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The development and applications of porous materials have been revolutionized over the past decades. To fine-tune their fascinating behaviors such as charge-transport, magnetic, and catalytic properties, one of the most effective strategies is incorporating mixed valency into the structures. This Concept provides recent progress on emerging crystalline porous materials, namely, metal-organic frameworks, metal-organic polyhedra, covalent organic frameworks, and hydrogen-bonded organic frameworks, where their mixed valency is either intrinsic or postsynthetically induced via an external stimulus. We further highlight the investigation of mixed valency and potential applications, which sheds light on the design and exploitation of mixed-valence crystalline porous materials., (© 2024 Wiley-VCH GmbH.)

All-solid-state lithium batteries, including sulfide electrolytes and nickel-rich layered oxide cathode materials, promise safer electrochemical energy storage with high gravimetric and volumetric densities. However, the poor electrical conductivity of the active material results in the requirement for additional conducive additives, which tend to react negatively with the sulfide electrolyte. The fundamental scientific principle uncovered through this work is simple and suggests that the electrical network benefits associated with the introduction of short-length carbons will eventually be overpowered by the increase in bulk resistance associated with their instability in the sulfide electrolyte. However, applying just the right amount of short carbon fibres minimizes degradation of the sulfide solid electrolyte and maximizes the electron movement. Therefore, we propose the application of a low-weight-percent carbon nanotubes (CNTs) coating on the nickel-rich cathode LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) along with large-aspect-ratio carbon nanofibers (CNFs) as the primary conductive additive. When only 0.3 wt % CNTs was utilized with 4.7 wt % CNFs, an initial Coulombic efficiency of 83.55% at 0.05 C and a notably excellent capacity retention of 90.1% over 50 cycles at 0.5 C were achieved along with a low ionic resistance. This work helps to confirm the validity of applying short carbon pathways in sulfide-electrolyte-based cathode composites and proposes their combination with a larger primary carbon additive as a solution to the ongoing all-solid-state battery rate and instability issues.

Prussian blue analogues (PBAs) have gained tremendous attention as promising low-cost electrochemically-tunable electrode materials, which can accommodate large Na + ions with attractive specific capacity and charge-discharge kinetics. However, poor cycling stability caused by lattice strain and volume change remains to be improved. Herein, metal-doping strategy has been demonstrated in FeNiHCF, Na 1.40 Fe 0.90 Ni 0.10 [Fe(CN) 6 ] 0.85  ⋅ 1.3H 2 O, delivering a capacity as high as 148 mAh g -1 at 10 mA g -1 . At an exceptionally high rate of 25.6 A g -1 , a reversible capacity of ~55 mAh g -1 still can be obtained with a very small capacity decay rate of 0.02 % per cycle for 1000 cycles, considered one of the best among all metal-doped PBAs. This exhibits the stabilizing effect of Ni doping which enhances structural stability and long-term cyclability. In situ synchrotron X-ray diffraction reveals an extremely small (~1 %) change in unit cell parameters. The Ni substitution is found to increase the electronic conductivity and redox activity, especially at the low-spin (LS) Fe center due to inductive effect. This larger capacity contribution from LS Fe 2+ C 6 /Fe 3+ C 6 redox couple is responsible for stable high-rate capability of FeNiHCF. The insight gained in this work may pave the way for the design of other high-performance electrode materials for sustainable sodium-ion batteries., (© 2024 Wiley-VCH GmbH.)

We report two novel three-dimensional copper-benzoquinoid metal-organic frameworks (MOFs), [Cu 4 L 3 ] n and [Cu 4 L 3  ⋅ Cu(iq) 3 ] n (LH 4 =1,4-dicyano-2,3,5,6-tetrahydroxybenzene, iq=isoquinoline). Spectroscopic techniques and computational studies reveal the unprecedented mixed valency in MOFs, formal Cu(I)/Cu(III). This is the first time that formally Cu(III) species are witnessed in metal-organic extended solids. The coordination between the mixed-valence metal and redox-non-innocent ligand L, which promotes through-bond charge transfer between Cu metal sites, allows better metal-ligand orbital overlap of the d-π conjugation, leading to strong long-range delocalization and semiconducting behavior. Our findings highlight the significance of the unique mixed valency between formal Cu(I) and highly-covalent Cu(III), non-innocent ligand, and pore environments of these bench stable Cu(III)-containing frameworks on multielectron transfer and electrochemical properties., (© 2023 Wiley-VCH GmbH.)

