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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(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.
2024, 43(10): 100321
doi: 10.1016/j.cjsc.2024.100321
摘要:
In summary, the integrated conductivity and hydrophilic gradient imprinted gradient zinc anode can effectively inhibit side reactions and regulate zinc deposition behavior, thus achieving long-term cycling under high current/capacity. When multiple materials are composited for use as zinc anode coatings, different structural designs may have a dramatic effect on the electrochemical performance, even though the components are the same. The gradient imprinted design and related analysis method can be applied to other zinc anode coating materials, which will contribute to the design of future AZIBs. Moreover, at high current density/capacity, other metal-anode secondary batteries (e.g., lithium-ion batteries, sodium-ion batteries, aluminum-ion batteries, etc.) almost always suffer from serious dendrite problems, and thereby this work can also provide new research inspiration.
In summary, the integrated conductivity and hydrophilic gradient imprinted gradient zinc anode can effectively inhibit side reactions and regulate zinc deposition behavior, thus achieving long-term cycling under high current/capacity. When multiple materials are composited for use as zinc anode coatings, different structural designs may have a dramatic effect on the electrochemical performance, even though the components are the same. The gradient imprinted design and related analysis method can be applied to other zinc anode coating materials, which will contribute to the design of future AZIBs. Moreover, at high current density/capacity, other metal-anode secondary batteries (e.g., lithium-ion batteries, sodium-ion batteries, aluminum-ion batteries, etc.) almost always suffer from serious dendrite problems, and thereby this work can also provide new research inspiration.
2024, 43(10): 100322
doi: 10.1016/j.cjsc.2024.100322
摘要:
This study reports for the first time the synthesis of homogeneous high-order metalla[4]catenane through coordination driven self-assembly strategy, and the complicated topology could be transformed into corresponding organometallic macrocyclic compound accompanied by a decrease in concentration in methanol solution. Besides, the strong interlayer π…π stacking interaction and non-classical hydrogen bonding play a crucial role in the formation and stability of metalla[4]catenane structure, which contributes to a deeper understanding of the driving forces behind the formation of molecular metalla catenanes and also has important theoretical and practical significance for promoting the development of this research system. These findings will further motivate researchers to explore the construction of mechanically interlocked supramolecular topological complexes.
This study reports for the first time the synthesis of homogeneous high-order metalla[4]catenane through coordination driven self-assembly strategy, and the complicated topology could be transformed into corresponding organometallic macrocyclic compound accompanied by a decrease in concentration in methanol solution. Besides, the strong interlayer π…π stacking interaction and non-classical hydrogen bonding play a crucial role in the formation and stability of metalla[4]catenane structure, which contributes to a deeper understanding of the driving forces behind the formation of molecular metalla catenanes and also has important theoretical and practical significance for promoting the development of this research system. These findings will further motivate researchers to explore the construction of mechanically interlocked supramolecular topological complexes.
2024, 43(10): 100325
doi: 10.1016/j.cjsc.2024.100325
摘要:
In summary, the booming development of c-MOFs brings opportunities for the development of new electromagnetic functional materials and devices, and the design and customization of MOF structural units, overall topology modulation, and the construction of three-dimensional structures based on the understanding of electromagnetic properties and energy conversion provide new insights for further investigation of the EMW absorption mechanism and enhancement of dielectric properties. However, conductive MOFs also face challenges such as few available types, poor impedance matching, and narrow absorption bandwidth. Furthermore, in practical potential applications, conductive MOF can also be made into MOF films for stealth coatings for military equipment and EMW protection for civilian use.
In summary, the booming development of c-MOFs brings opportunities for the development of new electromagnetic functional materials and devices, and the design and customization of MOF structural units, overall topology modulation, and the construction of three-dimensional structures based on the understanding of electromagnetic properties and energy conversion provide new insights for further investigation of the EMW absorption mechanism and enhancement of dielectric properties. However, conductive MOFs also face challenges such as few available types, poor impedance matching, and narrow absorption bandwidth. Furthermore, in practical potential applications, conductive MOF can also be made into MOF films for stealth coatings for military equipment and EMW protection for civilian use.
