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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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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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Methods to Make Conductive Covalent Organic Frameworks for Electrocatalytic Applications
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Uncovering the Mechanism for Urea Electrochemical Synthesis by Coupling N2 and CO2 on Mo2C-MXene
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2025, 44(4): 100459
doi: 10.1016/j.cjsc.2024.100459
摘要:
While ultrasmooth 2D c-MOF films have demonstrated enhanced charge mobility within the conjugated plane, it is equally imperative to enhance the interlayer pathways for out-of-plane charge transport in three dimensions. This can be achieved through the strategic expansion of conjugated systems, optimization of stacking models, and modification of functional groups. Moreover, there is an urgent need to develop alternative and simpler synthesis methods for defect-free single-crystal thin films, addressing the challenges of low yield and harsh synthesis conditions associated with chemical vapor deposition (CVD) and subsequent separation and washing processes involving gallium. Finally, the integration of density functional theory calculations with machine learning approaches could be a great opportunity in predicting and synthesizing the next generation of conductive 2D c-MOFs.
While ultrasmooth 2D c-MOF films have demonstrated enhanced charge mobility within the conjugated plane, it is equally imperative to enhance the interlayer pathways for out-of-plane charge transport in three dimensions. This can be achieved through the strategic expansion of conjugated systems, optimization of stacking models, and modification of functional groups. Moreover, there is an urgent need to develop alternative and simpler synthesis methods for defect-free single-crystal thin films, addressing the challenges of low yield and harsh synthesis conditions associated with chemical vapor deposition (CVD) and subsequent separation and washing processes involving gallium. Finally, the integration of density functional theory calculations with machine learning approaches could be a great opportunity in predicting and synthesizing the next generation of conductive 2D c-MOFs.
2025, 44(4): 100464
doi: 10.1016/j.cjsc.2024.100464
摘要:
This study outlines the design principles and potential applications of dynamic 2D COFs, emphasizing the crucial roles of rigid columns and flexible bridges. It serves as a valuable reference for understanding and creating novel COFs with tunable properties. Future research can utilize the design principle of ‘wine rack’ frames to achieve lateral offset of π-stacked columns by introducing branched chains with strong spatial positional resistance at COF nodes and connecting them with flexible connectors, thus ensuring the robustness and flexibility of the COF structure to enable dynamic structural transformations in response to external stimuli. This structural adaptability can be utilized to control pore size, pore volume, and exciton coupling within the material, enabling practical applications of COFs in gas separation, molecular adsorption, and photoelectrocatalysis.
This study outlines the design principles and potential applications of dynamic 2D COFs, emphasizing the crucial roles of rigid columns and flexible bridges. It serves as a valuable reference for understanding and creating novel COFs with tunable properties. Future research can utilize the design principle of ‘wine rack’ frames to achieve lateral offset of π-stacked columns by introducing branched chains with strong spatial positional resistance at COF nodes and connecting them with flexible connectors, thus ensuring the robustness and flexibility of the COF structure to enable dynamic structural transformations in response to external stimuli. This structural adaptability can be utilized to control pore size, pore volume, and exciton coupling within the material, enabling practical applications of COFs in gas separation, molecular adsorption, and photoelectrocatalysis.
2025, 44(4): 100465
doi: 10.1016/j.cjsc.2024.100465
摘要:
In summary, this research marks a major advancement in the development of medium-temperature PEMFCs. The novel COF ionomer offers solutions to long-standing challenges related to water retention, proton transport, and oxygen mass transport at elevated temperatures. The improved performance of MT PEMFCs using this material opens possibilities for broader applications in the energy sector, particularly in automotive and stationary power generation. This innovation could pave the way for the next generation of PEMFCs, overcoming some of the key obstacles that have limited their application in more demanding applications. Future research should focus on optimizing the synthesis process for large-scale production and exploring the ionomer's performance under a wider range of operating conditions.
In summary, this research marks a major advancement in the development of medium-temperature PEMFCs. The novel COF ionomer offers solutions to long-standing challenges related to water retention, proton transport, and oxygen mass transport at elevated temperatures. The improved performance of MT PEMFCs using this material opens possibilities for broader applications in the energy sector, particularly in automotive and stationary power generation. This innovation could pave the way for the next generation of PEMFCs, overcoming some of the key obstacles that have limited their application in more demanding applications. Future research should focus on optimizing the synthesis process for large-scale production and exploring the ionomer's performance under a wider range of operating conditions.
2025, 44(4): 100449
doi: 10.1016/j.cjsc.2024.100449
摘要:
A series of structural characterizations demonstrated that the introduction of Li-ions with over-stoichiometric ratios led to the localized formation of a unique nanophase (S-phase), which stabilized the coplanar Li-ion conformation and enabled lithium superionic conduction. The construction of this face-sharing lithium structure has great application prospects for improving the ionic conductivity of FCC-type oxides. The research in this work deepens the understanding of the mechanism of rapid lithium ion migration in oxide materials and will accelerate the development of new oxide electrolytes for all-solid-state batteries. Although the present materials exhibit almost equal lithium ion conduction with the current hot oxide-based solid electrolyte (such as lithium garnet, lithium peroxide, Na superionic conductor (NASICON) lithium oxide), there are still many challenges to overcome for their potential applications. For example, the preparation conditions of the material are harsh, requiring high temperature quenching at 1050 ℃. Secondly, the o-LISO compounds are sensitive to air and need to be stored in the glove box. Nonetheless, the face-sharing strategy proposed by Chen et al. is inspiring for the exploration of new solid functional materials in structures that were previously overlooked.
A series of structural characterizations demonstrated that the introduction of Li-ions with over-stoichiometric ratios led to the localized formation of a unique nanophase (S-phase), which stabilized the coplanar Li-ion conformation and enabled lithium superionic conduction. The construction of this face-sharing lithium structure has great application prospects for improving the ionic conductivity of FCC-type oxides. The research in this work deepens the understanding of the mechanism of rapid lithium ion migration in oxide materials and will accelerate the development of new oxide electrolytes for all-solid-state batteries. Although the present materials exhibit almost equal lithium ion conduction with the current hot oxide-based solid electrolyte (such as lithium garnet, lithium peroxide, Na superionic conductor (NASICON) lithium oxide), there are still many challenges to overcome for their potential applications. For example, the preparation conditions of the material are harsh, requiring high temperature quenching at 1050 ℃. Secondly, the o-LISO compounds are sensitive to air and need to be stored in the glove box. Nonetheless, the face-sharing strategy proposed by Chen et al. is inspiring for the exploration of new solid functional materials in structures that were previously overlooked.
2025, 44(4): 100452
doi: 10.1016/j.cjsc.2024.100452
摘要:
Although mimicking protein functions using supramolecular systems remains a daunting challenge, the impressive work by Aprahamian et al. suggests that future efforts may focus on nonequilibrium rather than equilibrium states, and that combining dynamic chemistry with host-guest chemistry is a worthwhile direction for creating more complex and biomimetic smart molecules.
Although mimicking protein functions using supramolecular systems remains a daunting challenge, the impressive work by Aprahamian et al. suggests that future efforts may focus on nonequilibrium rather than equilibrium states, and that combining dynamic chemistry with host-guest chemistry is a worthwhile direction for creating more complex and biomimetic smart molecules.
