The design and synthesis of metal‐organic frameworks (MOFs) as photocatalytic molecular reactors for varied reactions have drawn great attention. In this work, we designed a novel photoactive ...perylenediimides‐based (PDI) carboxylate ligand N,N’‐di(3’,3”,5’,5”‐tetrakis(4‐carboxyphenyl))‐1,2,6,7‐tetrachloroperylene‐3,4,9,10‐tetracarboxylic acid diimide (Cl‐PDI‐TA) and use it to successfully synthesize a novel Zr(IV)‐based MOF 1 constructed from Zr6O8(H2O)88+ clusters bridged by Cl‐PDI‐TA ligands. Structural analysis revealed that Zr‐MOF 1 manifests a 3D framework with (4,8)‐connected csq topology and possesses triangular channels of ~17 Å and mesoporous hexagonal channels of ~26 Å along c‐axis. Moreover, the synthesized Zr‐MOF 1 exhibits visible‐light absorption and efficient photoinduced free radical generation property, making it a promising photocatalytic molecular reactor. When Zr‐MOF 1 was used as a photocatalyst for the aerobic oxidation of sulfides under irradiation of visible light, it could afford the corresponding sulfoxides with high yield and selectivity. Experimental results demonstrated that the substrate sulfides could be fixed in the pores of 1 and directly transformed to the products sulfoxides in the solid state. Furthermore, the mechanism for the photocatalytic transformation was also investigated and the results revealed that the singlet oxygen (1O2) and superoxide radical (O2⋅−) generated by the energy transfer and electron transfer from the photoexcited Zr‐MOF to oxidants were the main active species for the catalytic reactions. This work offers a perceptive comprehension of the mechanism in PDI‐based MOFs for further study on photocatalytic reactions.
Herein, we designed a novel PDI‐based Zr‐MOF as a photocatalytic molecular reactor for the solid‐ and liquid‐phase photocatalytic oxidation of sulfur ethers to sulfoxides. High yields and excellent selectivity and recyclability were demonstrated, which provide a basis for further investigation of the mechanism of action of PDI‐MOF in other photocatalytic reactions.
Covalent organic frameworks (COFs) have received increased interest in recent years as an advanced class of materials. By virtue of the available monomers, multiple conformations and various ...linkages, COFs offer a wide range of opportunities for complex structural design and specific functional development of materials, which has facilitated the widespread application in many fields, including multi‐valent metal ion batteries (MVMIBs), described as the attractive candidate replacing lithium‐ion batteries (LIBs). With their robust skeletons, diverse pores, flexible structures and abundant functional groups, COFs are expected to help realize a high performance MVMIBs. In this review, we present an overview of COFs, describe advances in topology design and synthetic reactions, and study the application of COFs in MVMIBs, as well as discuss challenges and solutions in the preparation of COFs electrodes, in the hope of providing constructive insights into the future direction of COFs.
Covalent organic frameworks (COFs) offer an opportunity for complex structural design and specific functional development, facilitating, for example, the applications of multi‐valent metal ion batteries (Zn2+, Mg2+, Al3+). This comprehensive review describes COF synthesis and applications, provides advances in topology design and synthetic reactions, surveys the application of COFs in multi‐valent ion batteries, discusses the key issues of COF electrodes, and predicts future applications.
Sodium‐ion batteries (SIBs) have gradually become one of the most promising energy storage techniques in the current era of post‐lithium‐ion batteries. For anodes, transitional metal selenides (TMSe) ...based materials are welcomed choices , owing to relatively higher specific capacities and enriched redox active sites. Nevertheless, current bottlenecks are blamed for their poor intrinsic electronic conductivities, and uncontrollable volume expansion during redox reactions. Given that, an interfacial‐confined isochronous conversion strategy is proposed, to prepare orthorhombic/cubic biphasic TMSe heterostructure, namely CuSe/Cu3VSe4, through using MXene as the precursor, followed by Cu/Se dual anchorage. As‐designed biphasic TMSe heterostructure endows unique hierarchical structure, which contains adequate insertion sites and diffusion spacing for Na ions, besides, the surficial pseudocapacitive storage behaviors can be also proceeded like 2D MXene. By further investigation on electronic structure, the theoretical calculations indicate that biphasic CuSe/Cu3VSe4 anode exhibits well‐enhanced properties, with smaller bandgap and thus greatly improves intrinsic poor conductivities. In addition, the dual redox centers can enhance the electrochemical Na ions storage abilities. As a result, the as‐designed biphasic TMSe anode can deliver a reversible specific capacity of 576.8 mAh g−1 at 0.1 A g−1, favorable Na affinity, and reduced diffusion barriers. This work discloses a synchronous solution toward demerits in conductivities and lifespan, which is inspiring for TMSe‐based anode development in SIBs systems.