2024, 43(10): 100329
doi: 10.1016/j.cjsc.2024.100329
摘要:
In the future, the nanoconfined water monolayer concept may also work for the aligning assembly of heterostructures of other types of 2D materials. Indeed, the confinement engineering has provided a universal guideline for designing catalysts, membranes and chemical reactions. First, the synergy of chemical and spatial confinement elevated the secondary battery performances by innovative microstructures and properties. Second, the confinement effect may enhance the supercapacitor performances by the load of redox-active nanowires between MXene nanosheets. Third, the Marangoni effect results in the confinement of carbon nanotubes at MXene interfaces, which compose a fast-response humidity sensor. More interesting behaviors could be expected after improving the in-plane alignment of the heterostructures of 2D materials, which may exhibit enhanced magnetic and half-metallic properties as well as enhanced proton and spin-transport performances.
In the future, the nanoconfined water monolayer concept may also work for the aligning assembly of heterostructures of other types of 2D materials. Indeed, the confinement engineering has provided a universal guideline for designing catalysts, membranes and chemical reactions. First, the synergy of chemical and spatial confinement elevated the secondary battery performances by innovative microstructures and properties. Second, the confinement effect may enhance the supercapacitor performances by the load of redox-active nanowires between MXene nanosheets. Third, the Marangoni effect results in the confinement of carbon nanotubes at MXene interfaces, which compose a fast-response humidity sensor. More interesting behaviors could be expected after improving the in-plane alignment of the heterostructures of 2D materials, which may exhibit enhanced magnetic and half-metallic properties as well as enhanced proton and spin-transport performances.
2024, 43(10): 100330
doi: 10.1016/j.cjsc.2024.100330
摘要:
In conclusion, Xiong et al. developed a HEA/SrTiO3 catalyst for efficient photothermal methane dry reforming. This work proposes a unique carbon exchange mechanism based on in-depth spectroscopic techniques, providing a new perspective on overcoming stability and selectivity issues in the DRM process. The work would be expected to inspire the development of efficient DRM catalysts under mild conditions.
In conclusion, Xiong et al. developed a HEA/SrTiO3 catalyst for efficient photothermal methane dry reforming. This work proposes a unique carbon exchange mechanism based on in-depth spectroscopic techniques, providing a new perspective on overcoming stability and selectivity issues in the DRM process. The work would be expected to inspire the development of efficient DRM catalysts under mild conditions.
2024, 43(10): 100331
doi: 10.1016/j.cjsc.2024.100331
摘要:
In summary, this work establishes a correlation between OVs and bound exciton luminescence by single-particle spectroscopy. It confirms that the PL emission of m-BiVO4 originates from the defect state. Additionally, the study achieves visual imaging of the spatial distribution of oxygen defects by PL lifetime imaging maps. Furthermore, single-particle spectroscopy can be used to monitor charge transfer during photocatalysis in situ, indicating that the generation of OVs at specific crystal facets facilitates efficient charge transfer between electrons and reactants. This work provides an imaging technique to accurately monitor the spatial distribution of defects in single-crystal materials, and a method for spatial high-resolution real-time monitoring of multiphase catalytic reactions, aiming to provide an in-depth understanding of the relationship between the structure-activity of materials.
In summary, this work establishes a correlation between OVs and bound exciton luminescence by single-particle spectroscopy. It confirms that the PL emission of m-BiVO4 originates from the defect state. Additionally, the study achieves visual imaging of the spatial distribution of oxygen defects by PL lifetime imaging maps. Furthermore, single-particle spectroscopy can be used to monitor charge transfer during photocatalysis in situ, indicating that the generation of OVs at specific crystal facets facilitates efficient charge transfer between electrons and reactants. This work provides an imaging technique to accurately monitor the spatial distribution of defects in single-crystal materials, and a method for spatial high-resolution real-time monitoring of multiphase catalytic reactions, aiming to provide an in-depth understanding of the relationship between the structure-activity of materials.