2025, 44(4): 100450
doi: 10.1016/j.cjsc.2024.100450
摘要:
In summary, the fabrication of oxide photoelectrodes are still attractive and challenging filed towards various application. Although some fast preparation methods have been developed, the performance of related oxide photoelectrodes are still relatively low comparing to their maximum theoretical performance. As a perspective on oxide photoelectrodes, we offer suggestions for the fast fabrication of photoelectrodes. First, the formation mechanism of photoelectrodes should be elucidated in details and how to prepare high performance photoelectrodes should be answered. Second, the devices for fast fabrication photoelectrodes should be simplistic and low cost. Furthermore, more effort should be put on developing large scale preparation strategies by fast annealing processes.
In summary, the fabrication of oxide photoelectrodes are still attractive and challenging filed towards various application. Although some fast preparation methods have been developed, the performance of related oxide photoelectrodes are still relatively low comparing to their maximum theoretical performance. As a perspective on oxide photoelectrodes, we offer suggestions for the fast fabrication of photoelectrodes. First, the formation mechanism of photoelectrodes should be elucidated in details and how to prepare high performance photoelectrodes should be answered. Second, the devices for fast fabrication photoelectrodes should be simplistic and low cost. Furthermore, more effort should be put on developing large scale preparation strategies by fast annealing processes.
2025, 44(4): 100456
doi: 10.1016/j.cjsc.2024.100456
摘要:
Despite these challenges, nano-thermometry possesses great potentialss for highly sensitive, non-contact temperature measurements with sub-microscopic resolution towards in-depth understanding on optimized catalysis. Further technological advances of nano-thermometry in photothermal catalysis could focus on developing generalized, high-precision and in-situ temperature measurement techniques under working conditions to clearly distinguish between thermal and non-thermal contributions, and to deepen understandings on photothermal catalytic reaction mechanisms, which could, in turn, provide important design principles for efficient catalytic systems. In addition, future nano-thermometry could be more integrated and intelligent, incorporating real-time big-data processing and principal-component analysis systems to carry out more accurate and efficient temperature measurement. Finally, the development of nano-thermometry could be combined with multi-spectroscopy technology to provide more comprehensive solutions for catalytic reactions. These developments will help significantly improve the accuracy and reliability of temperature measurement for catalytic reactions.
Despite these challenges, nano-thermometry possesses great potentialss for highly sensitive, non-contact temperature measurements with sub-microscopic resolution towards in-depth understanding on optimized catalysis. Further technological advances of nano-thermometry in photothermal catalysis could focus on developing generalized, high-precision and in-situ temperature measurement techniques under working conditions to clearly distinguish between thermal and non-thermal contributions, and to deepen understandings on photothermal catalytic reaction mechanisms, which could, in turn, provide important design principles for efficient catalytic systems. In addition, future nano-thermometry could be more integrated and intelligent, incorporating real-time big-data processing and principal-component analysis systems to carry out more accurate and efficient temperature measurement. Finally, the development of nano-thermometry could be combined with multi-spectroscopy technology to provide more comprehensive solutions for catalytic reactions. These developments will help significantly improve the accuracy and reliability of temperature measurement for catalytic reactions.
2025, 44(4): 100515
doi: 10.1016/j.cjsc.2025.100515
摘要:
In conclusion, the synthesis of nine heterometallic Sn-Co/Mn nanoclusters has been achieved through a stepwise self-assem bly approach, utilizing polynuclear oxygen donors as key precur sors. The tBuPO32- ligands play a pivotal role in bridging trinuclear organotin clusters with Co2+/Mn2+ ions. Shielded by O/N/P-con taining ligands, the Co2+ and Mn2+ ions assume distorted tetrahe dral and hexahedral coordination environments, respectively. Lig ands featuring two or three N/P coordination sites facilitate the bridging of multiple [(nBuSn)3(MeO)3(μ3-O)(tBuPO3)3Co] substruc tures, highlighting their structural robustness. Significantly, the dy namic magnetization measurements indicated that (Sn3-Co1)2-1,5-naphyd NC exhibits a slow relaxation behavior of magnetiza tion. This study delves into the intricate self-assembly process of Sn-Co/Mn nanoclusters at the molecular level, offering valuable insights for the development of novel SMMs.
In conclusion, the synthesis of nine heterometallic Sn-Co/Mn nanoclusters has been achieved through a stepwise self-assem bly approach, utilizing polynuclear oxygen donors as key precur sors. The tBuPO32- ligands play a pivotal role in bridging trinuclear organotin clusters with Co2+/Mn2+ ions. Shielded by O/N/P-con taining ligands, the Co2+ and Mn2+ ions assume distorted tetrahe dral and hexahedral coordination environments, respectively. Lig ands featuring two or three N/P coordination sites facilitate the bridging of multiple [(nBuSn)3(MeO)3(μ3-O)(tBuPO3)3Co] substruc tures, highlighting their structural robustness. Significantly, the dy namic magnetization measurements indicated that (Sn3-Co1)2-1,5-naphyd NC exhibits a slow relaxation behavior of magnetiza tion. This study delves into the intricate self-assembly process of Sn-Co/Mn nanoclusters at the molecular level, offering valuable insights for the development of novel SMMs.
2025, 44(4): 100542
doi: 10.1016/j.cjsc.2025.100542
摘要:
H2O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface (AEI) limit the electrochemical performances of aqueous zinc ion batteries. Herein, methionine (Met) is introduced as an electrolyte additive to solve the above issues by three aspects: Firstly, Met is anchored on Zn anode by amino/methylthio groups to form an H2O-poor AEI, thus increasing the overpotential of hydrogen evolution reaction (HER); secondly, Met serves as a pH buffer to neutralize the HER generated OH-, thereby preventing the formation of by-products (e.g. Zn4SO4(OH)6·xH2O); thirdly, Zn2+ could be captured by carboxyl group of the anchored Met through electrostatic interaction, which promotes the dense and flat Zn deposition. Consequently, the Zn||Zn symmetric cell obtains a long cycle life of 3200 h at 1.0 mA cm-2, 1.0 mAh cm-2, and 1400 h at 5.0 mA cm-2, 5.0 mAh cm-2. Moreover, Zn||VO2 full cell exhibits a capacity retention of 91.0% after operating for 7000 cycles at 5.0 A g-1. This study offers a novel strategy for modulating the interface microenvironment of AEI via integrating the molecular adsorption, pH buffer, and Zn2+ capture strategies to design advanced industrial-oriented batteries.
