Pore Environmental Modification by Amino Groups in Robust Microporous MOFs for SF6 Capturing and SF6/N2 Separation.

Capturing and separating the greenhouse gas SF6 from nitrogen N2 have significant greenhouse mitigation potential and economic benefits. We used a pore engineering strategy to manipulate the pore environment of the metal-organic framework (MOF) by incorporating organic functional groups (-NH2). This resulted in an enhanced adsorption of SF6 and separation of the SF6/N2 mixture in the MOF. The introduction of amino (-NH2) groups into YTU-29 resulted in a reduction of the Brunauer-Emmett-Teller surface but an increase in interactions with SF6 within the confined pores. Water-stable YTU-29-NH2 showed a significantly higher SF6 uptake (95.5 cm3/g) than YTU-29 (77.4 cm3/g). The results of the breakthrough experiments show that YTU-29-NH2 has a significantly improved separation performance for SF6/N2 mixtures, with a high SF6 capture of 0.88 mmol/g compared to 0.56 mmol/g by YTU-29. This improvement is due to the suitable pore confinement and accessible -NH2 groups on pore surfaces. Considering its excellent regeneration ability and cycling performance, ultrastable YTU-29-NH2 demonstrates great potential for SF6 capturing and SF6/N2 separation.

Covalent Organic Frameworks Composites Containing Bipyridine Metal Complex for Oxygen Evolution and Methane Conversion.

Novel covalent organic framework (COF) composites containing a bipyridine multimetal complex were designed and obtained via the coordination interaction between bipyridine groups and metal ions. The obtained Pt and polyoxometalate (POM)-loaded COF complex (POM-Pt@COF-TB) exhibited excellent oxidation of methane. In addition, the resultant Co/Fe-based COF composites achieved great performance in an electrocatalytic oxygen evolution reaction (OER). Compared with Co-modified COFs (Co@COF-TB), the optimized bimetallic modified COF composites (Co0.75Fe0.25@COF-TB) exhibited great performance for electrocatalytic OER activity, showing a lower overpotential of 331 mV at 10 mA cm-2. Meanwhile, Co0.75Fe0.25@COF-TB also possessed a great turnover frequency (TOF) value (0.119 s-1) at the overpotential of 330 mV, which exhibited high efficiency in the utilization of metal atoms and was better than that of many reported COF-based OER electrocatalysts. This work provides a new perspective for the future coordination of COFs with bimetallic or polymetallic ions, and broadens the application of COFs in methane conversion and electrocatalytic oxygen evolution.

Hierarchical Porous and Three-Dimensional MXene/SiO2 Hybrid Aerogel through a Sol-Gel Approach for Lithium-Sulfur Batteries.

A unique porous material, namely, MXene/SiO2 hybrid aerogel, with a high surface area, was prepared via sol-gel and freeze-drying methods. The hierarchical porous hybrid aerogel possesses a three-dimensional integrated network structure of SiO2 cross-link with two-dimensional MXene; it is used not only as a scaffold to prepare sulfur-based cathode material, but also as an efficient functional separator to block the polysulfides shuttle. MXene/SiO2 hybrid aerogel as sulfur carrier exhibits good electrochemical performance, such as high discharge capacities (1007 mAh g-1 at 0.1 C) and stable cycling performance (823 mA h g-1 over 200 cycles at 0.5 C). Furthermore, the battery assembled with hybrid aerogel-modified separator remains at 623 mA h g-1 over 200 cycles at 0.5 C based on the conductive porous framework and abundant functional groups in hybrid aerogel. This work might provide further impetus to explore other applications of MXene-based composite aerogel.

Total Synthesis of the Proposed Microcyclamides MZ602 and MZ568.

The first convergent total synthesis for the proposed structures of microcyclamides MZ602 (1) and MZ568 (2) has been accomplished in 11 linear steps with 12.5 and 16.8% overall yield, respectively. Key features of the syntheses include a one-pot cascade reaction to construct core Boc-l-Ile-Thz-OAllyl fragment 5, and a removable pseudoproline (ΨMe,Me pro) inducer assisted cyclization of thiazole-containing all-l linear peptides. The spectral data (1H NMR, 13C NMR, and HRMS) of synthetic MZ602 (1) were quite similar to those of the proposed natural microcyclamide MZ602, except to an opposite sign of the optical rotation value. Surprisingly, the synthetic MZ568 (2) presented large discrepancies in characteristic spectral data from those of the reported natural product, although the absolute configuration of key intermediate 36 was unambiguously determined by single-crystal X-ray analysis in our work. These findings revealed that the proposed structures of natural microcyclamides MZ602 and MZ568 required revision.