Manipulating Fenton chemistry in tumor microenvironment (TME) for the generation of reactive oxygen species is an effective strategy for chemodynamic therapy. However, this is usually restricted by limited intracellular content of H 2 O 2 and insufficient acidic environment at the tumor site. Herein, a ferric metal-organic framework (MOF) is covalently grafted with a prodrug of cisplatin (Pt(IV) prodrug) and loaded with a biocatalyst glucose oxidase (GOx) to afford a nanozyme MOF-Pt(IV)@GOx for cascade reactions. In this system, the attached Pt(IV) prodrug on MOF plays a significant role in the cooperative enhancement of GOx loading and chemotherapy. The high concentration of glutathione in TME reduces Fe(III) to Fe(II) for Fenton reaction, and converts Pt(IV) prodrug to cisplatin for DNA targeting and H 2 O 2 production. Meanwhile, glucose oxidation catalyzed by GOx not only consumes glucose for starvation therapy, but also promotes the intracellular acidity and H 2 O 2 supply in TME, which are in favor of Fenton reaction. Both in vitro and in vivo studies demonstrate that MOF-Pt(IV)@GOx enables remarkable anticancer efficacy due to the synergistic trimodal therapy consisting of ferroptosis, starvation therapy, and chemotherapy., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Lignin is the most abundant natural aromatic polymer, especially in plant biomass. Lignin-derived phenolic compounds can be processed into high-value liquid fuel. This study aimed to determine the yield of lignin by the microwave-assisted solvent extraction method and to characterize some essential properties of the extracted lignin. Rubberwood sawdust ( Hevea brasiliensis ) was extracted for lignin with an organic-based solvent, either ethanol or isopropanol, in a microwave oven operating at 2450 MHz. Two levels of power of microwave, 100 W and 200 W, were tested as well as five extraction times (5, 10, 15, 20, 25, and 30 min). The extracted lignin was characterized by Klason lignin, Fourier transform infrared spectroscopy (FT-IR), 2D HSQC NMR, Ultraviolet-visible spectrophotometry (UV-vis), and Bomb calorimeter. The results showed that the yield of extracted lignin increased with the extraction time and power of the microwave. In addition, the extraction yield with ethanol was higher than the yield with isopropanol. The highest yield was 6.26 wt.%, with ethanol, 30 min extraction time, and 200 W microwave power.

A porous molecular crystal (PMC) assembled by macrocyclic cyclotetrabenzoin acetate is an efficient adsorbent for CO 2 separations. The 7.1×7.1 Å square pore of PMC and its ester C=O groups play important roles in improving its affinity for CO 2 molecules. The benzene walls of macrocycle engage in an apparent [π⋅⋅⋅π] interaction with the molecule of CO 2 at low pressure. In addition, the polar carbonyl groups pointing inward the square channels reduce the size of aperture to a 5.0×5.0 Å square, which offers kinetic selectivity for CO 2 capture. The PMC features water tolerance and high structural stability under vacuum and various gas adsorption conditions, which are rare among intrinsically porous organic molecules. Most importantly, the moderate adsorbate-adsorbent interaction allows the PMC to be readily regenerated, and therefore applied to pressure swing adsorption processes. The eluted N 2 and CH 4 are obtained with over 99.9 % and 99.8 % purity, respectively, and the separation performance is stable for 30 cycles. Coupled with its easy synthesis, cyclotetrabenzoin acetate is a promising adsorbent for CO 2 separations from flue and natural gases., (© 2021 Wiley-VCH GmbH.)

Natural kaolin-based Ni catalysts have been developed for low-temperature CO 2 methanation. The catalysts were prepared via a one-step co-impregnation of Ni and Ce onto a natural kaolin-derived metakaolin using a microwave-assisted hydrothermal method as an acid-/base-free synthesis method. The influences of microwave irradiation and Ce promotion on the catalytic enhancement including the CO 2 conversion, CH 4 selectivity, and CH 4 yield were experimentally investigated by a catalytic test of as-prepared catalysts in a fixed-bed tubular reactor. The relationship between the catalyst properties and its methanation activities was revealed by various characterization techniques including X-ray fluorescence, X-ray diffraction, Brunauer-Emmett-Teller, scanning electron microscopy, selected area electron diffraction, transmission electron microscopy, elemental mapping, H 2 temperature-programmed reduction, and X-ray absorption near-edge structure analyses. Among the two enhancement methods, microwave and Ce promotion, the microwave-assisted synthesis could produce a catalyst containing highly dispersed Ni particles with a smaller Ni crystallite size and higher catalyst reducibility, resulting in a higher CO 2 conversion from 1.6 to 7.5% and a better CH 4 selectivity from 76.3 to 79.9% at 300 °C. Meanwhile, the enhancement by Ce addition exhibited a great improvement on the catalyst activities. It was experimentally found that the CO 2 conversion increased approximately 7-fold from 7.5 to 52.9%, while the CH 4 selectivity significantly improved from 79.9 to 98.0% at 300 °C. Though the microwave-assisted synthesis could further improve the catalyst activities of Ce-promoted catalysts, the Ce addition exhibited a more prominent impact than the microwave enhancement. Cerium oxide (CeO 2 ) improved the catalyst activities through mechanisms of higher CO 2 adsorption capacity with its basic sites and the unique structure of CeO 2 with a reversible valence change of Ce 4+ and Ce 3+ and high oxygen vacancies. However, it was found that the catalyst prepared by microwave-assisted synthesis and Ce promotion proved to be the optimum catalyst in this study. Therefore, the present work demonstrated the potential to synthesize a nickel-based catalyst with improved catalytic activities by adding a small amount of Ce as a catalytic promoter and employing microwave irradiation for improving the Ni dispersion., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