H2O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface (AEI) limit the electrochemical performances of aqueous zinc ion batteries. Herein, methionine (Met) is introduced as an electrolyte additive to solve the above issues by three aspects: Firstly, Met is anchored on Zn anode by amino/methylthio groups to form an H2O-poor AEI, thus increasing the overpotential of hydrogen evolution reaction (HER); secondly, Met serves as a pH buffer to neutralize the HER generated OH-, thereby preventing the formation of by-products (e.g. Zn4SO4(OH)6·xH2O); thirdly, Zn2+ could be captured by carboxyl group of the anchored Met through electrostatic interaction, which promotes the dense and flat Zn deposition. Consequently, the Zn||Zn symmetric cell obtains a long cycle life of 3200 h at 1.0 mA cm-2, 1.0 mAh cm-2, and 1400 h at 5.0 mA cm-2, 5.0 mAh cm-2. Moreover, Zn||VO2 full cell exhibits a capacity retention of 91.0% after operating for 7000 cycles at 5.0 A g-1. This study offers a novel strategy for modulating the interface microenvironment of AEI via integrating the molecular adsorption, pH buffer, and Zn2+ capture strategies to design advanced industrial-oriented batteries.
2025, 44(4): 100544
doi: 10.1016/j.cjsc.2025.100544
摘要:
The investigation of thermal transport properties of materials has become increasingly important in technological applications, including thermal management and energy conversion. Recently, ultrahigh or low thermal conductivity has been reported in nitride, boride, and chalcogenide by different strategies. However, the strategy to design oxide crystals with unique thermal properties is also a challenge. In this work, a new ternary oxide crystal Ga2TeO6 is designed and expected to show high thermal conductivity due to its lone pairs-free octahedra connected along the c-axis by sharing edges. The thermal conductivities of Ga2TeO6 crystal are determined to be 19.2 W m-1 K-1 and 23.9 W m-1 K-1 along the a- and c-axes directions at 323 K, respectively, which are significantly higher than those of most reported oxide crystals. First-principles calculations and crystal structure analyses reveal that the Ga2TeO6 crystal shows high sound velocity and weak lattice anharmonicity due to lone pairs-free octahedra and highly symmetric group arrangement. The results suggest that much attention must be paid to the polyhedron with lone pairs and its arrangement in materials design to balance the functions and thermal properties.
The investigation of thermal transport properties of materials has become increasingly important in technological applications, including thermal management and energy conversion. Recently, ultrahigh or low thermal conductivity has been reported in nitride, boride, and chalcogenide by different strategies. However, the strategy to design oxide crystals with unique thermal properties is also a challenge. In this work, a new ternary oxide crystal Ga2TeO6 is designed and expected to show high thermal conductivity due to its lone pairs-free octahedra connected along the c-axis by sharing edges. The thermal conductivities of Ga2TeO6 crystal are determined to be 19.2 W m-1 K-1 and 23.9 W m-1 K-1 along the a- and c-axes directions at 323 K, respectively, which are significantly higher than those of most reported oxide crystals. First-principles calculations and crystal structure analyses reveal that the Ga2TeO6 crystal shows high sound velocity and weak lattice anharmonicity due to lone pairs-free octahedra and highly symmetric group arrangement. The results suggest that much attention must be paid to the polyhedron with lone pairs and its arrangement in materials design to balance the functions and thermal properties.
2025, 44(4): 100560
doi: 10.1016/j.cjsc.2025.100560
摘要:
Negatively charged open-framework metal sulfides (NOSs), taking advantages of the characteristics of excellent visible light absorption, easily exchanged cations, and abundant active sites, hold significant promise as highly efficient photocatalysts for hydrogen evolution. However, their applications in photocatalytic hydrogen evolution (PHE) are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored. Herein, we excavated a novel NOS photocatalyst of (Me2NH2)6In10S18 (MIS) with a three-dimensional (3D) structure, and successfully incorporated divalent Co(II) and metal Co(0) into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions. As the introduced Co(0) allows for more efficient light utilization and adroitly surficial hydrogen desorption, and meanwhile acts as the ‘electron pump’ for rapid charge transfer, Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis. With the prolonging of illumination, metal Co(0) gradually escapes from MIS framework, resulting in the declining of PHE performance. By stark contrast, the incorporated Co(II) can establish a strong interaction with MIS framework, and meanwhile capture photogenerated electrons from MIS to produce Co(0), which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers. Thus, Co(II)-modified MIS exhibits a robust and highly stable PHE activity of ~4944 μmol/g/h during the long-term photocatalytic reactions, surpassing most of previously reported In-S-framework photocatalysts. This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts, and sheds light on the design of guest confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.
Negatively charged open-framework metal sulfides (NOSs), taking advantages of the characteristics of excellent visible light absorption, easily exchanged cations, and abundant active sites, hold significant promise as highly efficient photocatalysts for hydrogen evolution. However, their applications in photocatalytic hydrogen evolution (PHE) are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored. Herein, we excavated a novel NOS photocatalyst of (Me2NH2)6In10S18 (MIS) with a three-dimensional (3D) structure, and successfully incorporated divalent Co(II) and metal Co(0) into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions. As the introduced Co(0) allows for more efficient light utilization and adroitly surficial hydrogen desorption, and meanwhile acts as the ‘electron pump’ for rapid charge transfer, Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis. With the prolonging of illumination, metal Co(0) gradually escapes from MIS framework, resulting in the declining of PHE performance. By stark contrast, the incorporated Co(II) can establish a strong interaction with MIS framework, and meanwhile capture photogenerated electrons from MIS to produce Co(0), which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers. Thus, Co(II)-modified MIS exhibits a robust and highly stable PHE activity of ~4944 μmol/g/h during the long-term photocatalytic reactions, surpassing most of previously reported In-S-framework photocatalysts. This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts, and sheds light on the design of guest confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.
2025, 44(4): 100561
doi: 10.1016/j.cjsc.2025.100561
摘要:
As a highly reactive reaction intermediate, surface gallium hydride (Ga-H) has garnered significant attention due to its critical role in various catalytic reactions. However, the detailed experimental characterization of this unique species remains challenging. Recently, we demonstrated that solid-state NMR can be an effective tool for studying surface Ga-H. In this work, we report a comparative solid-state NMR study on H2 activation over different Ga2O3 polymorphs, specifically α-, β- and γ-Ga2O3. 1H solid-state NMR enabled the identification of Ga-H species formed on all the three samples following high-temperature H2 treatment. The characteristic 1H NMR signals of the Ga-H species were resolved using J-coupling-based double-resonance NMR methods, revealing highly similar lineshapes of Ga-H for all the Ga2O3 samples. This suggests potentially similar surface Ga-H configurations among the different Ga2O3 polymorphs. In addition, the local hydrogen environments on the oxide surfaces were further explored using two-dimensional (2D) 1H-1H homonuclear correlation spectra, revealing multiple spatially proximate Ga-H pairs and Ga-H/-OH pairs on different Ga2O3 polymorphs. These findings provide insights into the potential mechanism of H2 dissociation. Overall, this work offers new perspectives on the local structure of surface Ga-H on Ga2O3, and the analytical approach presented here can be further extended to the study of other Ga-based catalysts and other metal hydride species.
