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2026 Volume 45 Issue 3
2026, 45(3): 100773
doi: 10.1016/j.cjsc.2025.100773
Abstract:
Amorphous solids, which do not possess the long-range order, hold great promise in mechanical, optical, and chemical properties, etc., and have also been revealed as critical biomineralization precursors. However, fundamental questions about their three-dimensional (3D) atomic structure remain challenging due to the long-range disorder. Conventional protocols probe such molecular structures through scattering or real-space imaging. The former provides ensemble-averaged data that masks local structural deviations, while the latter is hampered by the electron-beam sensitivity of materials. Nevertheless, based on distance-sensitive heteronuclear coupling, rotational echo double resonance (REDOR), a specialized solid-state nuclear magnetic resonance (NMR) measurement, is efficient in detecting local deviations and usually nondestructive. Here, using amorphous calcium carbonate/phosphate Ca(CO3)x(PO4)2(1-x)/3 (0 < x <1, CaCPs) solids synthesized by ion cross-linking as an example, we develop a nondestructive method to reveal local deviations of amorphous ionic solids by combining REDOR, Monte Carlo (MC), and molecular dynamic (MD) simulation. Briefly, MC simulations generated atomic structures with heterogeneous medium-range spatial apportionment of ions, and MD simulations relaxed the initial configuration to rationalize short-range order. Then, theoretical REDOR decay curves of MC/MD-generated structures were compared with experimental values to check the medium-range order. We revealed that there was heterogeneous medium-range spatial apportionment of anions in CaCPs. Because solid-state NMR applies to virtually any spin-bearing material, this methodology provides an alternative route to resolve the atomic structure of amorphous solids.
Amorphous solids, which do not possess the long-range order, hold great promise in mechanical, optical, and chemical properties, etc., and have also been revealed as critical biomineralization precursors. However, fundamental questions about their three-dimensional (3D) atomic structure remain challenging due to the long-range disorder. Conventional protocols probe such molecular structures through scattering or real-space imaging. The former provides ensemble-averaged data that masks local structural deviations, while the latter is hampered by the electron-beam sensitivity of materials. Nevertheless, based on distance-sensitive heteronuclear coupling, rotational echo double resonance (REDOR), a specialized solid-state nuclear magnetic resonance (NMR) measurement, is efficient in detecting local deviations and usually nondestructive. Here, using amorphous calcium carbonate/phosphate Ca(CO3)x(PO4)2(1-x)/3 (0 < x <1, CaCPs) solids synthesized by ion cross-linking as an example, we develop a nondestructive method to reveal local deviations of amorphous ionic solids by combining REDOR, Monte Carlo (MC), and molecular dynamic (MD) simulation. Briefly, MC simulations generated atomic structures with heterogeneous medium-range spatial apportionment of ions, and MD simulations relaxed the initial configuration to rationalize short-range order. Then, theoretical REDOR decay curves of MC/MD-generated structures were compared with experimental values to check the medium-range order. We revealed that there was heterogeneous medium-range spatial apportionment of anions in CaCPs. Because solid-state NMR applies to virtually any spin-bearing material, this methodology provides an alternative route to resolve the atomic structure of amorphous solids.
2026, 45(3): 100800
doi: 10.1016/j.cjsc.2025.100800
Abstract:
2026, 45(3): 100802
doi: 10.1016/j.cjsc.2025.100802
Abstract:
Research on high-performance birefringent crystals with birefringence values greater than 0.3 has grown rapidly in recent years. These materials hold great promise for enabling the compactness and miniaturization of optical components that manipulate the phase and polairization of light. Crystals based on organic π-conjugated units frequently exhibit birefringence values exceeding 0.3, establishing them as effective building blocks for next-generation birefringent materials. This work highlights recent progress in the development of birefringent crystals derived from organic π-conjugated units. We emphasize the pivotal role of these functional building blocks in crystal design and materials discovery, and review representative studies that report high-performance birefringent crystals. The article concludes with a discussion of current challenges and outlines future research directions in this emerging field.
