Metal-organic frameworks bonded with metal N-heterocyclic carbenes for efficient catalysisOA

Metal N-heterocyclic carbenes(M-NHCs) on the pore walls of a porous metal-organic framework(MOF)can be used as active sites for efficient organic catalysis. Traditional approaches that need strong alkaline reagents or insoluble Ag₂O are not, however, suitable for the incorporation of NHCs on the backbones of MOFs because such reagents could destroy their frameworks or result in low reactivity. Accordingly,development of facile strategies toward functional MOFs with covalently bound M-...     

Metal-organic frameworks as effective sensors and scavengers for toxic environmental pollutants

Metal-organic frameworks (MOFs) constructed from a rich library of organic struts and metal ions/clusters represent promising candidates for a wide range of applications. The unique structure, porous nature, easy tunability and processability of these materials make them an outstanding class of materials for tackling serious global problems relating to energy and environment. Among them, environmental pollution is one aspect that has increased at an alarming rate in the past decade or so. With rapid urbanization and industrialization, toxic environmental pollutants are constantly released and accumulated leading to serious contamination in water bodies and thereby having adverse effects on human health. Recent studies have shown that many toxic pollutants, as listed by the World Health Organization and the US Environmental Protection Agency, can be selectively detected, captured, sequestered and removed by MOFs from air and aquatic systems. Most of these sensing/capture processes in MOFs are quantifiable and effective for even a trace amount of the targeted chemical species. The functional sites (ligands and metals) play a critical role in such recognition processes and offer an extensive scope of structural tunability for guest (pollutants, toxic entities) recognition. Whereas on the one hand, the underlying mechanisms governing such sensing and capture are important, it is also crucial to identify MOFs that are best suited for commercial applications for the future. In this review article, we provide an overview of the most recent progress in the sensing, capture and removal of various common toxic pollutants, including neutral and ionic, inorganic and organic species, with brief discussions on the mechanism and efficacy of selected MOFs.     

Cyclic-anion salt for high-voltage stable potassium-metal batteries

Electrolyte anions are critical for achieving high-voltage stable potassium-metal batteries (PMBs). However, the common anions cannot simultaneously prevent the formation of ‘dead K’ and the corrosion of Al current collector, resulting in poor cycling stability. Here, we demonstrate cyclic anion of hexafluoropropane-1,3-disulfonimide-based electrolytes that can mitigate the ‘dead K’ and remarkably enhance the high-voltage stability of PMBs. Particularly, even using low salt concentration (0.8 M) and additive-free carbonate-based electrolytes, the PMBs with a high-voltage polyanion cathode (4.4 V) also exhibit excellent cycling stability of 200 cycles with a good capacity retention of 83%. This noticeable electrochemical performance is due to the highly efficient passivation ability of the cyclic anions on both anode and cathode surfaces. This cyclic-anion-based electrolyte design strategy is also suitable for lithium and sodium-metal battery technologies.     

Integrated ‘all-in-one’ strategy to stabilize zinc anodes for high-performance zinc-ion batteries

Many optimization strategies have been employed to stabilize zinc anodes of zinc-ion batteries (ZIBs). Although these commonly used strategies can improve anode performance, they simultaneously induce specific issues. In this study, through the combination of structural design, interface modification, and electrolyte optimization, an ‘all-in-one’ (AIO) electrode was developed. Compared to the three-dimensional (3D) anode in routine liquid electrolytes, the new AIO electrode can greatly suppress gas evolution and the occurrence of side reactions induced by active water molecules, while retaining the merits of a 3D anode. Moreover, the integrated AIO strategy achieves a sufficient electrode/electrolyte interface contact area, so that the electrode can promote electron/ion transfer, and ensure a fast and complete redox reaction. As a result, it achieves excellent shelving-restoring ability (60 hours, four times) and 1200 cycles of long-term stability without apparent polarization. When paired with two common cathode materials used in ZIBs (α-MnO₂ and NH₄V₄O₁₀), full batteries with the AIO electrode demonstrate high capacity and good stability. The strategy of the ‘all-in-one’ architectural design is enlightened to solve the issues of zinc anodes in advanced Zn-based batteries.     