As a highly reactive reaction intermediate, surface gallium hydride (Ga-H) has garnered significant attention due to its critical role in various catalytic reactions. However, the detailed experimental characterization of this unique species remains challenging. Recently, we demonstrated that solid-state NMR can be an effective tool for studying surface Ga-H. In this work, we report a comparative solid-state NMR study on H2 activation over different Ga2O3 polymorphs, specifically α-, β- and γ-Ga2O3. 1H solid-state NMR enabled the identification of Ga-H species formed on all the three samples following high-temperature H2 treatment. The characteristic 1H NMR signals of the Ga-H species were resolved using J-coupling-based double-resonance NMR methods, revealing highly similar lineshapes of Ga-H for all the Ga2O3 samples. This suggests potentially similar surface Ga-H configurations among the different Ga2O3 polymorphs. In addition, the local hydrogen environments on the oxide surfaces were further explored using two-dimensional (2D) 1H-1H homonuclear correlation spectra, revealing multiple spatially proximate Ga-H pairs and Ga-H/-OH pairs on different Ga2O3 polymorphs. These findings provide insights into the potential mechanism of H2 dissociation. Overall, this work offers new perspectives on the local structure of surface Ga-H on Ga2O3, and the analytical approach presented here can be further extended to the study of other Ga-based catalysts and other metal hydride species.
2025, 44(4): 100562
doi: 10.1016/j.cjsc.2025.100562
摘要:
Partitioning of actinides from lanthanides is pivotal for advancing nuclear waste management and sustaining nuclear energy development, yet it remains a formidable challenge due to the intricate chemical behavior of these f-block elements. In this study, we introduce 3,6-di-2-pyridyl-1,2,4,5-tetrazine (L1), whose hydrolysis product of pyridine-2-carbox-aldehyde (pyridine-2-carbonyl)-hydrazone (L2) can fractionally crystallize U(VI) ions over Ln(III) cations with high selectivity and efficiency. Through hydrolysis-induced C–N bond cleavage, L2 acts as a tetradentate ligand, coordinating with two UO22+ ions in a planar arrangement to form a zero-dimensional cluster, [(UO2)2(μ3-O)(L2)(CH3COO)]·DMF (U-L2), while lanthanide ions (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Yb, and Lu) remain in solution due to their inability to achieve similar coordination. This selective crystallization strategy yields exceptional separation factors between U(VI) and Ln(III), with a separation factor of 756276 between U(VI) and Sm(III), the highest reported to date. Furthermore, this fractional crystallization separation process can be achieved under mild ambient conditions with high separation factors, enabling the development of a rapid, safe, and energy-efficient strategy for once-through separation of high oxidation state actinides from lanthanides.
Partitioning of actinides from lanthanides is pivotal for advancing nuclear waste management and sustaining nuclear energy development, yet it remains a formidable challenge due to the intricate chemical behavior of these f-block elements. In this study, we introduce 3,6-di-2-pyridyl-1,2,4,5-tetrazine (L1), whose hydrolysis product of pyridine-2-carbox-aldehyde (pyridine-2-carbonyl)-hydrazone (L2) can fractionally crystallize U(VI) ions over Ln(III) cations with high selectivity and efficiency. Through hydrolysis-induced C–N bond cleavage, L2 acts as a tetradentate ligand, coordinating with two UO22+ ions in a planar arrangement to form a zero-dimensional cluster, [(UO2)2(μ3-O)(L2)(CH3COO)]·DMF (U-L2), while lanthanide ions (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Yb, and Lu) remain in solution due to their inability to achieve similar coordination. This selective crystallization strategy yields exceptional separation factors between U(VI) and Ln(III), with a separation factor of 756276 between U(VI) and Sm(III), the highest reported to date. Furthermore, this fractional crystallization separation process can be achieved under mild ambient conditions with high separation factors, enabling the development of a rapid, safe, and energy-efficient strategy for once-through separation of high oxidation state actinides from lanthanides.
2025, 44(4): 100564
doi: 10.1016/j.cjsc.2025.100564
摘要:
The advancement in catalysis techniques for sustainable environmental applications, particularly an alternative to the current Haber-Bosch process for NH3, has recently gained widespread attention. Although photocatalytic conversion of N2 to NH3 using solar energy is an eco-friendly method, it has the limitation of low quantum yield. Recently, 2D Bi-based photocatalysts have been an active research topic which exhibit higher visible light absorption than TiO2 and higher stability than MXene. The performance of Bi-based photocatalysts can be enhanced through improved visible light absorption properties by incorporating plasmonic gold nanoparticles while nitrogen adsorption could be enhanced through oxygen vacancy processes. In the present study, we explore the application of 2D nano-sized Bi2O3-x and gold nanoparticles for visible light photo generation of NH3. HRTEM and XPS reveal that the formation of AuNP and nano-sized Bi2O3-x in AuNP/Bi2O3-x heterozygote structure which promotes the charge carrier mobility and charge transport at the interface resulting in a 2.6-fold increase in the photocatalytic activity compared to micro-sized Bi2O3-x with AuNP. The improved photocatalytic performance can be ascribed to significant enhancement of visible light absorption by plasmonic nanoparticles, fast charge transport and mobility (due to sheet morphology) and the N2 activation by oxygen vacancy in AuNP/Bi2O3-x heterozygote. Through a systematic experimental investigation involving catalysts, concentration, pH, and scavengers, the highest photocatalytic performance was achieved with the heterozygote structures of AuNP/n-Bi2O3-x under optimized conditions, yielding 432.5 μmol gcat-1 h-1 of NH3.
The advancement in catalysis techniques for sustainable environmental applications, particularly an alternative to the current Haber-Bosch process for NH3, has recently gained widespread attention. Although photocatalytic conversion of N2 to NH3 using solar energy is an eco-friendly method, it has the limitation of low quantum yield. Recently, 2D Bi-based photocatalysts have been an active research topic which exhibit higher visible light absorption than TiO2 and higher stability than MXene. The performance of Bi-based photocatalysts can be enhanced through improved visible light absorption properties by incorporating plasmonic gold nanoparticles while nitrogen adsorption could be enhanced through oxygen vacancy processes. In the present study, we explore the application of 2D nano-sized Bi2O3-x and gold nanoparticles for visible light photo generation of NH3. HRTEM and XPS reveal that the formation of AuNP and nano-sized Bi2O3-x in AuNP/Bi2O3-x heterozygote structure which promotes the charge carrier mobility and charge transport at the interface resulting in a 2.6-fold increase in the photocatalytic activity compared to micro-sized Bi2O3-x with AuNP. The improved photocatalytic performance can be ascribed to significant enhancement of visible light absorption by plasmonic nanoparticles, fast charge transport and mobility (due to sheet morphology) and the N2 activation by oxygen vacancy in AuNP/Bi2O3-x heterozygote. Through a systematic experimental investigation involving catalysts, concentration, pH, and scavengers, the highest photocatalytic performance was achieved with the heterozygote structures of AuNP/n-Bi2O3-x under optimized conditions, yielding 432.5 μmol gcat-1 h-1 of NH3.