A nanostructured porous carbon/MoO2 composite with efficient catalysis in polysulfide conversion for lithium-sulfur batteries.

Lithium-sulfur batteries are considered as the next generation of energy storage systems because of their high theoretical specific capacity and energy density. Unfortunately, the sluggish reaction kinetics, weak adsorption toward to lithium polysulfides, and slow lithium ion diffusion impede the smooth electrochemical process, resulting in the lithium-sulfur batteries with the unsatisfactory cycling stability and rate performance. Since it is recognized that polar metal oxides and doped nitrogen in carbon materials have chemical interaction with lithium polysulfides, a nanostructured nitrogen-doped porous carbon/MoO2 composite is synthesized through a simple hydrothermal method by using graphene oxide nanoribbon and phosphomolybdic acid hydrate as precursors. The porous nanostructure promotes the charge and mass transport, while MoO2 nanoparticles immobilize lithium polysulfides via strong chemisorption and enhance the redox kinetics of polysulfides owing to the efficient catalytic activity in liquid-solid boundary. Consequently, the as-obtained nanostructured porous carbon/MoO2-based sulfur cathode exhibits low polarization, high initial discharge capacity (1403 mAh g-1 at 0.1 C), good rate capabilities (584 mAh g-1 at 4 C), and impressive cycling performance at 1 C (503 mAh g-1 after 500 cycles with capacity fade rate of 0.07% per cycle).

Tuning Both Surface Chemistry and Porous Properties of Polymer-Derived Porous Carbons for High-Performance Gas Adsorption.

In this study, we have prepared novel pyrrole-formaldehyde polymers through polymerizing pyrrole and formaldehyde in the mixture solvent of water and ethanol by using hydrochloric acid as a catalyst. The as-synthesized polymers possess a nitrogen content of 6.7 atom % and are composed of spherical particles with the diameter of approximately 1-3 µm. A series of nitrogen-doped porous carbons with high specific surface areas (680-2340 m2 g-1) were successfully obtained through the activation treatment of the polymer spheres. The porous properties and surface chemistry of the as-prepared porous carbons are tuned by choosing different activating agents and changing the activation temperature. The morphology, porous properties, and chemical composition of the obtained nitrogen-doped porous carbons are revealed by various characterization methods, such as scanning electron microscopy, nitrogen sorption measurement, and X-ray photoelectron spectroscopy. The as-prepared nitrogen-doped porous carbons as gas adsorbents display high carbon dioxide uptake capacities of 3.80-5.81 mmol g-1 at 273 K and 1.0 bar. They also show excellent carbon dioxide adsorption capacities (2.40-3.37 mmol g-1 at 1.0 bar) and good gas selectivities (CO2/N2 selectivities of 16.9-70.2) at 298 K.

Effect of Porosity Parameters and Surface Chemistry on Carbon Dioxide Adsorption in Sulfur-Doped Porous Carbons.

In this work, a series of highly porous sulfur-doped carbons are prepared through physical activation methods by using polythiophene as a precursor. The morphology, structure, and physicochemical properties are revealed by a variety of characterization methods, such as scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and nitrogen sorption measurement. Their porosity parameters and chemical compositions can be well-tuned by changing the activating agents (steam and carbon dioxide) and reaction temperature. These sulfur-doped porous carbons possess specific surface area of 670-2210 m2 g-1, total pore volume of 0.31-1.26 cm3 g-1, and sulfur content of 0.6-4.9 atom %. The effect of porosity parameters and surface chemistry on carbon dioxide adsorption in sulfur-doped porous carbons is studied in detail. After a careful analysis of carbon dioxide uptake at different temperatures (273 and 293 K), pore volumes from small pore size (less than 1 nm) play an important role in carbon dioxide adsorption at 273 K, whereas surface chemistry is the key factor at a higher adsorption temperature or lower relative pressure. Furthermore, sulfur-doped porous carbons also possess good gas adsorption selectivity and excellent recyclability for regeneration.

Synthesis of Core-Shell Structured Porous Nitrogen-Doped Carbon@Silica Material via a Sol-Gel Method.

