As hot topics in the chemical conversion of CO2, the photo‐/electrocatalytic reduction of CO2 and use of CO2 as a supporter for energy storage have shown great potential for the utilization of CO2. ...However, many obstacles still exist on the road to realizing highly efficient chemical CO2 conversion, such as inefficient uptake/activation of CO2 and mass transport in catalysts. Covalent organic frameworks (COFs), as a kind of porous material, have been widely explored as catalysts for the chemical conversion of CO2 owing to their unique features. In particular, COF‐based functional materials containing diverse active sites (such as single metal sites, metal nanoparticles, and metal oxides) offer great potential for realizing CO2 conversion and energy storage. This Minireview discusses recent breakthroughs in the basic knowledge, mechanisms, and pathways of chemical CO2 conversion strategies that use COF‐based functional catalysts. In addition, the challenges and prospects of COF‐based functional catalysts for the efficient utilization of CO2 are also introduced.
This Minireview discusses recent developments in the basic knowledge, mechanisms, and CO2 utilization strategies regarding the use of functional materials based on covalent‐organic frameworks (COFs) with diverse active sites as catalysts. Insight is provided into the challenges and prospects of COF‐based catalysts for the design of the next‐generation photo‐/electrocatalysts for the utilization of CO2.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Aqueous Zn‐metal batteries are the most promising system for large‐scale energy storage due to their high capacity, high safety, and low cost. The Zn‐metal anode, however, suffers from continuous ...parasitic reactions, random dendrite growth, and sluggish kinetics in aqueous electrolytes. Herein, a high donor number solvent, tetramethylurea (TMU), is introduced as electrolyte additive to enable highly reversible Zn‐metal anode, where the TMU can 1) preferentially adsorb on the Zn surface to inhibit Zn corrosion and suppress parasitic reaction, 2) solvate with Zn2+ and exclude the H2O from Zn2+ solvation sheath to weaken water activity significantly, and 3) contribute to form an inorganic‐organic bilayer solid electrolyte interphase to enable homogeneous and rapid Zn2+ transport kinetic for dendrite‐free Zn deposition. Benefiting from these three merits, the resulting aqueous electrolyte demonstrates a highly reversible Zn plating/stripping cycling in a Zn||Ti asymmetric cell for over 1200 cycles and in a Zn||Zn symmetric cell for over 4000 h. As a proof‐of‐concept, the aqueous Zn‐metal full cells assembled with various state‐of‐the‐art cathodes also deliver excellent cycling performance even with a 10 µm thin Zn anode, favoring the practical application.
A high donor solvent, tetramethylurea, is introduced as an electrolyte additive to enable highly reversible Zn‐metal anode with superior cyclability under harsh conditions. Rationally, the tetramethylurea can adsorb on the Zn surface to suppress parasitic reaction, solvate with Zn2+ to weaken water activity, and contribute to form an inorganic‐organic bilayer solid electrolyte interphase to enable homogeneous Zn deposition and rapid Zn2+ transport kinetic.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Lithium metal batteries hold great promise for promoting energy density and operating at low temperatures, yet they still suffer from insufficient Li compatibility and slow kinetic, especially at ...ultra‐low temperatures. Herein, we rationally design and synthesize a new amphiphilic solvent, 1,1,2,2‐tetrafluoro‐3‐methoxypropane, for use in battery electrolytes. The lithiophilic segment is readily to solvate Li+ to induce self‐assembly of the electrolyte solution to form a peculiar core‐shell‐solvation structure. Such unique solvation structure not only largely improves the ionic conductivity to allow fast Li+ transport and lower the desolvation energy to enable facile desolvation, but also leads to the formation of a highly robust and conductive inorganic SEI. The resulting electrolyte demonstrates high Li efficiency and superior cycling stability from room temperature to −40 °C at high current densities. Meanwhile, anode‐free high‐voltage cell retains 87 % capacity after 100 cycles.