Research on high-performance birefringent crystals with birefringence values greater than 0.3 has grown rapidly in recent years. These materials hold great promise for enabling the compactness and miniaturization of optical components that manipulate the phase and polairization of light. Crystals based on organic π-conjugated units frequently exhibit birefringence values exceeding 0.3, establishing them as effective building blocks for next-generation birefringent materials. This work highlights recent progress in the development of birefringent crystals derived from organic π-conjugated units. We emphasize the pivotal role of these functional building blocks in crystal design and materials discovery, and review representative studies that report high-performance birefringent crystals. The article concludes with a discussion of current challenges and outlines future research directions in this emerging field.
2026, 45(3): 100813
doi: 10.1016/j.cjsc.2025.100813
Abstract:
Organic near-infrared (NIR) fluorophores are being considered as next-gen tools for targeted imaging of HeLa cells and cervical cancer because they have less phototoxicity, less background autofluorescence, and better tissue penetration than traditional fluorophores. Through this review article, we have discussed how recent developments in rational molecular engineering have resulted in probes that are more attuned to particular tumor microenvironmental signals as viscosity, pH, reactive oxygen species, and enzyme overexpression. These probes are brighter, have larger Stokes shifts, and can be tuned through techniques like π-extension, donor-acceptor frameworks, heteroatom incorporation, and aggregation-induced emission algorithms. Potential platforms for image-guided therapy in cervical malignancies include BODIPY, carbazole, phenothiazine/phenoxazine, phenyl derivatives, and rhodamine/xanthene analogues. Early diagnosis, surgical guiding, and theranostic applications are just a few of the many uses for these platforms. Efforts within the scientific community to enhance clinical accuracy should focus on three key areas: (1) expanding the NIR-II window for fluorophore emission to improve tissue penetration and signal quality; (2) developing activatable probes specific to organelles; and (3) integrating these systems with cutting-edge optical imaging tools analysis. Nevertheless, there are still challenges to be solved, including issues with photostability, synthesis complexity, nonspecific interactions, water solubility, and gaps in the translation of results from preclinical models to human applications. These limitations must be overcome through systematic evaluation, scalable synthesis, and thorough safety profiling if organic NIR probes for imaging and treatment of cervical cancer can be quickly brought into clinical uses.
Organic near-infrared (NIR) fluorophores are being considered as next-gen tools for targeted imaging of HeLa cells and cervical cancer because they have less phototoxicity, less background autofluorescence, and better tissue penetration than traditional fluorophores. Through this review article, we have discussed how recent developments in rational molecular engineering have resulted in probes that are more attuned to particular tumor microenvironmental signals as viscosity, pH, reactive oxygen species, and enzyme overexpression. These probes are brighter, have larger Stokes shifts, and can be tuned through techniques like π-extension, donor-acceptor frameworks, heteroatom incorporation, and aggregation-induced emission algorithms. Potential platforms for image-guided therapy in cervical malignancies include BODIPY, carbazole, phenothiazine/phenoxazine, phenyl derivatives, and rhodamine/xanthene analogues. Early diagnosis, surgical guiding, and theranostic applications are just a few of the many uses for these platforms. Efforts within the scientific community to enhance clinical accuracy should focus on three key areas: (1) expanding the NIR-II window for fluorophore emission to improve tissue penetration and signal quality; (2) developing activatable probes specific to organelles; and (3) integrating these systems with cutting-edge optical imaging tools analysis. Nevertheless, there are still challenges to be solved, including issues with photostability, synthesis complexity, nonspecific interactions, water solubility, and gaps in the translation of results from preclinical models to human applications. These limitations must be overcome through systematic evaluation, scalable synthesis, and thorough safety profiling if organic NIR probes for imaging and treatment of cervical cancer can be quickly brought into clinical uses.