2025, 44(4): 100545
doi: 10.1016/j.cjsc.2025.100545
摘要:
Hydrogen peroxide (H2O2) is a crucial, eco-friendly oxidizing agent with a wide range of industrial, environmental, and biomedical applications. Traditional production methods, such as the anthraquinone process, face significant challenges in terms of energy consumption and environmental impact. As a sustainable alternative, photocatalytic H2O2 production, driven by solar energy, has emerged as a promising approach. This review discusses the key advancements in photocatalytic H2O2 synthesis, focusing on overcoming challenges such as charge recombination, selectivity for the two-electron oxygen reduction reaction (2e- ORR), and catalyst stability. Recent innovations in photocatalyst design, including high-entropy materials, single-atom catalysts, and covalent organic frameworks (COFs), have significantly enhanced efficiency and stability. Furthermore, novel strategies for optimizing charge separation, light harvesting, and mass transfer are explored. The integration of artificial intelligence and bioinspired systems holds potential for accelerating progress in this field. This review provides a comprehensive overview of current challenges and cutting-edge solutions, offering valuable insights for the development of scalable, decentralized H2O2 production systems that contribute to a more sustainable future.
Hydrogen peroxide (H2O2) is a crucial, eco-friendly oxidizing agent with a wide range of industrial, environmental, and biomedical applications. Traditional production methods, such as the anthraquinone process, face significant challenges in terms of energy consumption and environmental impact. As a sustainable alternative, photocatalytic H2O2 production, driven by solar energy, has emerged as a promising approach. This review discusses the key advancements in photocatalytic H2O2 synthesis, focusing on overcoming challenges such as charge recombination, selectivity for the two-electron oxygen reduction reaction (2e- ORR), and catalyst stability. Recent innovations in photocatalyst design, including high-entropy materials, single-atom catalysts, and covalent organic frameworks (COFs), have significantly enhanced efficiency and stability. Furthermore, novel strategies for optimizing charge separation, light harvesting, and mass transfer are explored. The integration of artificial intelligence and bioinspired systems holds potential for accelerating progress in this field. This review provides a comprehensive overview of current challenges and cutting-edge solutions, offering valuable insights for the development of scalable, decentralized H2O2 production systems that contribute to a more sustainable future.
2025, 44(1): 100381
doi: 10.1016/j.cjsc.2024.100381
摘要:
The ionic conductivity in high-performance solid-state electrolytes can reach 10-2 S cm-1 that is equivalent to the conductivity of liquid electrolytes, which has greatly promoted the vigorous development of quasi-solid-state batteries and all-solid-state batteries. Whether in polymer electrolytes, inorganic crystal electrolytes or composite solid electrolytes, the rapid transport mechanism of lithium-ion is the essential criterion used to guide high-performance solid electrolyte design. A comprehensive understanding of the rapid lithium-ion transport mechanism requires to focus on the structural characteristics of the material and developing relevant simulation methods to reveal the structure-activity relationship in rapid ion transport.
The ionic conductivity in high-performance solid-state electrolytes can reach 10-2 S cm-1 that is equivalent to the conductivity of liquid electrolytes, which has greatly promoted the vigorous development of quasi-solid-state batteries and all-solid-state batteries. Whether in polymer electrolytes, inorganic crystal electrolytes or composite solid electrolytes, the rapid transport mechanism of lithium-ion is the essential criterion used to guide high-performance solid electrolyte design. A comprehensive understanding of the rapid lithium-ion transport mechanism requires to focus on the structural characteristics of the material and developing relevant simulation methods to reveal the structure-activity relationship in rapid ion transport.
2025, 44(1): 100382
doi: 10.1016/j.cjsc.2024.100382
摘要:
In conclusion, the development of IrVI-ado represents a major leap forward in PEM water electrolysis technology. By dramatically reducing the amount of iridium required while enhancing catalytic performance and stability, this innovation holds the potential to make H2 production via PEM electrolysis more economically viable and scalable. To transition this breakthrough from the laboratory to industrial applications, further research and development will be crucial, thereby paving the way for a more sustainable energy future.
In conclusion, the development of IrVI-ado represents a major leap forward in PEM water electrolysis technology. By dramatically reducing the amount of iridium required while enhancing catalytic performance and stability, this innovation holds the potential to make H2 production via PEM electrolysis more economically viable and scalable. To transition this breakthrough from the laboratory to industrial applications, further research and development will be crucial, thereby paving the way for a more sustainable energy future.
2025, 44(1): 100383
doi: 10.1016/j.cjsc.2024.100383
摘要:
It is noteworthy that the work combined plasma discharge with electroreduction processes, resulting in the sustainable synthesis of NH2OH from ambient air and H2O. The proposed mechanism not only mitigates the energy consumption problem during NH2OH electrosynthesis but also reduces the emission of NOx. Furthermore, it provides an important scientific reference for the renewable electrosynthesis of NH2OH and other nitrogen-containing compounds. Nevertheless, the large-scale synthesis of HNO3 plasma continues to present significant challenges, including high energy consumption and low air conversion efficiency. In particular, the key to industrialisation is the further realisation of high-concentration HNO3, the advancement of the scale-up and low-cost preparation of catalytic electrodes, and the rational construction of the reactive electrostack.
It is noteworthy that the work combined plasma discharge with electroreduction processes, resulting in the sustainable synthesis of NH2OH from ambient air and H2O. The proposed mechanism not only mitigates the energy consumption problem during NH2OH electrosynthesis but also reduces the emission of NOx. Furthermore, it provides an important scientific reference for the renewable electrosynthesis of NH2OH and other nitrogen-containing compounds. Nevertheless, the large-scale synthesis of HNO3 plasma continues to present significant challenges, including high energy consumption and low air conversion efficiency. In particular, the key to industrialisation is the further realisation of high-concentration HNO3, the advancement of the scale-up and low-cost preparation of catalytic electrodes, and the rational construction of the reactive electrostack.
2025, 44(1): 100407
doi: 10.1016/j.cjsc.2024.100407
摘要:
In conclusion, the electrochemical stability of Zn metal anodes in wide-pH electrolytes can be enhanced by the strategy of electrolyte engineering and electrode design. On the one hand, the optimization mechanism of electrolyte engineering can be considered as the manipulation of the chemical environment at the electrode/electrolyte interface. In particular, the amphipathic organics-based EDL and fluorinated polymer interphase can mitigate the wide range of pH and act as a protective layer, thus ensuring the highly reversible redox conversion of Zn anodes. On the other hand, the main guideline of electrode design consists in the growth of the zincophilic and hydrogen-inert sites, intending to successfully address the suboptimal utilization rate of the Zn metal over a wide pH range. Although the above electrolyte additives and electrode alloying strategies have shown significant results in improving the reversibility of deposition/stripping of Zn anode in wide pH aqueous electrolytes, however, there is still a lack of suitable modification strategies for the development of AZMBs with ultra-high energy densities, as well as a shortage of synergistic optimization of the cathode materials for wide pH aqueous electrolytes. In short, this work expounds on the optimization strategy of zinc-electrolytes and zinc-electrodes compatible with a wide range of pH, which might be an inspiration in the fields of practical Zn anodes for the state-of-art AZMBs.