A new amphiphilic solvent is rationally designed to induce self‐assembly of the electrolyte solution to form a peculiar core‐shell‐solvation structure. Such unique solvation structure bestows improved ionic conductivity, low desolvation energy, and highly robust and conductive SEI, which overcomes the long‐standing Li compatibility and deposition kinetic challenges, enabling the stable operation of Li‐metal battery under ultra‐low temperature.
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The precise tuning and multi‐dimensional processing of covalent organic frameworks (COFs)‐based materials into multicomponent superstructures with appropriate diversity are essential to maximize ...their advantages in catalytic reactions. However, up to now, it remains an ongoing challenge for the precise design of COFs‐based multicomponent nanocomposites with diverse architectures. Herein, a metal organic framework (MOF)‐sacrificed in situ acid‐etching (MSISAE) strategy that enables continuous synthesis of core‐shell, yolk‐shell, and hollow‐sphere COFs‐based nanocomposites through tuning of core decomposition (NH2‐MIL‐125 into TiO2) rate is developed. More importantly, due to the multiple active sites, fast transfer of carriers, increased light utilization ability, et al, one of the obtained samples, NH2‐MIL‐125/TiO2@COF‐366‐Ni‐OH‐HAc (yolk‐shell) with special three components, exhibits high photocatalytic CO2‐to‐CO conversion efficiency in the gas‐solid mode. The MSISAE strategy developed in this work achieves the precise morphology design and control of multicomponent hybrid composites based on COFs, which may pave a new way in devealoping porous crystalline materials with powerful superstructures for multifunctional catalytic reactions.
A metal–organic‐framework‐sacrificed in situ acid‐etching strategy to bring about the controllable synthesis of a series of covalent organic framework based multicomponent nanocomposites from core–shell, yolk–shell, and hollow‐sphere structures is presented. Combining the unique yolk–shell structure with the synergistic effects of the three components, the MTCN‐H (ys) demon strates remarkable catalytic performance in photocatalytic reduction of CO2 with H2O.
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Si microparticle (SiMP) anodes feature much lower production cost and higher tap density compared to their nanosized counterparts, which hold great promise for high‐energy‐density lithium‐ion ...batteries, yet they suffer from unavoidable particle pulverization during repeated cycling, thus making their practical application extremely challenging. Herein, a non‐flammable localized high‐concentration electrolyte (LHCE) is rationally formulated using a fluorinated solvent, 2,2,2‐trifluoroethyl methyl carbonate (FEMC), to induce fluorinated solvent‐coupled anion‐derived interfacial chemistry. Unlike other LHCEs, the FEMC‐based LHCE is demonstrated to build a highly robust and stable F‐rich inorganic–organic bilayer solid–electrolyte interphase on SiMP anode, which endows stable cycling of SiMP anode (≈3.4 mAh cm−2) with an ultrahigh Coulombic efficiency of ≈99.7%. Coupled with its high anodic stability, the FEMC‐based LHCE endows unprecedented cycling stability for high‐energy‐density batteries containing high‐capacity SiMP anodes with Ni‐rich LiNi8Mn1Co1O2 or 5 V‐class LiNi0.5Mn1.5O4 cathodes. Remarkably, a 1.0 Ah‐level SiMP||LiNi8Mn1Co1O2 pouch‐cell stably operates for more than 200 cycles, representing the pioneering report in pouch cells containing SiMP anodes.
A fluorinated solvent is incorporated into localized high‐concentration electrolyte to induce fluorinated solvent‐coupled anion‐derived interfacial chemistry, which yields a highly robust and stable F‐rich inorganic–organic bilayer solid–electrolyte interphase to enable stable cycling of Si microparticle anode. This electrolyte overcomes the longstanding challenges of Si microparticle pulverization and high‐voltage incompatibility, endowing the stable operation of high‐energy‐density Li‐ion batteries.