2026, 45(3): 100814
doi: 10.1016/j.cjsc.2025.100814
Abstract:
2026, 45(3): 100828
doi: 10.1016/j.cjsc.2025.100828
Abstract:
Polymeric hole transport layers (HTLs) are emerging as one of the most promising classes of hole transporting materials for inverted (p–i–n) perovskite solar cells, offering tunable molecular design, reliable film formation, and potential for scalable processing. Within this class, fluorene-based polymers stand out due to their rigid π-conjugated backbone, which imparts thermal stability and optical transparency, and the unique C9 substitution site, which enables precise control over solubility, morphology, interfacial chemistry, and energy alignment. By linking the fluorene core with alkyl, functionalised alkyl, vinylene, biphenyl/spiro, or in situ crosslinkable motifs, researchers have created a diverse family of HTLs that balance mobility, stability, and manufacturability. Recent studies show that well-engineered fluorene polymers can deliver power conversion efficiencies above 20% and retain over 90% of their initial performance after 1000 hours of operational stress. Despite advances, challenges remain, as fabrication and stability inconsistencies hinder comparison, and few fluorene-based systems combine efficiency, stability, and scalability. Bridging this gap will require systematic mapping of C9 substitution patterns to device metrics, hybrid designs that merge complementary traits, and ISOS-compliant benchmarking. This review provides a unifying framework to guide the development of next-generation fluorene-based polymeric HTLs for durable, commercially viable perovskite photovoltaics.
Polymeric hole transport layers (HTLs) are emerging as one of the most promising classes of hole transporting materials for inverted (p–i–n) perovskite solar cells, offering tunable molecular design, reliable film formation, and potential for scalable processing. Within this class, fluorene-based polymers stand out due to their rigid π-conjugated backbone, which imparts thermal stability and optical transparency, and the unique C9 substitution site, which enables precise control over solubility, morphology, interfacial chemistry, and energy alignment. By linking the fluorene core with alkyl, functionalised alkyl, vinylene, biphenyl/spiro, or in situ crosslinkable motifs, researchers have created a diverse family of HTLs that balance mobility, stability, and manufacturability. Recent studies show that well-engineered fluorene polymers can deliver power conversion efficiencies above 20% and retain over 90% of their initial performance after 1000 hours of operational stress. Despite advances, challenges remain, as fabrication and stability inconsistencies hinder comparison, and few fluorene-based systems combine efficiency, stability, and scalability. Bridging this gap will require systematic mapping of C9 substitution patterns to device metrics, hybrid designs that merge complementary traits, and ISOS-compliant benchmarking. This review provides a unifying framework to guide the development of next-generation fluorene-based polymeric HTLs for durable, commercially viable perovskite photovoltaics.
2026, 45(3): 100829
doi: 10.1016/j.cjsc.2025.100829
Abstract:
It is of vital importance to effectively capture 137Cs for human health and ecological protection due to its strong radioactivity and biotoxicity. Herein, the efficient uptake of Cs+ has been achieved by a new layered gallium oxalatophosphonate {[(CH3)2NH2][CH3CH2NH3]}2[Ga4(PO4)4(H2PO4)2(C2O4)] (FJSM-NGAPC), whose structure features the anionic gallium oxalatophosphate layer of [Ga4(PO4)4(H2PO4)2(C2O4)]n4n- with [(CH3)2NH2]+ and [CH3CH2NH3]+ cations in the interlayer spaces. The maximum Cs+ adsorption capacity of FJSM-NGAPC can reach 407.81 mg/g, which surpasses that of common Cs+ scavengers. In the presence of a large excess of interfering Na+ ions, it shows high selectivity for Cs+ ions and the maximum KdCs can reach 1.36 × 104 mL/g. In particular, FJSM-NGAPC can maintain removal performance for Cs+ in the pH range from 3.07 to 10.01 with KdCs values all above 103 mL/g. Impressively, the Cs+ adsorption mechanism is clearly revealed at the molecular level by the single crystal to single crystal (SC-SC) structural transformation. This process confirms ion exchange between Cs+ and interlayer [(CH3)2NH2]+ and [CH3CH2NH3]+ cations, accompanied by strong Cs···O interactions. This work provides an efficient metal oxalatophosphate as the scavenger for radiocesium and clearly elucidates the radiocesium capture mechanism, facilitating the design of new oxalatophosphates materials for radionuclide remediation.