Core-shell structured nitrogen-doped porous carbon@silica material with uniform structure and morphology was synthesized via a sol-gel method. During this process, a commercial triblock copolymer and the in situ formed pyrrole-formaldehyde polymer acted as cotemplates, while tetraethyl orthosilicate acted as silica precursor. The synergetic effect of the triblock copolymer and the pyrrole-formaldehyde polymer enables the formation of the core-shell structure. Herein, the pyrrole-formaldehyde polymer acted as not only the template, but also the nitrogen-doped carbon precursor of the core. The obtained core-shell structured porous material possesses moderate Brunauer-Emmett-Teller specific surface area (410 m2 g-1) and pore volume (0.53 cm3 g-1). Moreover, corresponding hollow silica spheres or nitrogen-doped porous carbon spheres can be synthesized by calcining the core-shell structured material in air or etching it with HF. The X-ray photoelectron spectroscopy results reveal that the nitrogen states of the obtained material are mainly pyridinic-N and pyridonic-N/pyrrolic-N, which are beneficial for carbon dioxide adsorption. The carbon dioxide uptake capacity of the nitrogen-doped carbon spheres can reach 12.3 wt % at 273 K and 1.0 bar, meanwhile, the material shows good gas adsorption selectivities for CO2/CH4 and CO2/N2.

Nitrogen-doped graphene aerogel as both a sulfur host and an effective interlayer for high-performance lithium-sulfur batteries.

Lithium-sulfur batteries have attracted great concern because of the high theoretical capacity of sulfur (1675 mA h g-1). However, the poor electrical conductivity and volumetric expansion of sulfur along with the dissolution of lithium polysulfides largely limit their practical application. In this study, nitrogen-doped graphene aerogel (NGA) with high nitrogen content and porosity is used as a host for the impregnation of sulfur. The effects of sulfur impregnation on the specific surface area, pore volume, and microstructure of NGA supported sulfur composite (S@NGA) are well investigated. Furthermore, NGA is also processed into a NGA film, which is sandwiched between a separator and S@NGA cathode. The lithium-sulfur battery with such a configuration delivers a high reversible capacity of 1514 mA h g-1 at 0.1 C, excellent rate performance (822 mA h g-1 at 2.0 C), and good cycling stability (946 mA h g-1 at 0.5 C even after 100 cycles). The enhanced electrochemical performance can be ascribed to the introduction of the NGA interlayer, the unique interconnected porous structure, and strong interaction between the three-dimensional nitrogen-doped graphene network and the homogeneously dispersed sulfur and/or lithium polysulfides.

Preparation and characterization of a composite hydrogel with graphene oxide as an acid catalyst.

In this study, a facile method for synthesizing a novel graphene oxide/pyrrole-formaldehyde (GOP-1) composite hydrogel was developed via in situ polymerization of pyrrole and formaldehyde in the presence of graphene oxide sheets without any additional catalyst. During the polymerization, graphene oxide can act as a two-dimensional template to regulate the aggregation state of polymer and as an acid catalyst to accelerate the reaction rate of pyrrole and formaldehyde. The morphology and microstructure were investigated by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, respectively. The chemical properties were analyzed via X-ray photoelectron spectroscopy, infrared spectroscopy, and Raman spectroscopy. The freeze-dried GOP-1 composite hydrogel exhibited a large specific surface area, high nitrogen content, and three-dimensional network structure. Based on the above features, the freeze-dried GOP-1 composite hydrogel used as a gas adsorbent showed a high carbon dioxide uptake capacity at 1.0 bar and 273 K (11.1 wt%), in sharp contrast to that of graphene oxide (7.4 wt%). Furthermore, the as-prepared composite hydrogel may possess attractive potential in the fields of electrode material, tissue engineering, and water treatment.

Oxygen vacancy induced superior catalytic performance in Nd-Ce confined inside carbon nanotubes for N2O-assisted dehydrogenation of ethylbenzene.