Hybrid solid electrolyte enabled dendrite-free Li anodes for high-performance quasi-solid-state lithium-oxygen batteries

The dendrite growth of Li anodes severely degrades the performance of lithium-oxygen (Li-O₂) batteries. Recently, hybrid solid electrolyte (HSE) has been regarded as one of the most promising routes to tackle this problem. However, before this is realized, the HSE needs to simultaneously satisfy contradictory requirements of high modulus and even, flexible contact with Li anode, while ensuring uniform Li⁺ distribution. To tackle this complex dilemma, here, an HSE with rigid Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) core@ultrathin flexible poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) shell interface has been developed. The introduced large amount of nanometer-sized LAGP cores can not only act as structural enhancer to achieve high Young''s modulus but can also construct Li⁺ diffusion network to homogenize Li⁺ distribution. The ultrathin flexible PVDF-HFP shell provides soft and stable contact between the rigid core and Li metal without affecting the Li⁺ distribution, meanwhile suppressing the reduction of LAGP induced by direct contact with Li metal. Thanks to these advantages, this ingenious HSE with ultra-high Young''s modulus of 25 GPa endows dendrite-free Li deposition even at a deposition capacity of 23.6 mAh. Moreover, with the successful inhibition of Li dendrites, the HSE-based quasi-solid-state Li-O₂ battery delivers a long cycling stability of 146 cycles, which is more than three times that of gel polymer electrolyte-based Li-O₂ battery. This new insight may serve as a starting point for further designing of HSE in Li-O₂ batteries, and can also be extended to various battery systems such as sodium-oxygen batteries.     

Hierarchically porous metal–organic frameworks: synthetic strategies and applications

Despite numerous advantages, applications of conventional microporous metal–organic frameworks (MOFs) are hampered by their limited pore sizes, such as in heterogeneous catalysis and guest delivery, which usually involve large molecules. Construction of hierarchically porous MOFs (HP-MOFs) is vital to achieve the controllable augmentation of MOF pore size to mesopores or even macropores, which can enhance the diffusion kinetics of guests and improve the storage capacity. This review article focuses on recent advances in the methodology of HP-MOF synthesis, covering preparation of HP-MOFs with intrinsic hierarchical pores, and modulated, templated and template-free synthetic strategies for HP-MOFs. The key factors which affect the formation of HP-MOF architectures are summarized and discussed, followed by a brief review of their applications in heterogeneous catalysis and guest encapsulation. Overall, this review presents a roadmap that will guide the future design and development of HP-MOF materials with molecular precision and mesoscopic complexity.     

A partially fluorinated ligand for two super-hydrophobic porous coordination polymers with classic structures and increased porosities

3-Ethyl-5-trifluoromethyl-1,2,4-triazole is synthesized by a one-pot reaction. Using this asymmetric triazole ligand bearing one trifluoromethyl and one ethyl as side groups, we construct two new porous coordination polymers, MAF-9 and MAF-2F, being isostructural with the classic hydrophobic and flexible materials, FMOF-1 and MAF-2, based on symmetric triazole ligands bearing two trifluoromethyl groups or two ethyl groups, respectively. MAF-9 and MAF-2F can adsorb large amounts of organic solvents but completely exclude water, showing superhydrophobicity with water contact angles of 152^o in between those of FMOF-1 and MAF-2. MAF-9 exhibits very large N₂-induced breathing and colossal positive and negative thermal expansions like FMOF-1, but the lower molecular weight and smaller volume of MAF-9 give 16% and 4% higher gravimetric and volumetric N₂ uptakes, respectively. In contrast, MAF-2F is quite rigid and does not show the inversed temperature-dependent N₂ adsorption and large guest-induced expansion like MAF-2. Further, despite the higher molecular weight and larger volume, MAF-2F possesses 6% and 25% higher gravimetric and volumetric CO₂ uptakes, respectively. These results can be explained by the different pore sizes and side group arrangements in the two classic framework prototypes, which demonstrate the delicate roles of ligand side groups in controlling porosity, surface characteristic and flexibility.     

Redox mediators for high-performance lithium–oxygen batteries

Aprotic lithium–oxygen (Li–O₂) batteries are receiving intense research interest by virtue of their ultra-high theoretical specific energy. However, current Li–O₂ batteries are suffering from severe barriers, such as sluggish reaction kinetics and undesired parasitic reactions. Recently, molecular catalysts, i.e. redox mediators (RMs), have been explored to catalyse the oxygen electrochemistry in Li–O₂ batteries and are regarded as an advanced solution. To fully unlock the capability of Li–O₂ batteries, an in-depth understanding of the catalytic mechanisms of RMs is necessary. In this review, we summarize the working principles of RMs and their selection criteria, highlight the recent significant progress of RMs and discuss the critical scientific and technical challenges on the design of efficient RMs for next-generation Li–O₂ batteries.     