It is of vital importance to effectively capture 137Cs for human health and ecological protection due to its strong radioactivity and biotoxicity. Herein, the efficient uptake of Cs+ has been achieved by a new layered gallium oxalatophosphonate {[(CH3)2NH2][CH3CH2NH3]}2[Ga4(PO4)4(H2PO4)2(C2O4)] (FJSM-NGAPC), whose structure features the anionic gallium oxalatophosphate layer of [Ga4(PO4)4(H2PO4)2(C2O4)]n4n- with [(CH3)2NH2]+ and [CH3CH2NH3]+ cations in the interlayer spaces. The maximum Cs+ adsorption capacity of FJSM-NGAPC can reach 407.81 mg/g, which surpasses that of common Cs+ scavengers. In the presence of a large excess of interfering Na+ ions, it shows high selectivity for Cs+ ions and the maximum KdCs can reach 1.36 × 104 mL/g. In particular, FJSM-NGAPC can maintain removal performance for Cs+ in the pH range from 3.07 to 10.01 with KdCs values all above 103 mL/g. Impressively, the Cs+ adsorption mechanism is clearly revealed at the molecular level by the single crystal to single crystal (SC-SC) structural transformation. This process confirms ion exchange between Cs+ and interlayer [(CH3)2NH2]+ and [CH3CH2NH3]+ cations, accompanied by strong Cs···O interactions. This work provides an efficient metal oxalatophosphate as the scavenger for radiocesium and clearly elucidates the radiocesium capture mechanism, facilitating the design of new oxalatophosphates materials for radionuclide remediation.
2026, 45(3): 100830
doi: 10.1016/j.cjsc.2025.100830
Abstract:
Reversible multicolor photochromic materials based on electron donor-acceptor (EDA) systems have recently attracted considerable attention due to their potential applications in displaying, ink-free erasable printing and anti-counterfeiting. However, it is extremely challenging to realize multicolor photochromism by using same EDA system. Herein, a novel EDA iodoargentate hybrid, [(2-Bz-pyH)(Ag5I6)]·MeCN (1) (2-Bz-pyH+ = N-protonated 2-benzylpyridinium, MeCN = acetonitrile), has been obtained via solvent evaporation method at room temperature. Interestingly, upon ∼ 365 nm Hg lamp irradiation, 1 and MeCN-desolvated 1 (denoted 1-H) display lattice solvent-modulated multicolor photochromic performance (pale yellow to brown for 1, yellow to reddish brown for 1-H) and fast response time (within 1 s). Additionally, 1-H was separately fumigated with DMF/DMSO/THF/DIOX vapors, and these samples also exhibit different photochromic properties under the same light conditions. Meanwhile, the new photochromic mechanism of intermolecular charge transfer composite with photolysis iodoargentate frameworks has been proposed through the combination of experimental and theoretical investigations. These results provide a new perspective for designing multicolor photochromic materials through lattice solvent-modulated same EDA system.
Reversible multicolor photochromic materials based on electron donor-acceptor (EDA) systems have recently attracted considerable attention due to their potential applications in displaying, ink-free erasable printing and anti-counterfeiting. However, it is extremely challenging to realize multicolor photochromism by using same EDA system. Herein, a novel EDA iodoargentate hybrid, [(2-Bz-pyH)(Ag5I6)]·MeCN (1) (2-Bz-pyH+ = N-protonated 2-benzylpyridinium, MeCN = acetonitrile), has been obtained via solvent evaporation method at room temperature. Interestingly, upon ∼ 365 nm Hg lamp irradiation, 1 and MeCN-desolvated 1 (denoted 1-H) display lattice solvent-modulated multicolor photochromic performance (pale yellow to brown for 1, yellow to reddish brown for 1-H) and fast response time (within 1 s). Additionally, 1-H was separately fumigated with DMF/DMSO/THF/DIOX vapors, and these samples also exhibit different photochromic properties under the same light conditions. Meanwhile, the new photochromic mechanism of intermolecular charge transfer composite with photolysis iodoargentate frameworks has been proposed through the combination of experimental and theoretical investigations. These results provide a new perspective for designing multicolor photochromic materials through lattice solvent-modulated same EDA system.
