Metal-Organic Framework Confined Solvent Ionic Liquid Enables Long Cycling Life Quasi-Solid-State Lithium Battery in Wide Temperature Range.

Solid-state Li batteries are receiving increasing attention as a prospective energy storage system due to the high energy density and improved safety. However, the high interfacial resistance between solid-state electrolyte and electrode results in sluggish Li+ transport kinetics. To tackle the interfacial problem and prolong the cycle life of solid-state Li batteries, a quasi-solid-state electrolyte (QSSE) based on a solvate ionic liquid (SIL) space-restricted in nanocages of UIO-66 (SIL/UIO-66) is prepared in this study. Benefiting from the effective spatial confinement of the TFSI- by the pore UIO-66 and the strong chemical interactions between the SIL and metal atoms, SIL/UIO-66 QSSE exhibits high ionic conductivity and good compatibility with electrodes. As a result, Li|QSSE|LFP cells demonstrate excellent rate capability and cycle stability in a wide temperature range of 25-90 °C. This study provides a realistic strategy for the fabrication of safe solid electrolytes with excellent compatibility and long cycle life for high-performance QSSE Li-ion batteries.

Effects of electrostatic interaction on the properties of ionic liquids correlated with the change of free volume.

In this study, the amount of free volume in ionic liquids (ILs) was calculated and found to be almost half to that of their isoelectronic neutral analogues. MD simulations revealed that the significantly compressed free volume in the ILs was dominantly attributed to the strong inter-ion electrostatic interactions, which are comparable to the application of an external pressure of ∼250 MPa to the neutral analogues. Furthermore, the change in the free volume shows an interconnection with other properties of ILs, especially viscosity. The inherent high viscosity of ILs was quantitatively correlated to a low free volume available for mass transfer, and the sharp decrease in the viscosity of ILs with the addition of organic solvents was essentially caused by the introduction of free volume.

Hetero-Diatomic CoN4-NiN4 Site Pairs with Long-Range Coupling as Efficient Bifunctional Catalyst for Rechargeable Zn-Air Batteries.

In this study, Co/Ni-NC catalyst with hetero-diatomic Co/Ni active sites dispersed on nitrogen-doped carbon matrix is synthesized via the controlled pyrolysis of ZIF-8 containing Co2+ and Ni2+ compounds. Experimental characterizations and theoretical calculations reveal that Co and Ni are atomically and uniformly dispersed in pairs of CoN4-NiN4 with an intersite distance ≈0.41 nm, and there is long-range d-d coupling between Co and Ni with more electron delocalization for higher bifunctional activity. Besides, the in situ grown carbon nanotubes at the edges of the catalyst particles allow high electronic conductivity for electrocatalysis process. Electrochemical evaluations demonstrate the superior ORR and OER bifunctionality of Co/Ni-NC catalyst with a narrow potential gap of only 0.691 V and long-term durability, significantly prevailing over the single-atom Co-NC and Ni-NC catalysts and the benchmark Pt/C and RuO2 catalysts. Co/Ni-NC catalyzed Zn-air batteries achieve a high specific capacity of 771 mAh g-1 and a long continuous operation period up to 340 h with a small voltage gap of ≈0.65 V, also much superior to Pt/C-RuO2.

Mechanistic Insights into Formation of Residual Solid in Lignin Depolymerization.

Current techniques of lignin conversion are challenged by the low carbon utilization efficiency resulting from the severe generation of residual solid (char). Therefore, a better understanding of pathway for char formation is significant and highly desired for lignin valorization. In this work, we propose a fundamental mechanistic insight into char formation in lignin depolymerization, using hydrothermal decomposition as model reaction. The results demonstrate that the char featuring a multi-layer construction of coke and oligomer contains mainly G units, primarily generated from native G-lignin and demethoxylation of S-lignin. Instead, H-lignin contributes to the formation of volatile monophenols. Furthermore, new methylene bridges form between the benzene rings in lignin, which consequently results in the formation of recalcitrant char. Based on these observations, a plausible mechanism for char formation is proposed and verified by the density functional theory calculation.

Producing Methyl p-Coumarate from Herbaceous Lignin via a "Clip-Off" Strategy.

As the most abundant renewable aromatic resource on Earth, lignin is a preferred starting material for producing bulk chemicals via a sustainable route. In this study, we provide a novel and efficient "clip-off" approach for producing methyl p-coumarate, an important and versatile fine chemical by selective cleavage of the ester linkage in herbaceous lignin in the presence of commercial metal chlorides. When bagasse lignin was depolymerized at 155 °C for 4 h, a 12.7% yield of aromatic chemicals was obtained in the presence of CuCl2, 71.7% of which was identified as methyl p-coumarate (the yield was 9.1%). Further investigation of the structural evolution of lignin revealed that the ester linkages in lignin were efficiently broken via intensive transesterification with methanol accompanied by the simultaneous weakening of the inter-/intramolecular hydrogen bonds. Moreover, this observation of selective cleavage of ester linkages could be further confirmed by the conversion of model compounds with characteristic bonds under identical reaction conditions. Therefore, this work provides a new insight into the production of value-added chemicals from renewable resources.