Serrated lithium fluoride nanofibers-woven interlayer enables uniform lithium deposition for lithium-metal batteries

The uncontrollable formation of Li dendrites has become the biggest obstacle to the practical application of Li-metal anodes in high-energy rechargeable Li batteries. Herein, a unique LiF interlayer woven by millimeter-level, single-crystal and serrated LiF nanofibers (NFs) was designed to enable dendrite-free and highly efficient Li-metal deposition. This high-conductivity LiF interlayer can increase the Li⁺ transference number and induce the formation of ‘LiF–NFs-rich’ solid–electrolyte interface (SEI). In the ‘LiF–NFs-rich’ SEI, the ultra-long LiF nanofibers provide a continuously interfacial Li⁺ transport path. Moreover, the formed Li–LiF interface between Li-metal and SEI film renders low Li nucleation and high Li⁺ migration energy barriers, leading to uniform Li plating and stripping processes. As a result, steady charge–discharge in a Li//Li symmetrical cell for 1600 h under 4 mAh cm⁻² and 400 stable cycles under a high area capacity of 5.65 mAh cm⁻² in a high-loading Li//rGO–S cell at 17.9 mA cm⁻² could be achieved. The free-standing LiF–NFs interlayer exhibits superior advantages for commercial Li batteries and displays significant potential for expanding the applications in solid Li batteries.     

Dual-ligand and hard-soft-acid-base strategies to optimize metal-organic framework nanocrystals for stable electrochemical cycling performance

Most metal-organic frameworks (MOFs) hardly maintain their physical and chemical properties after exposure to acidic, neutral, or alkaline aqueous solutions, resulting in insufficient stability, therefore limiting their applications. Thus, the design and synthesis of stable size/morphology-controlled MOF nanocrystals is critical but challenging. In this study, dual-ligand and hard-soft-acid-base strategies were used to fabricate a variety of 3D pillared-layer [Ni(thiophene-2,5-dicarboxylate)(4,4^′-bipyridine)]_n MOF nanocrystals (1D nanofibers, 2D nanosheets and 3D aggregates) with controllable morphology by varying the concentration of 4,4^′-bipyridine and thus controlling the crystal growth direction. Owing to the shorter ion diffusion length, enhanced electron/ion transfer and strong interactions between thiophene-2,5-dicarboxylate and 4,4^′-bipyridine, the 2D nanosheets showed much larger specific capacitance than 1D nanofibers and 3D aggregates. A single device with an output voltage as high as 3.0 V and exceptional cycling performance (95% of retention after 5000 cycles at 3 mA cm^–2) was realized by configuring two aqueous asymmetric supercapacitive devices in series. The excellent cycling property and charge–discharge mechanism are consistent with the hard-soft-acid-base theory.     

Multielectron transportation of polyoxometalate-grafted metalloporphyrin coordination frameworks for selective CO2-to-CH4 photoconversion

Photocatalytic CO₂ reduction into energy carriers is of utmost importance due to the rising concentrations of CO₂ and the depleting energy resource. However, the highly selective generation of desirable hydrocarbon fuel, such as methane (CH₄), from CO₂ remains extremely challenging. Herein, we present two stable polyoxometalate-grafted metalloporphyrin coordination frameworks (POMCFs), which are constructed with reductive Zn-ϵ-Keggin clusters and photosensitive tetrakis(4-carboxylphenyl)porphyrin (H₂TCPP) linkers, exhibiting high selectivity (>96%) for CH₄ formation in a photocatalytic CO₂-reduction system. To our knowledge, the high CH₄ selectivity of POMCFs has surpassed all of the reported coordination-framework-based heterogeneous photocatalysts for CO₂-to-CH₄ conversion. Significantly, the introduction of a Zn-ϵ-keggin cluster with strong reducing ability is the important origin for POMCFs to obtain high photocatalytic selectivity for CH₄ formation, considering that eight Mo^V atoms can theoretically donate eight electrons to fulfill the multielectron reduction process of CO₂-to-CH₄ transformation.     

Sieving carbons promise practical anodes with extensible low-potential plateaus for sodium batteries

Non-graphitic carbons are promising anode candidates for sodium-ion batteries, while their variable and complicated microstructure severely limits the rational design of high-energy carbon anodes that could accelerate the commercialization of sodium-ion batteries, as is the case for graphite in lithium-ion batteries. Here, we propose sieving carbons, featuring highly tunable nanopores with tightened pore entrances, as high-energy anodes with extensible and reversible low-potential plateaus (<0.1 V). It is shown that the tightened pore entrance blocks the formation of the solid electrolyte interphase inside the nanopores and enables sodium clustering to produce the plateau. Theoretical and spectroscopic studies also show that creating a larger area of sodiophilic pore surface leads to an almost linearly increased number of sodium clusters, and controlling the pore body diameter guarantees the reversibility of sodium cluster formation, producing a sieving carbon anode with a record-high plateau capacity of 400 mAh g^–1. More excitingly, this approach to preparing sieving carbons has the potential to be scalable for modifying different commercial porous carbons.     