Binary Nd-Ce oxides encapsuled in carbon nanotubes (CNTs) catalysts were synthesized and evaluated in the coupling reaction of ethylbenzene (EB) dehydrogenation and N2O decomposition, a promising strategy for styrene (ST) production while mitigating greenhouse gas emissions. The optimized Nd - Ce@CNTs exhibited competitive catalytic performance with an EB conversion of 76 % and a ST selectivity of 71 % compared to Ce@CNTs, highlighting a synergic effect between Ce and Nd in the oxidation dehydrogenation of EB with N2O as an oxidant (N2O-ODEB). Characterization results indicated that Nd incorporation induced lattice distortions, evident in the expansion or contraction of Ce - O bonds surrounding Nd. Defect densities increased to 1.381, 1.495 and 1.534 for CNTs, Ce@CNTs, and Nd - Ce@CNTs, respectively. This interaction not only facilitated the generation of oxygen vacancies, with a lower formation energy of oxygen vacancy on Nd - Ce@CNTs (2.13 eV) than that on Ce@CNTs (2.49 eV), thereby enhancing oxygen activation and migration, but also optimized the distribution of acid sites, promoting CH activation and EB dehydrogenation. In - situ diffuse reflectance infrared Fourier-transform spectra (DRIFTS) and density functional theory (DFT) calculations revealed that the lower adsorption energy of N2O (-1.84 eV) on Nd - Ce@CNTs suggested a more favorable coordinated configuration than Ce@CNTs (-0.90 eV), supported by stronger adsorption intensities at 1270 cm-1 and 1302 cm-1. Furthermore, the elongated NO bond (1.35 Å) of N2O on the Nd - Ce@CNTs surface indicated its greater ease of cleavage, providing active oxygen species that collectively contributed to the enhanced catalytic performance in the N2O-ODEB.

Vinyl-bearing sp2 carbon-conjugated covalent organic framework composites for enhanced electrochemical performance in hydrogen evolution reaction and lithium-sulfur batteries.

Vinyl-bearing triazine-functionalized covalent organic frameworks (COFs) have emerged as promising materials for electrocatalysis and energy storage. Guided by density functional theory calculations, a vinyl-enriched COF (VCOF-1) featuring a donor-acceptor structure was synthesized based on the Knoevenagel reaction. Moreover, the VCOF-1@Ru without pyrolysis was obtained through chemical coordination interactions between VCOF-1 and RuCl3, exhibiting enhanced electrocatalytic performance in the hydrogen evolution reaction when exposed to 0.5 M H2SO4. The results demonstrated that the protonation of VCOF-1@Ru enhanced the electrical conductivity and accelerated the generation of H2 on the catalytically active site Ru. Additionally, VCOF-1@CNT with a tubular structure was prepared by uniformly wrapping VCOF-1 onto carbon nanotubes (CNTs) and using it as a cathode for lithium-sulfur batteries by chemically and physically encapsulating S. The enhanced performance of VCOF-1@CNT was attributed to the effective suppression of lithium polysulfide migration. This suppression was achieved through several mechanisms, including the inverse vulcanization of vinyl on VCOF-1@CNT, the enhancement of material conductivity, and the interaction between N in the materials and Li ions. This study demonstrated a strategy for enhancing material performance by precisely modulating the COF structure at the molecular level.

Multi-functional carbon nanotube encapsulated by covalent organic frameworks for lithium-sulfur chemistry and photothermal electrocatalysis.

It is significant to tailor multifunctional electrode materials for storing sustainable energy in lithium-sulfur (Li-S) batteries and converting intermittent solar energy into H2, facilitated by electricity. In this context, COF-1@CNT obtained through interfacial interaction fulfilled both requisites via post-functionalization. Upon integrating COF-1@CNT with S as the cathode for Li-S batteries, the system exhibited an initial discharge capacity of 1360 mAh g-1. Subsequently, it maintained a sustained actual capacity even after undergoing 200 charge-discharge cycles at 0.5C. The performance improvement was attributed to the optimized conductivity due to the addition of carbon nanotubes (CNTs). Furthermore, the synergistic interaction between the nitrogen of COF-1 and lithium mitigated the shuttle effect in Li-S batteries. In the modified three-electrode electrolytic cell system, COF-1@CNT-Ru produced by COF-1@CNT with RuCl3 showed better electrochemical reactivity for photothermal-assisted hydrogen evolution reaction (HER). This effect was demonstrated by reducing the overpotential to 140 mV relative to the no-photothermal condition (180 mV) at a current density of 10 mA cm-2. This study marked the first simultaneous application of covalent organic frameworks (COFs) based materials in Li-S batteries and photothermal-assisted electrocatalysts. The modified electrocatalytic system held promise as a novel avenue for exploring solar thermal energy utilization.

Holey Ti3C2 MXene-Derived Anode Enables Boosted Kinetics in Lithium-Ion Capacitors.