In conclusion, the electrochemical stability of Zn metal anodes in wide-pH electrolytes can be enhanced by the strategy of electrolyte engineering and electrode design. On the one hand, the optimization mechanism of electrolyte engineering can be considered as the manipulation of the chemical environment at the electrode/electrolyte interface. In particular, the amphipathic organics-based EDL and fluorinated polymer interphase can mitigate the wide range of pH and act as a protective layer, thus ensuring the highly reversible redox conversion of Zn anodes. On the other hand, the main guideline of electrode design consists in the growth of the zincophilic and hydrogen-inert sites, intending to successfully address the suboptimal utilization rate of the Zn metal over a wide pH range. Although the above electrolyte additives and electrode alloying strategies have shown significant results in improving the reversibility of deposition/stripping of Zn anode in wide pH aqueous electrolytes, however, there is still a lack of suitable modification strategies for the development of AZMBs with ultra-high energy densities, as well as a shortage of synergistic optimization of the cathode materials for wide pH aqueous electrolytes. In short, this work expounds on the optimization strategy of zinc-electrolytes and zinc-electrodes compatible with a wide range of pH, which might be an inspiration in the fields of practical Zn anodes for the state-of-art AZMBs.
2025, 44(1): 100418
doi: 10.1016/j.cjsc.2024.100418
摘要:
In summary, the reported work proposes Pd/Ni(OH)2 catalysts with rich Ni2+-O-Pd interfaces for low-potential HMFOR with ∼100% FDCA selectivity. At Ni2+-O-Pd interfaces, efficient HMFOR originates from the formation of abundant OH* and the decreased activation energy of C-H bonds. It is proved that the construction of metal-metal hydroxide interfaces is very effective for efficient electrocatalytic oxidation of biomass-derived platform molecules. This work provides comprehensive theoretical insights for highly selective synthesis of high-value biomass-derived products at low potential through electrocatalytic oxidation technique.
In summary, the reported work proposes Pd/Ni(OH)2 catalysts with rich Ni2+-O-Pd interfaces for low-potential HMFOR with ∼100% FDCA selectivity. At Ni2+-O-Pd interfaces, efficient HMFOR originates from the formation of abundant OH* and the decreased activation energy of C-H bonds. It is proved that the construction of metal-metal hydroxide interfaces is very effective for efficient electrocatalytic oxidation of biomass-derived platform molecules. This work provides comprehensive theoretical insights for highly selective synthesis of high-value biomass-derived products at low potential through electrocatalytic oxidation technique.
2025, 44(1): 100408
doi: 10.1016/j.cjsc.2024.100408
摘要:
In this Perspectives, we discuss the role of electrocatalysts in improving the conversion reaction kinetics of conversion-type anodes and the strategies to enhance the effectiveness of electrocatalysts for alkali-ion batteries. Also, we provide suggestions for future research aspects of electrocatalysts for conversion-type anodes, which are regarding some of the challenging issues and possible solutions.
In this Perspectives, we discuss the role of electrocatalysts in improving the conversion reaction kinetics of conversion-type anodes and the strategies to enhance the effectiveness of electrocatalysts for alkali-ion batteries. Also, we provide suggestions for future research aspects of electrocatalysts for conversion-type anodes, which are regarding some of the challenging issues and possible solutions.
2025, 44(1): 100446
doi: 10.1016/j.cjsc.2024.100446
摘要:
CsCdPO4 adopts a periodic 3D Cd-P-O anionic network at room temperature. As the temperature increases above 440 K, thermal vibrations induced torsion and deformation within the PO4 units are constrained by the 3D Cd-P-O network, which is critical for the unique periodic to incommensurately modulated long-range ordered phase transition.
CsCdPO4 adopts a periodic 3D Cd-P-O anionic network at room temperature. As the temperature increases above 440 K, thermal vibrations induced torsion and deformation within the PO4 units are constrained by the 3D Cd-P-O network, which is critical for the unique periodic to incommensurately modulated long-range ordered phase transition.
2025, 44(1): 100438
doi: 10.1016/j.cjsc.2024.100438
摘要:
The industrially important selective hydrogenation of α,β-unsaturated aldehydes to allyl alcohol is still challenging to realize using heterogenous hydrogenation catalysts. Supported Cu catalysts have shown moderate selectivity, yet low activity for the reaction, due to the electronic structure of Cu. By anchoring atomically dispersed Pd atoms onto the exposed Cu surface of Cu@CeO2, we report in this work that hydrogen spillover activates the inert metal-oxide interfaces of Cu@CeO2 into highly effective and selective catalytic sites for hydrogenation under mild reaction conditions. The as-prepared catalysts exhibited much higher catalytic activity in the selective hydrogenation of acrolein than Cu@CeO2. Comprehensive studies revealed that atomically dispersed Pd species are critical for the activation and homolytic splitting of H2. The activated H atoms easily spill to the Cu-O-Ce interfaces as Cu-Hδ- and interfacial Ce-O-Hδ+ species, which makes the Cu-O-Ce interfaces as the active sites for the hydrogenation of polar C=O bonds. Moreover, the weak adsorption of allyl alcohol on the Pd and the Cu-O-Ce interfacial sites prevents deep hydrogenation, leading to selective hydrogenation of several α,β-unsaturated aldehydes. Overall, we demonstrate here a synergic effect between single atom alloy and the support for activation of an inert metal-oxide interface into selective catalytic sites.
The industrially important selective hydrogenation of α,β-unsaturated aldehydes to allyl alcohol is still challenging to realize using heterogenous hydrogenation catalysts. Supported Cu catalysts have shown moderate selectivity, yet low activity for the reaction, due to the electronic structure of Cu. By anchoring atomically dispersed Pd atoms onto the exposed Cu surface of Cu@CeO2, we report in this work that hydrogen spillover activates the inert metal-oxide interfaces of Cu@CeO2 into highly effective and selective catalytic sites for hydrogenation under mild reaction conditions. The as-prepared catalysts exhibited much higher catalytic activity in the selective hydrogenation of acrolein than Cu@CeO2. Comprehensive studies revealed that atomically dispersed Pd species are critical for the activation and homolytic splitting of H2. The activated H atoms easily spill to the Cu-O-Ce interfaces as Cu-Hδ- and interfacial Ce-O-Hδ+ species, which makes the Cu-O-Ce interfaces as the active sites for the hydrogenation of polar C=O bonds. Moreover, the weak adsorption of allyl alcohol on the Pd and the Cu-O-Ce interfacial sites prevents deep hydrogenation, leading to selective hydrogenation of several α,β-unsaturated aldehydes. Overall, we demonstrate here a synergic effect between single atom alloy and the support for activation of an inert metal-oxide interface into selective catalytic sites.
2025, 44(1): 100454
doi: 10.1016/j.cjsc.2024.100454
摘要:
Ultra-thin single crystal film (SCF) without grain boundary, inherits low charge recombination probability as bulk single crystals. However, its low depth brings a high surface defects ratio and hinders carrier transport and extraction, which affects the performance and stability of optoelectronic devices such as photodetectors, and thus surface defect passivation is of great practical significance. In this paper, we used the space confined method to grow MAPbBr3 SCF and selected BA2PbI4 for surface defect passivation. The results reveal that BA cation passivates MA vacancy surface defects, reduces carrier recombination, and enhances carrier lifetime. The carrier mobility is as high as 33.6 cm2V-1s-1, and the surface defect density is reduced to 3.4 × 1012 cm-3. Thus, the self-driven vertical MAPbBr3 SCF photodetector after surface passivation exhibits more excellent optoelectronic performance.