Less is More: Trace Amount of a Cyclic Sulfate Electrolyte Additive Enable Ultra-Stable Graphite Anode for High-Performance Potassium-Ion Batteries.

Graphite can be successfully used as an anode for potassium-ion batteries (PIBs), while its conversion to KC8 leads to huge volume expansion, destruction of solid electrolyte interphase (SEI), and thus poor cycling stability. Incorporating additives into electrolytes is an economical and effective way to construct robust SEI for high-performance PIBs. Herein, we developed a series of sulfur-containing additives for PIB graphite anodes, and the impacts of their molecular structure and contents on the SEI are also systematically investigated. Compared with butylene sulfites and 1,3-propane sultone, the 1,3,2-dioxathiolane 2,2-dioxide (DTD) additive endows the graphite electrode (GE) with a higher reversible capacity, and better cycling stability in both the dilute potassium bis(fluorosulfonyl)imide (KFSI)- and potassium hexafluorophosphate (KPF6)-based carbonate electrolyte, as a result of a thinner and sulfate-enriched SEI. Moreover, the addition of a trace amount (0.2 wt %) DTD to the electrolyte can effectively protect the GE running over 800 cycles at 1 C. Excessive additives in the electrolyte will induce continuous SEI growth and render a rapid capacity fading of the GE. This strategy using the electrolyte additive paves the way for the design of novel PIB electrolytes and thus provides a great opportunity for commercial PIBs.

Inorganic crosslinked supramolecular binder with fast Self-Healing for high performance silicon based anodes in Lithium-Ion batteries.

Capacity retention is one of the key factors affecting the performance of silicon (Si)-based lithium-ion batteries and other energy storage devices. Herein, a three dimension (3D) network self-healing binder (denoted as PVA + LB) consisting of polyvinyl alcohol (PVA) and lithium metaborate (LiBO2) solution is proposed to improve the cycle stability of Si-based lithium-ion batteries. The reversible capacity of the silicon electrode is maintained at 1767.3 mAh g-1 after 180 cycles when employing PVA + LB as the binder, exhibiting excellent cycling stability. In addition, the silicon/carbon (Si/C) anode with the PVA + LB binder presents superior electrochemical performance, achieving a stable cycle life with a capacity retention of 73.7% (858.3 mAh g-1) after 800 cycles at a current density of 1 A g-1. The high viscosity and flexibility, 3D network structure, and self-healing characteristics of the PVA + LB binder are the main reasons to improve the stability of the Si or Si/C contained electrodes. The novel self-healing binder shows great potential in designing the new generation of silicon-based lithium-ion batteries and even electrochemical energy storage devices.

Ultrasonication-assisted synthesis of alcohol-based deep eutectic solvents for extraction of active compounds from ginger.

An ultrasonication-assisted synthesis of alcohol-based deep eutectic solvents (DESs) is described. Several DESs were synthesized simultaneously under the same conditions. The prepared DESs were used for the extraction of gingerols from ginger powder via ultrasonication-assisted extraction. Notably, some of the prepared DESs exhibited superior extraction performance than those in traditional organic solvents. The viscosity of the DESs, which was suggested to be typically lower than 100 mPa*s had a critical effect on extraction performance. However, the higher gingerol contents in the extracts did not translate to higher active antioxidant abilities. The extraction temperature was found to be a key determinant of the antioxidant capability of the extracted gingerols while the use of higher temperatures (>50 °C) induced degradation and loss of phenolic compounds during extraction. Response surface methodology was applied for determining the optimal extraction conditions to achieve maximum antioxidant capacity with suitable gingerol content. All compounds used for the preparation of the DESs in this study have been widely employed in cosmetic and pharmaceutical fields. Therefore, the extracts in these DES solutions can be considered for direct application development without further product isolation.

Novel cyclic sulfonium-based ionic liquids: synthesis, characterization, and physicochemical properties.

A new series of ionic liquids composed of three cyclic sulfonium cations and four anions has been synthesized and characterized. Their physicochemical properties, including their spectroscopic characteristics, ion cluster behavior, surface properties, phase transitions, thermal stability, density, viscosity, refractive index, tribological properties, ion conductivity, and electrochemical window have been comprehensively studied. Eight of these salts are liquids at room temperature, at which some salts based on [NO(3)](-) and [NTf(2)](-) ions exhibit organic plastic crystal behaviors, and all the saccharin-based salts display relatively high refractive indices (1.442-1.594). In addition, some ionic liquids with the [NTf(2)](-) ion exhibit peculiar spectroscopic characteristics in FTIR and UV/Vis regions, whilst those salts based on the [DCA](-) ion show lower viscosities (34.2-62.6 mPa s at 20 degrees C) and much higher conductivities (7.6-17.6 mS cm(-1) at 20 degrees C) than most traditional 1,3-dialkylimidazolium salts.

Novel chemoselective hydrogenation of aromatic nitro compounds over ferric hydroxide supported nanocluster gold in the presence of CO and H2O.