2026, 45(3): 100831
doi: 10.1016/j.cjsc.2025.100831
Abstract:
The conversion of molecular dinitrogen (N2) into ammonia (NH3) is one of the most important chemical processes. The hemilabile axial bonding in the transition metal (TM) complexes with d-p, d-d and d-df interactions could provide an electron reservoir that controls the evolution of the oxidation state on the active center, which is potential to facilitate N2-to-NH3 conversion. In this perspective, the bionic nitrogen fixing process is illustrated on a molecular level, which features flexible axial bonding to regulate “electron reservoir”. The comprehensive overview summarizes the features of TM complexes with axial supporting ligand and focuses on how the axial ‘‘assistant” atom tunes the electronic properties of the metal center to facilitate dinitrogen binding, as well as proton/electron delivery in N2 reduction. To illustrate the mechanism of axial ‘‘electron reservoir” in dinitrogen fixation on different TM complexes with axial supporting ligand, the relationships of geometric parameters, the variation of electronic structure and oxidation state, the influence principles of axial bonding regulated by anchor atoms, the critical roles of peripheral ligands and the overall comprehension from orbital interaction are all involved. A preliminary view of the major challenges and future opportunities of TM dinitrogen complexes with flexible axial bonding is highlighted at the end. Through this perspective, we hope to give a comprehensive demonstration of the flexible axial bonding as “electron reservoir” in dinitrogen fixation, and shed light on the rational design for fabricating efficient catalysts in the future.
The conversion of molecular dinitrogen (N2) into ammonia (NH3) is one of the most important chemical processes. The hemilabile axial bonding in the transition metal (TM) complexes with d-p, d-d and d-df interactions could provide an electron reservoir that controls the evolution of the oxidation state on the active center, which is potential to facilitate N2-to-NH3 conversion. In this perspective, the bionic nitrogen fixing process is illustrated on a molecular level, which features flexible axial bonding to regulate “electron reservoir”. The comprehensive overview summarizes the features of TM complexes with axial supporting ligand and focuses on how the axial ‘‘assistant” atom tunes the electronic properties of the metal center to facilitate dinitrogen binding, as well as proton/electron delivery in N2 reduction. To illustrate the mechanism of axial ‘‘electron reservoir” in dinitrogen fixation on different TM complexes with axial supporting ligand, the relationships of geometric parameters, the variation of electronic structure and oxidation state, the influence principles of axial bonding regulated by anchor atoms, the critical roles of peripheral ligands and the overall comprehension from orbital interaction are all involved. A preliminary view of the major challenges and future opportunities of TM dinitrogen complexes with flexible axial bonding is highlighted at the end. Through this perspective, we hope to give a comprehensive demonstration of the flexible axial bonding as “electron reservoir” in dinitrogen fixation, and shed light on the rational design for fabricating efficient catalysts in the future.
2026, 45(3): 100832
doi: 10.1016/j.cjsc.2025.100832
Abstract:
Layered BiOCl photocatalyst exhibits great promise for photocatalytic wastewater treatment in environmental remediation. However, its structural instability hinders further development toward photodegrading organic pollutants due to the photocorrosion caused by slow photocarrier separation. To address this major challenge, the constructed BiOCl-based S-scheme heterojunction is considered as one wonderful strategy which can efficiently steer photocarrier separation by the internal electric field and synergistically achieve stable surface structure. In this work, 2D/2D FeOOH/BiOCl S-scheme heterojunction by coupling FeOOH and BiOCl nanoplate was prepared via in situ photodeposition approach. Photocatalytic results indicate that the optimal 10 wt% FeOOH/BiOCl exhibits excellent photocatalytic activity and stability in tetracycline (TC) degradation, obtaining over 89.14% photodegradation efficiency with a kinetic constant of 0.024 min−1, which is 5.2 times higher than that of bare BiOCl (0.0046 min−1). Moreover, based on the results of cycle experiment and structural characterization, FeOOH-modified BiOCl still maintains nearly 80% photodegradation efficiency after cyclic reaction, significantly boosting photocarrier separation rate and improving structural stability of BiOCl crystal. The present study offers a novel strategy for stabilizing oxyhalide crystals by construction of S-scheme heterojunction, enabling effective photodegradation of organic pollutants.