Ultra-thin single crystal film (SCF) without grain boundary, inherits low charge recombination probability as bulk single crystals. However, its low depth brings a high surface defects ratio and hinders carrier transport and extraction, which affects the performance and stability of optoelectronic devices such as photodetectors, and thus surface defect passivation is of great practical significance. In this paper, we used the space confined method to grow MAPbBr3 SCF and selected BA2PbI4 for surface defect passivation. The results reveal that BA cation passivates MA vacancy surface defects, reduces carrier recombination, and enhances carrier lifetime. The carrier mobility is as high as 33.6 cm2V-1s-1, and the surface defect density is reduced to 3.4 × 1012 cm-3. Thus, the self-driven vertical MAPbBr3 SCF photodetector after surface passivation exhibits more excellent optoelectronic performance.
2025, 44(1): 100455
doi: 10.1016/j.cjsc.2024.100455
摘要:
Birefringent crystals are crucial for manipulating light's phase and polarization, making them vital components in various optical devices. Traditionally, strategies for designing high-performance birefringent crystals have focused on modifying the parent structure. However, there are limited examples demonstrating how changing functional groups can effectively enhance birefringence (Δn), as such changes often significantly alter the crystal structure. In this study, we propose a "functional group implantation" strategy aimed at significantly improving birefringent performance within the chalcogenide system. This involves replacing the isotropic [S]2- ions with anisotropic π-conjugated [CO3]2- groups. We validated this approach through comprehensive comparisons between the chalcogenide [Ba3S][GeS4] and the oxychalcogenide [Ba3CO3][MS4] (where M = Ge and Sn), both of which adopt the same space group and feature the same arrangements of functional groups. Experimental characterization and theoretical calculations confirm that the [CO3]2- groups exhibit significantly greater polarization anisotropy than the [S]2- groups. This difference leads to a marked increase in Δn in [Ba3CO3][MS4] (ranging from 0.088 to 0.112 at 546 nm) compared to [Ba3S][GeS4] (0.021 at 546 nm). This finding not only broadens the structural chemistry of π-conjugated chalcogenides but also illustrates the potential of functional group implantation for designing infrared birefringent crystals with enhanced optical anisotropy.
Birefringent crystals are crucial for manipulating light's phase and polarization, making them vital components in various optical devices. Traditionally, strategies for designing high-performance birefringent crystals have focused on modifying the parent structure. However, there are limited examples demonstrating how changing functional groups can effectively enhance birefringence (Δn), as such changes often significantly alter the crystal structure. In this study, we propose a "functional group implantation" strategy aimed at significantly improving birefringent performance within the chalcogenide system. This involves replacing the isotropic [S]2- ions with anisotropic π-conjugated [CO3]2- groups. We validated this approach through comprehensive comparisons between the chalcogenide [Ba3S][GeS4] and the oxychalcogenide [Ba3CO3][MS4] (where M = Ge and Sn), both of which adopt the same space group and feature the same arrangements of functional groups. Experimental characterization and theoretical calculations confirm that the [CO3]2- groups exhibit significantly greater polarization anisotropy than the [S]2- groups. This difference leads to a marked increase in Δn in [Ba3CO3][MS4] (ranging from 0.088 to 0.112 at 546 nm) compared to [Ba3S][GeS4] (0.021 at 546 nm). This finding not only broadens the structural chemistry of π-conjugated chalcogenides but also illustrates the potential of functional group implantation for designing infrared birefringent crystals with enhanced optical anisotropy.
2025, 44(1): 100461
doi: 10.1016/j.cjsc.2024.100461
摘要:
Developing the renewable hydrogen technologies requires high-efficiency pH-universal hydrogen evolution reaction (HER) electrocatalysts. Ruthenium phosphides (RuPx) have the great potentials to replace the commercial Pt-based materials, whereas the optimization of their electronic structure for favorable reaction intermediate adsorption remains a significant challenge. Herein, we report an innovative phosphorization-controlled strategy for the in-situ immobilization of core/satellite-structured RuP/RuP2 heteronanoparticles onto N, P co-doped porous carbon nanosheets (abbreviated as RuP/RuP2@N/P-CNSs hereafter). Density functional theory (DFT) calculations further reveal that the electron shuttling at the RuP/RuP2 interface leads to a reduced energy barrier for H2O dissociation by electron-deficient Ru atoms in the RuP and the optimized H* adsorption of electron-gaining Ru atoms in the RuP2. Impressively, the as-synthesized RuP/RuP2@ N/P-CNSs exhibits low overpotentials of 8, 29, and 66 mV to achieve 10 mA cm-2 in alkaline, acid and neutral media electrolyte, respectively. This research presents a viable approach to synthesize high-efficiency transition metal phosphide-based electrocatalysts and offers a deeper comprehension of interface effects for HER catalysis.
Developing the renewable hydrogen technologies requires high-efficiency pH-universal hydrogen evolution reaction (HER) electrocatalysts. Ruthenium phosphides (RuPx) have the great potentials to replace the commercial Pt-based materials, whereas the optimization of their electronic structure for favorable reaction intermediate adsorption remains a significant challenge. Herein, we report an innovative phosphorization-controlled strategy for the in-situ immobilization of core/satellite-structured RuP/RuP2 heteronanoparticles onto N, P co-doped porous carbon nanosheets (abbreviated as RuP/RuP2@N/P-CNSs hereafter). Density functional theory (DFT) calculations further reveal that the electron shuttling at the RuP/RuP2 interface leads to a reduced energy barrier for H2O dissociation by electron-deficient Ru atoms in the RuP and the optimized H* adsorption of electron-gaining Ru atoms in the RuP2. Impressively, the as-synthesized RuP/RuP2@ N/P-CNSs exhibits low overpotentials of 8, 29, and 66 mV to achieve 10 mA cm-2 in alkaline, acid and neutral media electrolyte, respectively. This research presents a viable approach to synthesize high-efficiency transition metal phosphide-based electrocatalysts and offers a deeper comprehension of interface effects for HER catalysis.
2025, 44(1): 100468
doi: 10.1016/j.cjsc.2024.100468
摘要:
In the quest to align with industrial benchmarks, a noteworthy gap remains in the field of electrochemical nitrogen fixation, particularly in achieving high Faradaic efficiency (FE) and yield. The electrocatalytic nitrogen fixation process faces considerable hurdles due to the difficulty of cleaving the highly stable N≡N triple bond. Additionally, the electrochemical pathway for nitrogen fixation is often compromised by the concurrent hydrogen evolution reaction (HER), which competes aggressively for electrons and active sites on the catalyst surface, thereby reducing the FE of nitrogen reduction reactions (NRR). To surmount these challenges, this study introduces an innovative bimetallic catalyst, CuGa2, synthesized through p-d orbital hybridization to selectively facilitate N2 electroreduction. This catalyst has demonstrated a remarkable NH3 yield of 9.82 μg h-1 cm-2 and an associated Faradaic efficiency of 38.25%. Our findings elucidate that the distinctive p-d hybridization interaction between Ga and Cu enhances NH3 selectivity by reducing the reaction energy barrier for hydrogenation and suppressing hydrogen evolution. This insight highlights the significance of the p-d orbital hybridization in optimizing the electrocatalytic performance of CuGa2 for nitrogen fixation.