To design safe and electrochemically stable electrolytes for lithium-ion batteries, this study describes the synthesis and the utilization of new deep eutectic solvents (DESs) based on the mixture of 2,2,2-trifluoroacetamide (TFA) with a lithium salt (LiTFSI, lithium bis[(trifluoromethane)sulfonyl]imide). These prepared DESs were characterized in terms of thermal properties, ionic conductivity, viscosity, and electrochemical properties. Based on the appearance of the product and DSC measurements, it appears that this system is liquid at room temperature for LiTFSI mole fraction ranging from 0.25 to 0.5. At χ LiTFSI = 0.25, DESs exhibited favorable electrolyte properties, such as thermal stability (up to 148 °C), relatively low viscosity (42.2 mPa.s at 30 °C), high ionic conductivity (1.5 mS.cm -1 at 30 °C), and quite large electrochemical stability window up to 4.9-5.3 V. With these interesting properties, selected DES was diluted with slight amount of ethylene carbonate (EC). Different amounts of EC ( x = 0-30 %wt) were used to form hybrid electrolytes for battery testing with high voltage LiMn 2 O 4 cathode and Li anode. The addition of the EC solvent into DES expectedly aims at enhancing the battery cycling performance at room temperature due to reducing the viscosity. Preliminary results tests clearly show that LiTFSI-based DES can be successfully introduced as an electrolyte in the lithium-ion batteries cell with a LiMn 2 O 4 cathode material. Among all of the studied electrolytes, DES (LiTFSI: TFA = 4:1 + 10 %wt EC) is the most promising. The EC-based system exhibited a good specific capacity of 102 mAh.g -1 at C/10 with the theoretical capacity of 148 mAh.g -1 and a good cycling behavior maintaining at 84% after 50 cycles., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Porous molecular crystals are an emerging class of porous materials that is unique in being built from discrete molecules rather than being polymeric in nature. In this study, we examined the effects of molecular structure of the precursors on the formation of porous solid-state structures with a series of 16 rigid aromatics. The majority of these precursors possess pyrazole groups capable of hydrogen bonding, as well as electron-rich aromatics and electron-poor tetrafluorobenzene rings. These precursors were prepared using a combination of Pd- and Cu-catalyzed cross-couplings, careful manipulations of protecting groups on the nitrogen atoms, and solvothermal syntheses. Our study varied the geometry and dimensions of precursors, as well as the presence of groups capable of hydrogen bonding and [π···π] stacking. Thirteen derivatives were crystallographically characterized, and four of them were found to be porous with surface areas between 283 and 1821 m 2 g -1 . Common to these four porous structures were (a) rigid trigonal geometry, (b) [π···π] stacking of electron-poor tetrafluorobenzenes with electron-rich pyrazoles or tetrazoles, and, ((c) hydrogen bonding between the terminal heteroaromatic rings.)

Rechargeable batteries based on an abundant metal such as aluminum with a three-electron transfer per atom are promising for large-scale electrochemical energy storage. Aluminum can be handled in air, thus offering superior safety, easy fabrication, and low cost. However, the development of Al-ion batteries has been challenging due to the difficulties in identifying suitable cathode materials. This study presents the use of a highly open framework Mo 2.5 +  y VO 9 +  z as a cathode for Al-ion batteries. The open-tunnel oxide allows a facile diffusion of the guest species and provides sufficient redox centers to help redistribute the charge within the local host lattice during the multivalent-ion insertion, thus leading to good rate capability with a specific capacity among the highest reported in the literature for Al-based batteries. This study also presents the use of Mo 2.5 +  y VO 9 +  z as a model host to develop a novel ultrafast technique for chemical insertion of Al ions into host structures. The microwave-assisted method employing diethylene glycol and aluminum diacetate (Al(OH)(C 2 H 3 O 2 ) 2 ) can be performed in air in as little as 30 min, which is far superior to the traditional chemical insertion techniques involving moisture-sensitive organometallic reagents. The Al-inserted Al x Mo 2.5 +  y VO 9 +  z obtained by the microwave-assisted chemical insertion can be used in Al-based rechargeable batteries., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Potassium has as rich an abundance as sodium in the earth, but the development of a K-ion battery is lagging behind because of the higher mass and larger ionic size of K + than that of Li + and Na + , which makes it difficult to identify a high-voltage and high-capacity intercalation cathode host. Here we propose a cyanoperovskite K x MnFe(CN) 6 (0 ≤ x ≤ 2) as a potassium cathode: high-spin Mn III /Mn II and low-spin Fe III /Fe II couples have similar energies and exhibit two close plateaus centered at 3.6 V; two active K + per formula unit enable a theoretical specific capacity of 156 mAh g -1 ; Mn and Fe are the two most-desired transition metals for electrodes because they are cheap and environmental friendly. As a powder prepared by an inexpensive precipitation method, the cathode delivers a specific capacity of 142 mAh g -1 . The observed voltage, capacity, and its low cost make it competitive in large-scale electricity storage applications.