2024, 43(10): 100344
doi: 10.1016/j.cjsc.2024.100344
摘要:
In summary, the increasing interest in separating lanthanides and actinides for the purposes of spent nuclear fuel reprocessing has spurred renewed research efforts in this domain recently. Although the higher oxidation states of Am have been recognized for several decades, the development of separation techniques based on the control of Am oxidation state remains less advanced. The key challenge in spent fuel reprocessing lies in achieving complete oxidation and long-term stabilization of high-valence Am under practical conditions. This necessitates addressing the complexities of real-world spent fuel reprocessing scenarios (high acidity and radiation level) and minimizing the generation of secondary waste. In this perspective, we outline the most recent advances in lanthanide and actinide separation following redox-based protocols. High Am/Ln separation factors have been achieved in these works via judicious synergy between proper selection of chemical oxidants and stabilization of Am(V)/Am(VI) via complexation or ion sieving. Ongoing efforts to develop oxidation strategies and separation technologies hold the potential to yield an advanced process suitable for application within the nuclear industry. In addition, separation strategies based on oxidation state control holds promise for addressing the even more challenging task of Am/Cm separation in advanced nuclear fuel cycle.
In summary, the increasing interest in separating lanthanides and actinides for the purposes of spent nuclear fuel reprocessing has spurred renewed research efforts in this domain recently. Although the higher oxidation states of Am have been recognized for several decades, the development of separation techniques based on the control of Am oxidation state remains less advanced. The key challenge in spent fuel reprocessing lies in achieving complete oxidation and long-term stabilization of high-valence Am under practical conditions. This necessitates addressing the complexities of real-world spent fuel reprocessing scenarios (high acidity and radiation level) and minimizing the generation of secondary waste. In this perspective, we outline the most recent advances in lanthanide and actinide separation following redox-based protocols. High Am/Ln separation factors have been achieved in these works via judicious synergy between proper selection of chemical oxidants and stabilization of Am(V)/Am(VI) via complexation or ion sieving. Ongoing efforts to develop oxidation strategies and separation technologies hold the potential to yield an advanced process suitable for application within the nuclear industry. In addition, separation strategies based on oxidation state control holds promise for addressing the even more challenging task of Am/Cm separation in advanced nuclear fuel cycle.
2024, 43(10): 100390
doi: 10.1016/j.cjsc.2024.100390
摘要:
Interface is a necessary channel of carrier permeation in sulfide-based all-solid-state lithium battery (ASSLB). Homogeneous and fast lithium-ion (Li+) interfacial transport of cathode is the overriding premise for high capability of ASSLBs. However, the inherent transport heterogeneity of crystalline materials in cathode and the cathode active material (CAM)/sulfide solid electrolyte (SSE) interfacial issues result in high interfacial impedance, decreasing the Li+ transfer kinetics. In this review, we outline the Li+ transport properties of CAMs and SSEs, followed by a discussion of their interfacial electro-chemo-mechanical issues. Commentary is also provided on the solutions to the multiple-scale interfacial Li+ transport failure. Furthermore, the underlying interdependent mechanisms between electrodes are summarized and overviewed. Finally, we suggest future paths to better comprehend and promote the interfacial Li+ transport in ASSLBs. This review provides an in-depth understanding of cathodal interfacial issues and the proposed improvement strategies will provide guidance for further advancement of high-performance ASSLBs.
Interface is a necessary channel of carrier permeation in sulfide-based all-solid-state lithium battery (ASSLB). Homogeneous and fast lithium-ion (Li+) interfacial transport of cathode is the overriding premise for high capability of ASSLBs. However, the inherent transport heterogeneity of crystalline materials in cathode and the cathode active material (CAM)/sulfide solid electrolyte (SSE) interfacial issues result in high interfacial impedance, decreasing the Li+ transfer kinetics. In this review, we outline the Li+ transport properties of CAMs and SSEs, followed by a discussion of their interfacial electro-chemo-mechanical issues. Commentary is also provided on the solutions to the multiple-scale interfacial Li+ transport failure. Furthermore, the underlying interdependent mechanisms between electrodes are summarized and overviewed. Finally, we suggest future paths to better comprehend and promote the interfacial Li+ transport in ASSLBs. This review provides an in-depth understanding of cathodal interfacial issues and the proposed improvement strategies will provide guidance for further advancement of high-performance ASSLBs.