An interfacial‐confined isochronous conversion strategy is conducted to prepare a hierarchical biphasic selenide, by choosing metallic conductive V2CTx MXene as the precursor. As‐designed biphasic selenide exhibits excellent electronic conductivity and abundant active sites for Na ions. Besides, the carbonaceous matrix can serve as a stable buffer layer to alleviate the volume expansion of selenides during battery operation.
Cu(ii) supramolecular assemblies Cu2(tipe)2(H2O)2(NO3)4·2.5H2O (CuN4) and Cu2Cl4(tipe)(CH3CN)·H2O (CuN2Cl2) (tipe = 1,1,2,2-tetrakis(4-(imidazole-1-yl)phenyl)ethene) were synthesized and utilized for ...photocatalytic CO2 reduction. CuN4 exhibits CO production of up to 891 μmol gcat−1 with a selectivity of 79.9%, while CuN2Cl2 gives low CO production of 206 μmol gcat−1 but with a high selectivity of >99.9% in 5 h. The experimental and DFT calculation results indicate that the coordination environment and non-covalent interactions within the assemblies have a great impact on the photocatalytic CO2 reduction behavior. This work provides useful insights on Cu(ii) assembly catalyzed CO2 photoreduction.
The direct reuse of retired lithium-ion batteries (LIBs) cathode materials is one of the optimum choices for “waste-to-wealth” by virtue of sustainable and high economic efficiency. Considering the ...harmfulness of retired LIBs and the serious shortage of lithium resources, in this work, the spent oxide cathode materials after simple treatment are directly applied to the sodium-ion batteries (SIBs) and exhibit promising application possibilities in advanced SIBs. The spent oxide cathode shows an appropriate initial discharge capacity of 109 mAh·g
−1
and exhibits transition and activation processes at a current density of 25 mA·g
−1
. Further, it demonstrates decent cycle performance and comparatively good electrode kinetics performance (the apparent ion diffusion coefficient at steady state is about 1 × 10
–12
cm
2
·s
−1
). The “waste-to-wealth” concept of this work provides an economical and sustainable strategy for directly reusing the retired LIBs and supplies a large amount of raw material for the large-scale application of SIBs.
Graphical abstract
Endothelial dysfunction is considered to be an early change in atherosclerosis. Endocan, also known as endothelial cell specific molecule-1, is a soluble proteoglycan mainly secreted by endothelial ...cells. Inflammatory factors such as IL-1β and TNF-α can up regulate the expression of endocan and then affect the expression of cell adhesion molecules, such as ICAM-1 and VCAM-1, which play an important role in promoting leukocyte migration and inflammatory response. Elevated plasma levels of endocan may reflect endothelial activation and dysfunction, and is considered to be a potential immuno-inflammatory marker that may be related to cardiovascular disease. In the case of hypertension, diabetes, angina pectoris and acute myocardial infarction, the increase or decrease of serum endocan levels is of great significance. Here, we reviewed the current research on endocan, and emphasis its possible clinical value as a prognostic marker of cardiovascular disease. Endocan may be a useful biomarker for the prognosis of cardiovascular disease, but more research is needed on its mechanism of action.