Two mesoporous fluorinated metal-organic frameworks (MOFs) were synthesized from extensively fluorinated tritopic carboxylate- and tetrazolate-based ligands. The tetrazolate-based framework MOFF-5 has an accessible surface area of 2445 m(2) g(-1), the highest among fluorinated MOFs. Crystals of MOFF-5 adsorb hydrocarbons, fluorocarbons, and chlorofluorocarbons (CFCs)-the latter two being ozone-depleting substances and potent greenhouse species-with weight capacities of up to 225%. The material exhibits an apparent preference for the adsorption of non-spherical molecules, binding unusually low amounts of both tetrafluoromethane and sulfur hexafluoride., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Commonly used inhalation anesthetics-enflurane, isoflurane, sevoflurane, halothane, and methoxyflurane-are adsorbed within the pores of a porous fluorinated molecular crystal to the tune of up to 73.4(±0.2)% by weight. Uptake of all studied anesthetics is quite fast, typically reaching saturation in less than three minutes.

Atmospherically stable porous frameworks and materials are interesting for heterogeneous solid-gas applications. One motivation is the direct and selective uptake of pollutant/hazardous gases, where the material produces a measurable response in the presence of the analyte. In this report, we present a combined experimental and theoretical rationalization for the piezochromic response of a robust and porous molecular crystal built from an extensively fluorinated trispyrazole. The electronic response of the material is directly determined by analyte uptake, which provokes a subtle lattice contraction and an observable bathochromic shift in the optical absorption onset. Selectivity for fluorinated absorbates is demonstrated, and toluene is also found to crystallize within the pore. Furthermore, we demonstrate the application of electronic structure calculations to predict a physicochemical response, providing the foundations for the design of electronically tunable porous solids with the chemical properties required for development of novel gas-uptake media.

One of the enticing features of metal-organic frameworks (MOFs) is the potential to control the chemical and physical nature of the pores through postsynthetic modification. The incorporation of redox active guest molecules inside the pores of the framework represents one strategy toward improving the charge transport properties of MOFs. Herein, we report the vapor-phase redox intercalation of an electroactive organic compound, hydroquinone (H2Q) or benzene-1,4-diol, into the channels of the host [V(IV)O(bdc)], (bdc =1,4-benzenedicarboxylate) conventionally denoted as MIL-47. The temperatures and especially the atmosphere in which the reactions took place were found to determine the products. In ambient atmosphere, quinhydrone charge-transfer complexes are formed inside the channels. Under anhydrous conditions, the framework itself was functionalized by a radical anion species derived from the pyrolysis of hydroquinone. Both cases are accompanied by the reduction of V(4+) to V(3+) via single-crystal-to-single-crystal transformations. The products were characterized by single crystal X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and electron paramagnetic resonance spectroscopy.

Metal-organic and covalent organic frameworks are porous materials characterized by outstanding thermal stability, high porosities and modular synthesis. Their repeating structures offer a great degree of control over pore sizes, dimensions and surface properties. Similarly precise engineering at the nanoscale is difficult to achieve with discrete molecules, since they rarely crystallize as porous structures. Here we report a small organic molecule that organizes into a noncovalent organic framework with large empty pores. This structure is held together by a combination of [N-H···N] hydrogen bonds between the terminal pyrazole rings and [π···π] stacking between the electron-rich pyrazoles and electron-poor tetrafluorobenzenes. Such a synergistic arrangement makes this structure stable to at least 250 °C and porous, with an accessible surface area of 1,159 m(2) g(-1). Crystals of this framework adsorb hydrocarbons, CFCs and fluorocarbons-the latter two being ozone-depleting substances and potent greenhouse species-with weight capacities of up to 75%.

Mild solvothermal dehydration of 1,1'-ferrocenediboronic acid produces a triply ferrocene-bridged boroxine cyclophane. Its crystal structure reveals a rigid trigonal prism that presents a minimal boroxine-based covalent organic polyhedron (COP).