Lithium-ion capacitors (LICs) attract enormous attention because of the urgent demands for high power and energy density devices. However, the intrinsic imbalance between anodes and cathodes with different charge-storage mechanisms blocks the further improvement in energy and power density. MXenes, novel two-dimensional materials with metallic conductivity, accordion-like structure, and regulable interlayer spacing, are widely employed in electrochemical energy storage devices. Herein, we propose a holey Ti3C2 MXene-derived composite (pTi3C2/C) with enhanced kinetics for LICs. This strategy effectively decreases the surface groups (-F and -O) and generates expanded interplanar spacing. The in-plane pores of Ti3C2Tx lead to increased active sites and accelerated lithium-ion diffusion kinetics. Benefiting from the expanded interplanar spacing and accelerated lithium-ion diffusion, the pTi3C2/C as an anode implements excellent electrochemical property (capacity retention about 80% after 2000 cycles). Furthermore, the LIC fabricated with a pTi3C2/C anode and an activated carbon cathode displays a maximum energy density of 110 Wh kg-1 and a considerable energy density of 71 Wh kg-1 at 4673 W kg-1. This work provides an effective strategy to achieve high antioxidant capability and boosted electrochemical properties, which represents a new exploration of structural design and tuneable surface chemistry for MXene in LICs.

Sulfonic acid functionalized covalent organic frameworks for lithium-sulfur battery separator and oxygen evolution electrocatalyst.

Covalent organic frameworks (COFs) are considered as a class of potential candidates for energy storage and catalysis. In this work, a COF containing sulfonic groups was prepared to be a modified separator in lithium-sulfur batteries (LSBs). Benefiting from the charged sulfonic groups, the COF-SO3 cell exhibited higher ionic conductivity (1.83 mS⋅cm-1). Moreover, the modified COF-SO3 separator not only inhibited the shuttle of polysulfide but also promoted Li+ diffusion, thanks to the electrostatic interaction. The COF-SO3 cell also showed excellent electrochemical performance that the initial specific capacity of the battery was 890 mA h g-1 at 0.5 C and demonstrated 631 mA h g-1 after 200 cycles. In addition, COF-SO3 with satisfactory electrical conductivity was also used as an electrocatalyst toward oxygen evolution reaction (OER) via cation-exchange strategy. The electrocatalyst COF-SO3@FeNi possessed a low overpotential (350 mV at 10 mA cm-2) in an alkaline aqueous electrolyte. Furthermore, COF-SO3@FeNi exhibited exceptional stability, and the overpotential increased about 11 mV at a current density of 10 mA cm-2 after 1000 cycles. This work facilitates the application of versatile COFs in the electrochemistry field.

Metalation of functionalized benzoquinoline-linked COFs for electrocatalytic oxygen reduction and lithium-sulfur batteries.

It is worthwhile to explore and develop multifunctional composites with unique advantages for energy conversion and utilization. Post-synthetic modification (PSM) strategies can endow novel properties to already excellent covalent organic frameworks (COFs). In this study, we prepared a range of COF-based composites via a multi-step PSM strategy. COF-Ph-OH was acquired by demethylation between anhydrous BBr3 and - OMe, and then, M@COF-Ph-OH was further obtained by forming the N - M - O structure. COF-Ph-OH exhibited a 2e--dominated oxygen reduction reaction (ORR) pathway with high H2O2 selectivity, while M@COF-Ph-OH exhibited a 4e--dominated ORR pathway with low H2O2 selectivity, which was due to the introduction of a metal salt with a d electron structure that facilitated the acquisition of electrons and changed the adsorption energy of the reaction intermediate (*OOH). It was proven that the d electron structure was effective at regulating the reaction pathway of the electrocatalytic ORR. Moreover, Co@COF-Ph-OH showed better 4e- ORR properties than Fe@COF-Ph-OH and Ni@COF-Ph-OH. In addition, compared with the other sulfur-impregnated COF-based composites examined in this study, S-Co@COF-Ph-OH had a larger initial capacity, a weaker impedance, and a stronger cycling durability in Li-S batteries, which was attributed to the unique porous structure ensuring high sulfur utilization, the loaded cobalt accelerating LiPS electrostatic adsorption and promoting LiPS catalytic conversion, and the benzoquinoline ring structure being ultra-stable. This work offers not only a rational and feasible strategy for the synthesis of multifunctional COF-based composites, but also promotes their application in electrochemistry.

Functionalized triazine-based covalent organic frameworks containing quinoline via aza-Diels-Alder reaction for enhanced lithium-sulfur batteries performance.