Hard carbon (HC) is broadly recognized as an exceptionally prospective candidate for the anodes of sodium-ion batteries (SIBs), but their practical implementation faces substantial limitations linked ...to precursor factors, such as reduced carbon yield and increased cost. Herein, a cost-effective approach is proposed to prepare a coal-derived HC anode with simple pre-oxidation followed by a post-carbonization process which effectively expands the
d
002
layer spacing, generates closed pores and increases defect sites. Through these modifications, the resulting HC anode attains a delicate equilibrium between plateau capacity and sloping capacity, showcasing a remarkable reversible capacity of 306.3 mAh·g
−1
at 0.03 A·g
−1
. Furthermore, the produced HC exhibits fast reaction kinetics and exceptional rate performance, achieving a capacity of 289 mAh·g
−1
at 0.1 A·g
−1
, equivalent to ~ 94.5% of that at 0.03 A·g
−1
. When implemented in a full cell configuration, the impressive electrochemical performance is evident, with a notable energy density of 410.6 Wh·kg
−1
(based on cathode mass). In short, we provide a straightforward yet efficient method for regulating coal-derived HC, which is crucial for the widespread use of SIBs anodes.
Graphical abstract
Advanced polyanionic electrode materials for potassium-ion batteries are meticulously introduced. The basic insights into the material design, electrochemical feature, and energy storage mechanism of ...polyanionic compound and supply their future optimization with reasonable perspectives and strategies.
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Although potassium-ion batteries (KIBs) are considered a very promising energy storage system, their development for actual application still has a long way to go. Advanced electrode materials, as a fundamental component of KIBs, are essential for optimizing electrochemical performance and promoting effective energy storage. Due to their unique structural benefits in terms of cycle capability, strong ionic conductivity, and tunable operating voltage, polyanionic compounds are one type of viable electrode material for manufacturing high-performance KIBs. The huge size of K+ ion, on the other hand, places great demands on polyanionic materials, which must be able to withstand severe structural deformation during K+ intercalation/delamination. To maintain steady electrochemical performance, it is critical to follow the appropriate design guidelines for electrode materials. This paper provides a summary of current advancements in polyanionic compound for KIBs, with a focus on electrode material structural design. The effects of various parameters on electrochemical performance are examined and summarized. In addition, various viable solutions are proposed to address the impending issues posed by polyanionic compounds for KIBs, with the hope of providing a clearer picture of the field's future development path.
Due to the serious imbalance between demand and supply of lithium, lithium extraction from brine has become a research hotspot. With the demand for power lithium-ion batteries (LIBs) increased ...rapidly, a large number of spent LiFePO4 power batteries have been scrapped and entered the recycling stage. Herein, a novel and efficient strategy is proposed to extract lithium from brine by directly reusing spent LiFePO4 powder without any treatment. Various electrochemical test results show that spent LiFePO4 electrode has appropriate lithium capacity (14.62 mgLi/gLiFePO4), excellent separation performance (αLi-Na = 210.5) and low energy consumption (0.768 Wh/gLi) in electrochemical lithium extraction from simulated brine. This work not only provides a novel idea for lithium extraction from brine, but also develops an effective strategy for recycling spent LIBs. The concept of from waste to wealth is of great significance to the development of recycling the spent batteries.
The direct reuse of spent LiFePO4 powder for electrochemical lithium extraction from brine is proposed firstly, which exhibits appropriate capacity, excellent separation performance, low energy consumption, and provides a new avenue for electrochemical lithium extraction. Display omitted
Currently, the desired research focus in energy storage technique innovation has been gradually shifted to next-generation aqueous batteries holding both high performance and sustainability. However, ...aqueous Zn–I2 batteries have been deemed to have great sustainable potential, owing to the merits of cost-effective and eco-friendly nature. However, their commercial application is hindered by the serious shuttle effect of polyiodides during reversible operations. In this work, a Janus functional binder based on chitosan (CTS) molecules was designed and prepared; the polar terminational groups impart excellent mechanical robustness to hybrid binders; meanwhile, it can also deliver isochronous enhancement on physical adsorption and redox kinetics toward I2 species. By feat of highly effective remission to shuttle effect, the CTS cell exhibits superb electrochemical storage capacities with long-term robustness, specifically, 144.1 mAh g–1, at a current density of 0.2 mA g–1 after 1500 cycles. Simultaneously, the undesired self-discharging issue could be also well-addressed; the Coulombic efficiency could remain at 98.8 % after resting for 24 h. More importantly, CTS molecules endow good biodegradability and reusable properties; after iodine species were reloaded, the recycled devices could also deliver specific capacities of 73.3 mAh g–1, over 1000 cycles. This Janus binder provides a potential synchronous solution to realize high comprehensive performance with high iodine utilization and further make it possible for sustainable Zn–I2 batteries.
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