Layered BiOCl photocatalyst exhibits great promise for photocatalytic wastewater treatment in environmental remediation. However, its structural instability hinders further development toward photodegrading organic pollutants due to the photocorrosion caused by slow photocarrier separation. To address this major challenge, the constructed BiOCl-based S-scheme heterojunction is considered as one wonderful strategy which can efficiently steer photocarrier separation by the internal electric field and synergistically achieve stable surface structure. In this work, 2D/2D FeOOH/BiOCl S-scheme heterojunction by coupling FeOOH and BiOCl nanoplate was prepared via in situ photodeposition approach. Photocatalytic results indicate that the optimal 10 wt% FeOOH/BiOCl exhibits excellent photocatalytic activity and stability in tetracycline (TC) degradation, obtaining over 89.14% photodegradation efficiency with a kinetic constant of 0.024 min−1, which is 5.2 times higher than that of bare BiOCl (0.0046 min−1). Moreover, based on the results of cycle experiment and structural characterization, FeOOH-modified BiOCl still maintains nearly 80% photodegradation efficiency after cyclic reaction, significantly boosting photocarrier separation rate and improving structural stability of BiOCl crystal. The present study offers a novel strategy for stabilizing oxyhalide crystals by construction of S-scheme heterojunction, enabling effective photodegradation of organic pollutants.
2026, 45(3): 100833
doi: 10.1016/j.cjsc.2025.100833
Abstract:
Carrier recombination in polymer photocatalysts involves both undissociated exciton decay and charge recombination, which are the main obstacles limiting their photocatalytic activity. Achieving efficient charge generation and separation in a polymer system is a fundamental strategy for the potential success of solar energy conversion to hydrogen, but it remains a huge challenge. In this study, we propose an innovative intermolecular π–π stacking strategy to construct a π-delocalized all-polymer S-scheme heterojunction for photocatalytic hydrogen evolution. Two conjugated porous polymers (CPPs)—PyB, composed of benzo[1,2-b:4,5-b′]dithiophene (BDT) and pyrene units, and PhB, composed of BDT and benzene—were synthesized and integrated with CN nanosheets. The highly planar and π-extended structure of PyB facilitated strong interfacial π–π stacking with CN, forming an extended π-delocalized network that enhanced the internal electric field (IEF), improved charge separation, and boosted visible-light absorption. As a result, the optimized PyB/CN-20 composite achieved a remarkable hydrogen evolution rate (HER) of 23.84 mmol⋅h−1⋅g−1 under visible light, approximately 287 times higher than that of pristine CN. This work underscores the critical role of polymer planarity and π-conjugation in heterojunction efficiency, and provides new insights into the rational design of π-delocalized S-scheme systems and establishes a general strategy for developing highly efficient, metal-free photocatalysts by leveraging molecular-level structural control.
Carrier recombination in polymer photocatalysts involves both undissociated exciton decay and charge recombination, which are the main obstacles limiting their photocatalytic activity. Achieving efficient charge generation and separation in a polymer system is a fundamental strategy for the potential success of solar energy conversion to hydrogen, but it remains a huge challenge. In this study, we propose an innovative intermolecular π–π stacking strategy to construct a π-delocalized all-polymer S-scheme heterojunction for photocatalytic hydrogen evolution. Two conjugated porous polymers (CPPs)—PyB, composed of benzo[1,2-b:4,5-b′]dithiophene (BDT) and pyrene units, and PhB, composed of BDT and benzene—were synthesized and integrated with CN nanosheets. The highly planar and π-extended structure of PyB facilitated strong interfacial π–π stacking with CN, forming an extended π-delocalized network that enhanced the internal electric field (IEF), improved charge separation, and boosted visible-light absorption. As a result, the optimized PyB/CN-20 composite achieved a remarkable hydrogen evolution rate (HER) of 23.84 mmol⋅h−1⋅g−1 under visible light, approximately 287 times higher than that of pristine CN. This work underscores the critical role of polymer planarity and π-conjugation in heterojunction efficiency, and provides new insights into the rational design of π-delocalized S-scheme systems and establishes a general strategy for developing highly efficient, metal-free photocatalysts by leveraging molecular-level structural control.