In the quest to align with industrial benchmarks, a noteworthy gap remains in the field of electrochemical nitrogen fixation, particularly in achieving high Faradaic efficiency (FE) and yield. The electrocatalytic nitrogen fixation process faces considerable hurdles due to the difficulty of cleaving the highly stable N≡N triple bond. Additionally, the electrochemical pathway for nitrogen fixation is often compromised by the concurrent hydrogen evolution reaction (HER), which competes aggressively for electrons and active sites on the catalyst surface, thereby reducing the FE of nitrogen reduction reactions (NRR). To surmount these challenges, this study introduces an innovative bimetallic catalyst, CuGa2, synthesized through p-d orbital hybridization to selectively facilitate N2 electroreduction. This catalyst has demonstrated a remarkable NH3 yield of 9.82 μg h-1 cm-2 and an associated Faradaic efficiency of 38.25%. Our findings elucidate that the distinctive p-d hybridization interaction between Ga and Cu enhances NH3 selectivity by reducing the reaction energy barrier for hydrogenation and suppressing hydrogen evolution. This insight highlights the significance of the p-d orbital hybridization in optimizing the electrocatalytic performance of CuGa2 for nitrogen fixation.
2025, 44(1): 100470
doi: 10.1016/j.cjsc.2024.100470
摘要:
An effective strategy of regulating active sites in bifunctional oxygen electrocatalysts is essentially desired, especially in rechargeable metal-air batteries (RZABs). Herein, a highly efficient electrocatalyst of CoFe alloys embedded in pyridinic nitrogen enriched N-doped carbon (CoFe/P-NC) is intelligently constructed by pyrolysis strategy. The high concentration of pyridinic nitrogen in CoFe/P-NC can significantly reprogram the redistribution of electron density of metal active sites, consequently optimizing the oxygen adsorption behavior. As expected, the pyridinic nitrogen guarantees CoFe/P-NC providing the low overpotential of the overall oxygen electrocatalytic process (ΔEORR-OER = 0.73 V vs RHE) and suppresses the benchmark electrocatalysts (Pt/C & RuO2). Assembled rechargeable Zn-air battery using CoFe/P-NC demonstrates a promising peak power density of 172.0 mW·cm-2, a high specific capacity of 805.0 mAh·g-1Zn and an excellent stability. This work proposes an interesting strategy for design of robust oxygen electrocatalysts for energy conversion and storage fields.
An effective strategy of regulating active sites in bifunctional oxygen electrocatalysts is essentially desired, especially in rechargeable metal-air batteries (RZABs). Herein, a highly efficient electrocatalyst of CoFe alloys embedded in pyridinic nitrogen enriched N-doped carbon (CoFe/P-NC) is intelligently constructed by pyrolysis strategy. The high concentration of pyridinic nitrogen in CoFe/P-NC can significantly reprogram the redistribution of electron density of metal active sites, consequently optimizing the oxygen adsorption behavior. As expected, the pyridinic nitrogen guarantees CoFe/P-NC providing the low overpotential of the overall oxygen electrocatalytic process (ΔEORR-OER = 0.73 V vs RHE) and suppresses the benchmark electrocatalysts (Pt/C & RuO2). Assembled rechargeable Zn-air battery using CoFe/P-NC demonstrates a promising peak power density of 172.0 mW·cm-2, a high specific capacity of 805.0 mAh·g-1Zn and an excellent stability. This work proposes an interesting strategy for design of robust oxygen electrocatalysts for energy conversion and storage fields.
2025, 44(1): 100451
doi: 10.1016/j.cjsc.2024.100451
摘要:
Multiple-resonance thermally activated delayed fluorescence (MR-TADF) materials hold significant promise for advancing narrowband emissive organic light-emitting diodes (OLEDs) due to their attractive narrowband emission characteristics, high emission intensity, and tunable emission colors. However, the planar nature of MR-TADF materials leads to the serve π-π stacking, which can result in concentration quenching and spectral broadening, thereby limiting their further application in OLEDs. Currently, to mitigate the π-π stacking in MR-TADF materials, steric modulation is a reliable design strategy for optimizing the related molecular structures. Depending on the specific shape and scope of steric modulation, it can be categorized into the introduction of bulky groups around the resonance core, “face-to-edge” shielding between the resonance core and the steric hindrance moiety, and “face-to-face” shielding between the resonance core and the steric hindrance moiety. This review systematically summarizes the structural design of MR-TADF molecules based on the different steric modulation strategies and their progress in the doping concentration-independent OLEDs. It also discusses the challenges in this research area and offers an outlook on future developments. We believe that this review will drive the rapid industrialization of narrow-emission OLEDs.
Multiple-resonance thermally activated delayed fluorescence (MR-TADF) materials hold significant promise for advancing narrowband emissive organic light-emitting diodes (OLEDs) due to their attractive narrowband emission characteristics, high emission intensity, and tunable emission colors. However, the planar nature of MR-TADF materials leads to the serve π-π stacking, which can result in concentration quenching and spectral broadening, thereby limiting their further application in OLEDs. Currently, to mitigate the π-π stacking in MR-TADF materials, steric modulation is a reliable design strategy for optimizing the related molecular structures. Depending on the specific shape and scope of steric modulation, it can be categorized into the introduction of bulky groups around the resonance core, “face-to-edge” shielding between the resonance core and the steric hindrance moiety, and “face-to-face” shielding between the resonance core and the steric hindrance moiety. This review systematically summarizes the structural design of MR-TADF molecules based on the different steric modulation strategies and their progress in the doping concentration-independent OLEDs. It also discusses the challenges in this research area and offers an outlook on future developments. We believe that this review will drive the rapid industrialization of narrow-emission OLEDs.
2025, 44(1): 100467
doi: 10.1016/j.cjsc.2024.100467
摘要:
Plasmonic nanocrystals with intrinsic chirality are becoming a hot research focus and offer a wide range of applications in optics, biomedicine, asymmetric catalysis, and enantioselective sensing. Making use of the enantioselective interaction of the chiral biomolecules and plasmonic nanocrystals, the biomolecules-directed synthesis endows chiral plasmonic nanocrystals with tunable optical properties and excellent biocompatibility. Recent advances in the biomolecule-directed geometric control of intrinsically chiral plasmonic nanomaterials have further provided great opportunities for their widespread applications in many emerging technological areas. The review summarizes the recent progress of biomolecule-directed synthesis and potential applications of chiral plasmonic nanocrystals and discusses their development prospects.
Plasmonic nanocrystals with intrinsic chirality are becoming a hot research focus and offer a wide range of applications in optics, biomedicine, asymmetric catalysis, and enantioselective sensing. Making use of the enantioselective interaction of the chiral biomolecules and plasmonic nanocrystals, the biomolecules-directed synthesis endows chiral plasmonic nanocrystals with tunable optical properties and excellent biocompatibility. Recent advances in the biomolecule-directed geometric control of intrinsically chiral plasmonic nanomaterials have further provided great opportunities for their widespread applications in many emerging technological areas. The review summarizes the recent progress of biomolecule-directed synthesis and potential applications of chiral plasmonic nanocrystals and discusses their development prospects.