The development of functional covalent organic frameworks (COFs) with specific properties is an emerging research field. In the current work, COF-SQ-Ph was synthesized through the aza-Diels-Alder reaction between phenylacetylene and the matrix COF-SQ (triazine-based COF) generated from the organic monomers 2, 4, 6-tris(4-aminophenyl)-1, 3, 5-triazine and 2, 5-dimethoxyterephthalaldehyde in flask. The functionalized COF-SQ-Ph with an extended π-conjugated structure and enhanced structural stability was used as the sulfur loading recipient to prepare sulfur cathodes for lithium-sulfur batteries. Sulfur-impregnated COF-SQ-Ph marked as COF-SQ-Ph-S displayed better cycling stability with a specific capacity of 618 mA h g-1 after 150 cycles due to the lithiophilic interaction between lithium polysulfides and nitrogen atoms from quinoline and triazine moieties in COF-SQ-Ph-S. The functionalization of triazine-based COFs through a cycloaddition reaction in flask could promote the large-scale preparation of tailored COFs and the post-synthesis modification of COF-SQ.

Influences of pH and EDTA Additive on the Structure of Ni Films Electrodeposited by Using Bubble Templates as Electrocatalysts for Hydrogen Evolution Reaction.

The structure of Ni films is essential to their electrocatalytic performance for hydrogen evolution reaction (HER). The pH value and EDTA (ethylene diamine tetraacetic acid) additive are important factors for the structure control of electrodeposited metal films due to their adjustment of metal electrocrystallization and hydrogen evolution side reactions. The structures of Ni films from 3D (three-dimensional) porous to compact and flat structure are electrodeposited by adjusting solution pH values or adding EDTA. It is found that when pH value increases from 7.7 to 8.1, 3D porous films change to compact films with many protrusions. Further increasing the pH value or adding 0.1 M EDTA causes compact and flat films without protrusions to appear. When pH ≤ 7.7, hydrogen bubbles with large break-off diameter are easily adsorbed on film surface acting as porous structure templates, and the electroactive ion species, Ni2+ and Ni(NH3)n2+ complexes with low coordination number (n ≤ 3), possess high reduction overpotential, which is beneficial to forming protrusions and smaller particles. So, porous Ni films are electrodeposited. In solutions with pH ≥ 8.1 or 0.1 M EDTA, Ni(NH3)n2+ complexes with high coordination number (6 ≥ n ≥ 3) and hexadentate chelate are formed. Due to the improved wettability, bubbles with a small break-off diameter rapidly detach the film surface resulting in strong stirring. The reduction overpotential is reduced, leading to the formation of larger particles. Therefore, the solution leveling ability increases, and it is difficult to form protrusions, thus it forms a compact and flat film. The 3D porous film exhibits excellent catalytic performance for HER due to the large catalytic activity area.

Cationic covalent-organic framework for sulfur storage with high-performance in lithium-sulfur batteries.

Covalent organic frameworks (COFs) with pre-designed structure and customized properties have been employed as sulfur storage materials for lithium-sulfur (Li-S) batteries. In this work, a cationic mesoporous COF (COF-NI) was synthesized by grafting a quaternary ammonium salt group onto the pore channel of COFs via a one-pot three components tandem reaction strategy. The post-functionalized COFs were utilized as the matrix framework to successfully construct the Li-S battery with high-speed capacity and long-term stability. The experimental results showed that, after loading active material sulfur, cationic COF-NI effectively suppressed the shuttle effect of the intermediate lithium polysulfide species in Li-S batteries, and exhibited better cycle stability than the as-obtained neutral COF (COF-Bu). For example, compared with COF-Bu based sulfur cathode (521 mA h g-1), the cationic COF-NI based sulfur cathode maintained a discharge capacity of 758 mA h g-1 after 100 cycles. These results clearly showed that appropriate pore environment of COFs can be prepared by rational design, which can reduce the shuttle effect of lithium polysulfide species and improve the performance of Li-S battery.

Boosting the lithium storage performance of tin dioxide by carbon nanotubes supporting and surface engineering.

In order to reduce the negative impact of the extra carbon coating on the electrochemical properties of the commonly sandwiched carbon nanotubes@tin dioxide@carbon (CNT@SnO2@C) composites, the external C coating has been designed as a porous carbon in this work. The well-designed porous carbon coating offers an attractive advantage compared to the common carbon coatings, namely, it can not only better mitigate the volumetric variation of SnO2 by means of its spongy structure with better flexibility and rich free space, but also accelerate the lithium-ions diffusion by virtue of its open tunnel-like architecture. For this reason, this composite prepared here shows outstanding electrochemical performance stemming from the cooperative effect of inner CNT supporting and externally porous carbon coating, displaying 819.3 and 576.0 mAh g-1 at 200 and even 1000 mA g-1 after even 500 cycles, respectively. This surface engineering strategy may be valuable for enhancing the cyclical durability of other metal oxides with higher theoretical specific capacities.