2024, 43(10): 100393
doi: 10.1016/j.cjsc.2024.100393
摘要:
Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing, information encryption, and microelectronics. We report herein the binary assembly of a blue-emissive iridium complex and a red-emissive ruthenium complex into homogeneously-doped or optically-heterostructured microcrystals with thermo-responsive properties. Depending on the assembly conditions, lateral or longitudinal triblock heterostructures with a microplate shape are obtained, which display distinct emission pattern changes upon heating as a result of the decreased efficiency of energy transfer. In addition, branched heterostructures are prepared by a stepwise assembly. The luminescence polarization of the homogeneously-doped binary crystals and the waveguiding property of the longitudinal triblock heterostructure are further examined. This work evidences the versatility of transition metal complexes in the assembly into various luminescent nano/micro structures with potential applications in thermo-sensing and nanophotonics.
Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing, information encryption, and microelectronics. We report herein the binary assembly of a blue-emissive iridium complex and a red-emissive ruthenium complex into homogeneously-doped or optically-heterostructured microcrystals with thermo-responsive properties. Depending on the assembly conditions, lateral or longitudinal triblock heterostructures with a microplate shape are obtained, which display distinct emission pattern changes upon heating as a result of the decreased efficiency of energy transfer. In addition, branched heterostructures are prepared by a stepwise assembly. The luminescence polarization of the homogeneously-doped binary crystals and the waveguiding property of the longitudinal triblock heterostructure are further examined. This work evidences the versatility of transition metal complexes in the assembly into various luminescent nano/micro structures with potential applications in thermo-sensing and nanophotonics.
2024, 43(10): 100394
doi: 10.1016/j.cjsc.2024.100394
摘要:
The identical molecular size and similar physical properties of carbon dioxide (CO2) and acetylene (C2H2) make their adsorptive separation extremely challenging to achieve with most adsorbents. Reports on the separation of CO2 and C2H2 mixtures by zeolites are even rarer with the mechanism of adsorptive separation requiring further exploration. In this paper, we report that ion modulation of zeolite 5A promotes the difference in kinetic diffusion of CO2 and C2H2, realizing the inverse separation of zeolite from selective adsorption of C2H2 to selective adsorption of CO2. Creating a compact pore space restricting the orientation of gas molecules enables charge recognition. The positive electrostatic potential at the pore openings was utilized to hinder the diffusion of C2H2 between the cages while ensuring the transfer of CO2, increasing their diffusion differences in pore channels and leading to the CO2/C2H2 kinetic selectivity of 31.97. Grand canonical Monte Carlo (GCMC) simulation demonstrates that the CO2 distribution in K-5A-β is significantly higher than that of C2H2. Dynamic breakthrough experiments verify the excellent performance of material in practical CO2/C2H2 separation, for CO2/C2H2 (50/50 and 1/99, V/V) mixtures can be separated in one step, thus directly generating high purity C2H2 (> 99.95%), which provides a promising thought for the zeolite-based separation of CO2 and C2H2.
The identical molecular size and similar physical properties of carbon dioxide (CO2) and acetylene (C2H2) make their adsorptive separation extremely challenging to achieve with most adsorbents. Reports on the separation of CO2 and C2H2 mixtures by zeolites are even rarer with the mechanism of adsorptive separation requiring further exploration. In this paper, we report that ion modulation of zeolite 5A promotes the difference in kinetic diffusion of CO2 and C2H2, realizing the inverse separation of zeolite from selective adsorption of C2H2 to selective adsorption of CO2. Creating a compact pore space restricting the orientation of gas molecules enables charge recognition. The positive electrostatic potential at the pore openings was utilized to hinder the diffusion of C2H2 between the cages while ensuring the transfer of CO2, increasing their diffusion differences in pore channels and leading to the CO2/C2H2 kinetic selectivity of 31.97. Grand canonical Monte Carlo (GCMC) simulation demonstrates that the CO2 distribution in K-5A-β is significantly higher than that of C2H2. Dynamic breakthrough experiments verify the excellent performance of material in practical CO2/C2H2 separation, for CO2/C2H2 (50/50 and 1/99, V/V) mixtures can be separated in one step, thus directly generating high purity C2H2 (> 99.95%), which provides a promising thought for the zeolite-based separation of CO2 and C2H2.