2026, 45(3): 100834
doi: 10.1016/j.cjsc.2025.100834
Abstract:
2026, 45(3): 100841
doi: 10.1016/j.cjsc.2025.100841
Abstract:
The catalytic performance of single-atom catalysts in CO2 photoreduction can be optimized through precise modulation of the coordination structures of single-atoms. In this study, Ru single-atoms (Ru-SAs) immobilized on the Zr6O8 clusters of a porphyrinic metal–organic framework (Zn-PCN-222) were modified with sulfhydryl groups (–SH). The resulting RuS-SAs@Zn-PCN-222 exhibited high photocatalytic activity for CO2 reduction to HCOO− using ammonia borane as the H* donor, giving rise to a HCOO− production rate of 54.4 mmol·g–1·h–1 with 99.9% selectivity, which was approximately 20.1 and 4.5 times higher than that of Zn-PCN-222 and –SH-free Ru-SAs@Zn-PCN-222, respectively. Photoelectrochemical measurements demonstrated that the incorporated RuS-SAs enhanced the separation and migration of photogenerated charges in RuS-SAs@Zn-PCN-222. Further in situ experiments revealed that the RuS-SAs could accept photogenerated electrons from Zn-PCN-222 as well as electrons from the –SH groups, and then inject to inert CO2 molecules, thereby facilitating CO2 activation and its subsequent coupling with H* to form HCOO−.
The catalytic performance of single-atom catalysts in CO2 photoreduction can be optimized through precise modulation of the coordination structures of single-atoms. In this study, Ru single-atoms (Ru-SAs) immobilized on the Zr6O8 clusters of a porphyrinic metal–organic framework (Zn-PCN-222) were modified with sulfhydryl groups (–SH). The resulting RuS-SAs@Zn-PCN-222 exhibited high photocatalytic activity for CO2 reduction to HCOO− using ammonia borane as the H* donor, giving rise to a HCOO− production rate of 54.4 mmol·g–1·h–1 with 99.9% selectivity, which was approximately 20.1 and 4.5 times higher than that of Zn-PCN-222 and –SH-free Ru-SAs@Zn-PCN-222, respectively. Photoelectrochemical measurements demonstrated that the incorporated RuS-SAs enhanced the separation and migration of photogenerated charges in RuS-SAs@Zn-PCN-222. Further in situ experiments revealed that the RuS-SAs could accept photogenerated electrons from Zn-PCN-222 as well as electrons from the –SH groups, and then inject to inert CO2 molecules, thereby facilitating CO2 activation and its subsequent coupling with H* to form HCOO−.
2026, 45(3): 100842
doi: 10.1016/j.cjsc.2025.100842
Abstract:
In recent years, metal-organic frameworks (MOFs) have emerged as promising materials in modifying perovskite solar cells (PSCs) due to their unique porous structures, exceptional specific surface area, tunable organic–inorganic coordination environments, and abundant modification sites. These features endowed MOFs with the ability to regulate the crystallization rate of perovskite films, promote uniform crystal growth, and passivate both surface and grain boundary defects. This review systematically categorizes the applications of MOFs in PSCs based on MOF types and their corresponding functional mechanisms, while exploring the selection criteria for MOFs with different structures from five key dimensions: pores, framework structures, functional groups, MOF composites, and MOF derivatives. Focusing on the structural design of MOFs, this review further aims to forecast the development trends of MOFs at the MOF/PSCs interface and provide guidance for the rational design and selection of MOFs for propelling next-generation photovoltaic technologies.
In recent years, metal-organic frameworks (MOFs) have emerged as promising materials in modifying perovskite solar cells (PSCs) due to their unique porous structures, exceptional specific surface area, tunable organic–inorganic coordination environments, and abundant modification sites. These features endowed MOFs with the ability to regulate the crystallization rate of perovskite films, promote uniform crystal growth, and passivate both surface and grain boundary defects. This review systematically categorizes the applications of MOFs in PSCs based on MOF types and their corresponding functional mechanisms, while exploring the selection criteria for MOFs with different structures from five key dimensions: pores, framework structures, functional groups, MOF composites, and MOF derivatives. Focusing on the structural design of MOFs, this review further aims to forecast the development trends of MOFs at the MOF/PSCs interface and provide guidance for the rational design and selection of MOFs for propelling next-generation photovoltaic technologies.
