O hydrogen bonds are the dominant forces driving the three co-assembled structures. We have also conducted density functional theory (DFT) calculations to determine the molecular conformation and analyze the mechanisms underlying the formation of nanostructures.
The assembly behaviors of two low-symmetric carboxylic acid molecules (CTTA and BCBDA) containing naphthalene rings on graphite surfaces have been investigated using scanning tunneling microscopy (STM). The transformation of nanostructures induced by the second components (EDA and PEBP-C4) have been also examined. Both CTTA and BCBDA molecules self-assemble at the 1-heptanoic acid (HA)/HOPG interface, forming porous network structures. The dimer represents the most elementary building unit due to the formation of double hydrogen bonds. Moreover, the flipping of the naphthalene ring results in the isomerization of the BCBDA molecule. The introduction of the carboxylic acid derivative EDA disrupt the dimer, which subsequently undergoes a structural conformation to form a novel porous structure. Furthermore, upon the addition of the pyridine derivative PEBP-C4, N–H···O hydrogen bonds are the dominant forces driving the three co-assembled structures. We have also conducted density functional theory (DFT) calculations to determine the molecular conformation and analyze the mechanisms underlying the formation of nanostructures.