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A lithium-sulfur (Li-S) battery is regarded as the most promising candidate for next generation energy storage systems, because of its high theoretical specific capacity (1675 mA h g
) and specific ...energy (2500 W h kg
), as well as the abundance, low cost and environmental benignity of sulfur. However, the soluble polysulfides Li
S
(4 ≤ x ≤ 8) produced during the discharge process can cause the so-called "shuttle effect" and lead to low coulombic efficiency and rapid capacity fading of the batteries, which seriously restrict their practical application. Using porous materials as hosts to immobilize the polysulfides is proved to be an effective strategy. In this article, a dual functional cage-like metal-organic framework (Cu-MOF), Cu-TDPAT, combining the Lewis basic sites from the nitrogen atoms of the ligand H
TDPAT with the Lewis acidic sites from Cu(ii) open metal sites (OMSs), was employed as the sulfur host in a Li-S battery for lithium ions and polysulfide anions (S
). In addition, the size of nano-Cu-TDPAT was also optimized by microwave synthesis to reduce the internal resistance of the batteries. The electrochemical test results showed that the optimized Cu-TDPAT material can efficiently confine the polysulfides within the MOF, and the resultant porous S@Cu-TDPAT composite cathode material with the size of 100 nm shows good cycling performance with a reversible capacity of about 745 mA h g
at 1C (1C = 1675 mA g
) after 500 cycles, to the best of our knowledge, which is higher than those of all reported S@MOF cathode materials. The DFT calculation and XPS data indicate that the good cycling performance mainly results from the dual functional binding sites (that is, Lewis acid and base sites) in nanoporous Cu-TDPAT, providing the comprehensive and robust interaction with the polysulfides to overcome their dissolution and diffusion into the electrolyte. Clearly, our work provides a good example of designing MOFs with suitable interaction sites for the polysulfides to achieve S@MOF cathode materials with excellent cycling performance by multiple synergistic effects between nanoporous host MOFs and the polysulfides.
Necroptosis is an alternative form of programmed cell death that generally occurs under apoptosis‐deficient conditions. Our previous work showed that connexin32 (Cx32) promotes the malignant progress ...of hepatocellular carcinoma (HCC) by enhancing the ability of resisting apoptosis in vivo and in vitro. Whether triggering necroptosis is a promising strategy to eliminate the apoptosis‐resistant HCC cells with high Cx32 expression remains unknown. In this study, we found that Cx32 expression was positively correlated with the expression of necroptosis protein biomarkers in human HCC specimens, cell lines, and a xenograft model. Treatment with shikonin, a well‐used necroptosis inducer, markedly caused necroptosis in HCC cells. Interestingly, overexpressed Cx32 exacerbated shikonin‐induced necroptosis, but downregulation of Cx32 alleviated necroptosis in vitro and in vivo. Mechanistically, Cx32 was found to bind to Src and promote Src‐mediated caspase 8 phosphorylation and inactivation, which ultimately reduced the activated caspase 8‐mediated proteolysis of receptor‐interacting serine‐threonine protein kinase 1/3, the key molecule for necroptosis activation. In conclusion, we showed that Cx32 contributed to the activation of necroptosis in HCC cells through binding to Src and then mediating the inactivation of caspase 8. The present study suggested that necroptosis inducers could be more favorable than apoptosis inducers to eliminate HCC cells with high expression of Cx32.
Connexin32 promotes shikonin‐induced necroptosis in hepatocellular carcinoma by interacting with Src and enhancing Src‐mediated caspase 8 phosphorylation on Tyr380. We identified the novel role of connexin32 in necroptosis and elucidated connexin32 as a potential target for pronecroptosis therapy in hepatocellular carcinoma.