Molecular grafting towards high-fraction active nanodots implanted in N-doped carbon for sodium dual-ion batteries

Sodium-based dual-ion batteries (Na-DIBs) show a promising potential for large-scale energy storage applications due to the merits of environmental friendliness and low cost. However, Na-DIBs are generally subject to poor rate capability and cycling stability for the lack of suitable anodes to accommodate large Na⁺ ions. Herein, we propose a molecular grafting strategy to in situ synthesize tin pyrophosphate nanodots implanted in N-doped carbon matrix (SnP₂O₇@N-C), which exhibits a high fraction of active SnP₂O₇ up to 95.6 wt% and a low content of N-doped carbon (4.4 wt%) as the conductive framework. As a result, this anode delivers a high specific capacity ∼400 mAh g⁻¹ at 0.1 A g⁻¹, excellent rate capability up to 5.0 A g⁻¹ and excellent cycling stability with a capacity retention of 92% after 1200 cycles under a current density of 1.5 A g⁻¹. Further, pairing this anode with an environmentally friendly KS6 graphite cathode yields a SnP₂O₇@N-C||KS6 Na-DIB, exhibiting an excellent rate capability up to 30 C, good fast-charge/slow-discharge performance and long-term cycling life with a capacity retention of ∼96% after 1000 cycles at 20 C. This study provides a feasible strategy to develop high-performance anodes with high-fraction active materials for Na-based energy storage applications.     

Direct and green repairing of degraded LiCoO2 for reuse in lithium-ion batteries

Traditional recycling processes of LiCoO₂ rely on destructive decomposition, requiring high-temperature roasting or acid leaching to extract valuable Li and Co, which have significant environmental and economic concerns. Herein, a direct repairing method for degraded LiCoO₂ using a LiCl–CH₄N₂O deep eutectic solvent (DES) was established. The DES is not used to dissolve LiCoO₂ but directly serves as a carrier for the selective replenishment of lithium and cobalt. Replenishment of lithium restores LiCoO₂ at different states of charge to a capacity of 130 mAh/g (at 0.1 C rate), while replenishing the cobalt increases the capacity retention rate of 90% after 100 cycles, which is comparable to pristine LiCoO₂. The DES is collected and reused multiple times with a high repair efficiency. This process reduces energy consumption by 37.1% and greenhouse gas emissions by 34.8% compared with the current production process of LiCoO₂, demonstrating excellent environmental and economic viability.     

Anisotropic alignments of hierarchical Li2SiO3/TiO2 @nano-C anode//LiMnPO4@nano-C cathode architectures for full-cell lithium-ion battery

We report on low-cost fabrication and high-energy density of full-cell lithium-ion battery (LIB) models. Super-hierarchical electrode architectures of Li₂SiO₃/TiO₂@nano-carbon anode (LSO.TO@nano-C) and high-voltage olivine LiMnPO₄@nano-carbon cathode (LMPO@nano-C) are designed for half- and full-system LIB-CR2032 coin cell models. On the basis of primary architecture-power-driven LIB geometrics, the structure keys including three-dimensional (3D) modeling superhierarchy, multiscale micro/nano architectures and anisotropic surface heterogeneity affect the buildup design of anode/cathode LIB electrodes. Such hierarchical electrode surface topologies enable continuous in-/out-flow rates and fast transport pathways of Li⁺-ions during charge/discharge cycles. The stacked layer configurations of pouch LIB-types lead to excellent charge/discharge rate, and energy density of 237.6 Wh kg⁻¹. As the most promising LIB-configurations, the high specific energy density of hierarchical pouch battery systems may improve energy storage for long-driving range of electric vehicles. Indeed, the anisotropic alignments of hierarchical electrode architectures in the large-scale LIBs provide proof of excellent capacity storage and outstanding durability and cyclability. The full-system LIB-CR2032 coin cell models maintain high specific capacity of ∼89.8% within a long-term life period of 2000 cycles, and average Coulombic efficiency of 99.8% at 1C rate for future configuration of LIB manufacturing and commercialization challenges.