2024, 43(10): 100395
doi: 10.1016/j.cjsc.2024.100395
摘要:
Low-dimensional hybrid lead halides with responsive emissions have attracted considerable attention due to their potential applications in sensing. Herein, a new one-dimensional hybrid lead bromide CyPbBr3 (Cy = cytosine cation) was synthesized to explore its emission evolution in response to temperature and pressure. The compound possesses an edge-sharing 1D double-chain structure and emits warm white light across nearly the entire visible spectrum upon ultraviolet excitation. This emission arises from the self-trapped excitons and its broadband feature is attributed to the strong electron-phonon coupling as revealed by the variable-temperature photoluminescence experiments. Moreover, a 4.5-fold pressure-induced emission enhancement was observed at 2.7 GPa which is caused by the pressure suppressed non-radiative energy loss. Furthermore, in-situ powder X-ray diffraction and Raman experiments reveal the maxima of the emission enhancement is associated with a phase transition at the same pressure. Our work demonstrates that low-dimensional metal halides are a promising class of stimuli-responsive materials which could have potential applications in temperature and pressure sensing.
Low-dimensional hybrid lead halides with responsive emissions have attracted considerable attention due to their potential applications in sensing. Herein, a new one-dimensional hybrid lead bromide CyPbBr3 (Cy = cytosine cation) was synthesized to explore its emission evolution in response to temperature and pressure. The compound possesses an edge-sharing 1D double-chain structure and emits warm white light across nearly the entire visible spectrum upon ultraviolet excitation. This emission arises from the self-trapped excitons and its broadband feature is attributed to the strong electron-phonon coupling as revealed by the variable-temperature photoluminescence experiments. Moreover, a 4.5-fold pressure-induced emission enhancement was observed at 2.7 GPa which is caused by the pressure suppressed non-radiative energy loss. Furthermore, in-situ powder X-ray diffraction and Raman experiments reveal the maxima of the emission enhancement is associated with a phase transition at the same pressure. Our work demonstrates that low-dimensional metal halides are a promising class of stimuli-responsive materials which could have potential applications in temperature and pressure sensing.
2024, 43(10): 100397
doi: 10.1016/j.cjsc.2024.100397
摘要:
As an emerging class of inorganic hybrid materials, salt-inclusion chalcogenides (SICs) have garnered significant attention in the past decade owing to their distinct host-guest structural characteristics and outstanding performance in the field of optoelectronics. In this study, a novel quaternary SIC [Cs14Cl][Tm71Se110] has been discovered using an appropriate flux method. The structure comprises two distinct parts within the lattice: the host [Tm71Se110]13- framework and the guest [Cs14Cl]13+ polycation. Notably, this structure reveals the presence of mixed-valent Tm2+/Tm3+ and different types of closed cavities for the first time. Additionally, thermal transport performance testing shows that it has ultralow thermal conductivity, ranging from 0.29 to 0.24 W/m·K within the temperature range of 323–673 K, which is one of the lowest reported values among polycrystalline chalcogenides. This research not only advances the coordination chemistry of rare-earth-based compounds but also reaffirms that SIC semiconductors are promising systems for achieving ultralow thermal conductivity.
As an emerging class of inorganic hybrid materials, salt-inclusion chalcogenides (SICs) have garnered significant attention in the past decade owing to their distinct host-guest structural characteristics and outstanding performance in the field of optoelectronics. In this study, a novel quaternary SIC [Cs14Cl][Tm71Se110] has been discovered using an appropriate flux method. The structure comprises two distinct parts within the lattice: the host [Tm71Se110]13- framework and the guest [Cs14Cl]13+ polycation. Notably, this structure reveals the presence of mixed-valent Tm2+/Tm3+ and different types of closed cavities for the first time. Additionally, thermal transport performance testing shows that it has ultralow thermal conductivity, ranging from 0.29 to 0.24 W/m·K within the temperature range of 323–673 K, which is one of the lowest reported values among polycrystalline chalcogenides. This research not only advances the coordination chemistry of rare-earth-based compounds but also reaffirms that SIC semiconductors are promising systems for achieving ultralow thermal conductivity.