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Metal-organic framework (MOF)-derived hybrids are promising electrode materials in electrochemical energy storage, owing to their high surface area that offers enormous redox sites and excellent ...conductivity. In this work, MOF-derived cerium oxide/carbon integrated with molybdenum disulfide (CeO2/C/MoS2) hybrid is developed as an electrode material for supercapacitor. Remarkably, integration of CeO2/C with small amount of MoS2 has considerably enhanced the electrochemical performance. Moreover, CeO2/C/MoS2 hybrid exhibited both surface and diffusion-controlled mechanism towards charge storage. The CeO2/C/MoS2 hybrid showed an outstanding specific capacitance (specific capacity) of 1325.67 F g−1 (397.70 C g−1) and excellent cyclic stability with capacitance retention of 92.8% after 1000 charging-discharging cycles, which is significantly higher than that of CeO2/C (727.49 F g−1) or else that of MoS2 (300.33 F g−1) at 1 A g−1. In addition, asymmetric supercapacitor (ASC) fabricated with CeO2/C/MoS2 hybrid and activated carbon (AC) showed remarkable electrochemical performance with high specific capacitance (110.55 F g−1), excellent cyclic stability (even after 1000 cycles) and high energy density of 34.55 Wh kg−1 at a power density of 666.7 W kg−1. Thus, MOF derived CeO2/C integrated MoS2 hybrid is a potential electrode material for the ASCs.
MOF-derived CeO2/C integrated MoS2 (CeO2/C/MoS2) hybrid is developed as an electrode material with high-performance for asymmetric supercapacitor. Display omitted
•MOF-derived CeO2/C integrated MoS2 hybrid is prepared.•The charge storage mechanism for a hybrid electrode is investigated.•CeO2/C/MoS2 electrode exhibits specific capacitance of 1325.67 F g−1 at 1 A g −1.•The ASC exhibits an excellent energy density of 34.55 W h kg−1 at 666.7 W kg−1.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
In this work, we demonstrate cerium (Ce) based metal–organic frameworks (MOFs) combined with carbon nanotubes (CNTs) to form Ce-MOF/CNT composites as separator coating material in the Li–S battery ...system, which showed excellent electrochemical performance even under high sulfur loading and much better capacity retention. At the sulfur loading of 2.5 mg/cm2, initial specific capacity of 1021.8 mAh/g at 1C was achieved in the Li–S cell with the Ce-MOF-2/CNT coated separator, which was slowly reduced to 838.8 mAh/g after 800 cycles with a decay rate of only 0.022% and the Coulombic efficiency of nearly 100%. Even at a higher sulfur loading of 6 mg/cm2, the cell based on Ce-MOF-2/CNT separator coating still exhibited excellent performance with initial specific capacity of 993.5 mAh/g at 0.1 C. After 200 cycles, the specific capacity of 886.4 mAh/g was still retained. The excellent performance is ascribed to the efficient adsorption of the Ce-MOF-2 to Li2S6 species and its catalytic effect toward conversion of polysulfides, resulting in suppressed shuttle effect of polysulfides in the Li–S batteries.
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Transition-metal sulfide is a good kind of material for supercapacitors because of the large capacity. Nevertheless, the low electroconductivity, slow reaction kinetics, and limited active centers ...lead to poor electrochemical properties such as long-term cycling stability. In the present work, nano nickel metal–organic framework (Ni-MOF) was constructed by using the nitrogen-rich functional group ligand 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazin and compounded with carbon nanotubes (CNTs) to prepare Ni-MOF/CNTs composite, which was used as a precursor to prepare the MOFs-derived NC/Ni–Ni3S4/CNTs composite with the Ni3S4 uniformly distributed in the three-dimensional (3D) conductive network. The rich nitrogen doping and 3D conductive network constructed by CNTs improved the conductivity, prompted the rapid entry of electrolyte, and improved the reaction kinetics of NC/Ni–Ni3S4/CNTs, thus obtained excellent specific capacitance, coulomb efficiency, and cyclic stability. The specific capacitance of NC/Ni–Ni3S4/CNTs is 1489.9 F/g at 1 A/g, which remains 800 F/g at 10 A/g, showing good rate performance.
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