2026, 45(3): 100843
doi: 10.1016/j.cjsc.2025.100843
Abstract:
Organic cage compounds, which are among the most important classes of supramolecular hosts, have been found to be capable of capturing various guests through host-guest interactions due to their inherent cavities. To date, the exploration of potential applications based on such host-guest chemistry has been a subject of intensive research. Herein, we report a highly stable sp2 carbon-conjugated porous organic cage (POC), abbreviated as sp2c-POC3, formed via the Knoevenagel reaction between tetraformyl-functionalized calix[4]resorcinarene and V-shaped diacetonitrile subunits. X-ray crystallographic analysis reveals that sp2c-POC3 is a [2+4] long lantern-shaped cage. It contains four rhombic windows with an average edge length of approximately 2.1 nm and a large cavity with a volume of approximately 782 Å3. Notably, this cage can selectively capture perchlorate (ClO4-) anions. Taking advantage of such anion trapping ability and the porous nature, a quasi-solid-state electrolyte (QSSE) based on sp2c-POC3 and incorporating LiClO4 has been rationally designed. This sp2c-POC3-based QSSE exhibits a high ionic conductivity of 2.5×10-3 S cm-1 at room temperature.
Organic cage compounds, which are among the most important classes of supramolecular hosts, have been found to be capable of capturing various guests through host-guest interactions due to their inherent cavities. To date, the exploration of potential applications based on such host-guest chemistry has been a subject of intensive research. Herein, we report a highly stable sp2 carbon-conjugated porous organic cage (POC), abbreviated as sp2c-POC3, formed via the Knoevenagel reaction between tetraformyl-functionalized calix[4]resorcinarene and V-shaped diacetonitrile subunits. X-ray crystallographic analysis reveals that sp2c-POC3 is a [2+4] long lantern-shaped cage. It contains four rhombic windows with an average edge length of approximately 2.1 nm and a large cavity with a volume of approximately 782 Å3. Notably, this cage can selectively capture perchlorate (ClO4-) anions. Taking advantage of such anion trapping ability and the porous nature, a quasi-solid-state electrolyte (QSSE) based on sp2c-POC3 and incorporating LiClO4 has been rationally designed. This sp2c-POC3-based QSSE exhibits a high ionic conductivity of 2.5×10-3 S cm-1 at room temperature.
2026, 45(3): 100844
doi: 10.1016/j.cjsc.2025.100844
Abstract:
Nonlinear optical (NLO) crystals with efficient frequency conversion are essential for all-solid-state lasers, and exploring new second harmonic generation (SHG) enhancing strategy is crucial for the structure-property relationship research and application of NLO crystals. Conventional strategies focus on inducing parallel alignment of NLO active units. In this work, two new regulation means, i.e. bond polarization and flexible deformation, have been identified in rare earth carbonates REXCO3 (RE = La, Ce, Y; X = OH, F) with anionic motifs circular aligned through experimental characterization and first-principles calculations. They can promote the SHG effect in the form of electronic polarization and polyhedra distortion, respectively. Such regulation methods break the common acceptation that only carbonates aligning in a parallel pattern can effectively achieve the superposition of hyperpolarizabilities and result in considerable SHG effect. By realizing the synergistic effect of circular alignment and rare earth polyhedra, the polarizability and flexible stretching ability of the RE-O coordination bonds are effectively exerted in the designed structure, C2_La2O2CO3. This work unveils a new mechanism for SHG enhancement in rare earth carbonates and provides new insight for designing advanced NLO materials.
Nonlinear optical (NLO) crystals with efficient frequency conversion are essential for all-solid-state lasers, and exploring new second harmonic generation (SHG) enhancing strategy is crucial for the structure-property relationship research and application of NLO crystals. Conventional strategies focus on inducing parallel alignment of NLO active units. In this work, two new regulation means, i.e. bond polarization and flexible deformation, have been identified in rare earth carbonates REXCO3 (RE = La, Ce, Y; X = OH, F) with anionic motifs circular aligned through experimental characterization and first-principles calculations. They can promote the SHG effect in the form of electronic polarization and polyhedra distortion, respectively. Such regulation methods break the common acceptation that only carbonates aligning in a parallel pattern can effectively achieve the superposition of hyperpolarizabilities and result in considerable SHG effect. By realizing the synergistic effect of circular alignment and rare earth polyhedra, the polarizability and flexible stretching ability of the RE-O coordination bonds are effectively exerted in the designed structure, C2_La2O2CO3. This work unveils a new mechanism for SHG enhancement in rare earth carbonates and provides new insight for designing advanced NLO materials.