2024, 43(10): 100410
doi: 10.1016/j.cjsc.2024.100410
摘要:
Photoluminescence (PL) has been increasingly applied in anticounterfeiting and encryption as counterfeiting becomes more prevalent. However, common luminescent encryption techniques are based on static PL measurements and are easy to counterfeit. In this work, we have developed a thermal vapor deposition (TVD) approach using melem as the unique starting material to synthesize highly homogeneous carbon nitride (CN) thin films featuring unique dynamic PL switching properties. After being irradiated by a white LED, the blue PL intensity of the CN film increases significantly and then fades in darkness, demonstrating excellent recyclability. Experimental results prove that CN films contain cyano groups in the structure, and density functional theory (DFT) calculations indicate that the integration of cyano groups results in traps within the bandgap of CN, suggesting that the dynamic PL switching effect is essentially associated with the fullness of the trap states. We have therefore developed an advanced luminescent device for the secure transmission of encrypted information through controlled illumination. It can be easily read with a portable UV (365 nm) lamp and effectively erased using the white LED, thereby preventing information leakage and showing great potential for many applications.
Photoluminescence (PL) has been increasingly applied in anticounterfeiting and encryption as counterfeiting becomes more prevalent. However, common luminescent encryption techniques are based on static PL measurements and are easy to counterfeit. In this work, we have developed a thermal vapor deposition (TVD) approach using melem as the unique starting material to synthesize highly homogeneous carbon nitride (CN) thin films featuring unique dynamic PL switching properties. After being irradiated by a white LED, the blue PL intensity of the CN film increases significantly and then fades in darkness, demonstrating excellent recyclability. Experimental results prove that CN films contain cyano groups in the structure, and density functional theory (DFT) calculations indicate that the integration of cyano groups results in traps within the bandgap of CN, suggesting that the dynamic PL switching effect is essentially associated with the fullness of the trap states. We have therefore developed an advanced luminescent device for the secure transmission of encrypted information through controlled illumination. It can be easily read with a portable UV (365 nm) lamp and effectively erased using the white LED, thereby preventing information leakage and showing great potential for many applications.
2024, 43(10): 100411
doi: 10.1016/j.cjsc.2024.100411
摘要:
The ligand effects have been extensively investigated in Au and Ag nanoclusters, while corresponding research efforts focusing on Cu nanoclusters remain relatively insufficient. Such a scarcity could primarily be attributed to the inherent instability of Cu nanoclusters relative to their Au/Ag analogues. In this work, we report the controllable preparation and structural determination of a hydride-containing Cu28 nanocluster with a chemical formula of Cu28H10(SPhpOMe)18(DPPOE)3. The combination of Cu28H10(SPhpOMe)18(DPPOE)3 and previously reported Cu28H10(SPhoMe)18(TPP)3 constructs a structure-correlated cluster pair with comparable structures and properties. Accordingly, the ligand effects in directing the geometric structures and physicochemical properties (including optical absorptions and catalytic activities towards the selected hydrogenation) of copper nanoclusters were analyzed. Overall, this work presents a structure-correlated Cu28 pair that enables the atomic-level understanding of ligand effects on the structures and properties of metal nanoclusters.
The ligand effects have been extensively investigated in Au and Ag nanoclusters, while corresponding research efforts focusing on Cu nanoclusters remain relatively insufficient. Such a scarcity could primarily be attributed to the inherent instability of Cu nanoclusters relative to their Au/Ag analogues. In this work, we report the controllable preparation and structural determination of a hydride-containing Cu28 nanocluster with a chemical formula of Cu28H10(SPhpOMe)18(DPPOE)3. The combination of Cu28H10(SPhpOMe)18(DPPOE)3 and previously reported Cu28H10(SPhoMe)18(TPP)3 constructs a structure-correlated cluster pair with comparable structures and properties. Accordingly, the ligand effects in directing the geometric structures and physicochemical properties (including optical absorptions and catalytic activities towards the selected hydrogenation) of copper nanoclusters were analyzed. Overall, this work presents a structure-correlated Cu28 pair that enables the atomic-level understanding of ligand effects on the structures and properties of metal nanoclusters.