Chemoselective hydrogenation of aromatic nitro compounds were first efficiently achieved over Au/Fe(OH)(x) at 100-120 degrees C for 1.5-6 h (depending on different substrates) in the presence of CO and H(2)O.

In Situ Self-Assembly of Ultrastable Gold Nanoparticles on Polyvinyl Alcohol Nanofibrous Mats for Use as Highly Reusable Catalysts.

Designing highly stable and reusable catalytic systems based on Au nanoparticles (NPs) is a significant challenge in nanocatalysis research. Here, we have fabricated polyvinyl alcohol (PVA) nanofibrous mat/Au NP composite catalysts with NPs in uniform size and good distribution by use of a developed in situ growth approach. In this method, Au seeds were first adsorbed on PVA nanofibrous mat surfaces rather than on relatively large Au NPs and then used to grow NPs in Au seed solution; thus, the steric hindrance effect was alleviated and a high loading was used for Au NPs up to 11 wt %. Strong interfacial interactions between the Au NPs and the PVA nanofibrous mats due to introducing a large number of hydrogen bonds provide high thermal stability for the PVA side chains, long-term catalytic stability, and excellent reusability. Consequently, the proposed in situ grown PVA/Au NP nanofibrous mats produce high catalytic activity for at least 15 cycles over a 30 d period. This work provides a potential approach for fabricating highly stable and reusable metal NPs on polymer nanofibrous mats to facilitate a wide variety of applications.

Correction to "In Situ Self-Assembly of Ultrastable Gold Nanoparticles on Polyvinyl Alcohol Nanofibrous Mats for Use as Highly Reusable Catalysts".

[This corrects the article DOI: 10.1021/acsomega.9b03436.].

Catalytic conversion of duckweed to methyl levulinate in the presence of acidic ionic liquids.

In this study, an efficient strategy is proposed for selective methyl levulinate production from duckweed, a typical fast-growing aquatic microalgae in warm and humid regions, in the presence of acidic ionic liquids (ILs). The results show that IL structure has a significant effect on its acidic strength, which finally determines the process efficiency for levulinate methyl generation. With the optimized catalyst of [C3H6SO3HPy]HSO4, 88.0% duckweed is consumed, resulting in a comparable methyl levulinate yield of 73.7% and a process efficiency of 81.8% at 170 °C for 5 h. Furthermore, this process is substantially influenced by the reaction condition, particularly, it is significantly temperature-dependent. In addition, solvent has a remarkable intensified effect on the process efficiency, which dramatically decreases from 81.8 to 53.7% when methanol is replaced by water.

Organosolv liquefaction of sugarcane bagasse catalyzed by acidic ionic liquids.

An efficient and eco-friendly process is proposed for sugarcane bagasse liquefaction under mild condition using IL catalyst and environmental friendly solvent of ethanol/H2O. The relationship between IL acidic strength and its catalytic performance is investigated. The effects of reaction condition parameters such as catalyst dosage, temperature, time and solvent are also intensively studied. The results show that ethanol/H2O has a significant promotion effect on the simultaneous liquefaction of sugarcane bagasse carbohydrate and lignin. 97.5% of the bagasse can be liquefied with 66.46% of volatile product yield at 200°C for 30min. Furthermore, the IL catalyst shows good recyclability where no significant loss of the catalytic activity is exhibited even after five runs.

Protic-salt-derived nitrogen/sulfur-codoped mesoporous carbon for the oxygen reduction reaction and supercapacitors.

Nitrogen/sulfur-co-doped mesoporous carbon (Phen-HS) was obtained through direct carbonization of a single protic salt, that is, 1,10-phenanthrolinium dibisulfate ([Phen][2 HSO4 ]), in the presence of a colloidal silica template without the use of additional acid or metal catalysts for prepolymerization prior to carbonization. Phen-HS was prepared in a relatively high yield (30.0 %) and has a large surface area (1161 m(2) g(-1) ), large pore volume (2.490 cm(3) g(-1) ), large mesopores (≈12 nm), narrow pore-size distribution (7-16 nm), and high nitrogen (7.5 at %) and sulfur (1.3 at %) contents. The surface area/pore-size distribution is much higher/narrower than that of most reported carbon materials obtained from traditional precursors by using the same template. Phen-HS was directly used as an electrocatalyst for the oxygen reduction reaction (ORR) and as an electrode material for supercapacitors. As an efficient metal-free catalyst, Phen-HS exhibited good electrocatalytic activity toward the ORR in a 0.1 M KOH aqueous solution, which is comparable to the activity of a commercial Pt/C catalyst. Electrochemical measurements for Phen-HS used in a double-layer capacitor showed high specific capacitances of 160 and 140 F g(-1) in 1 M H2 SO4 and 6 M KOH, respectively, with good rate capabilities and high cycling stabilities.

The effect of procyanidine crosslinking on the properties of the electrospun gelatin membranes.

In this study, the effect of different crosslinkers including glutaraldehyde (GTA), genipin (GIP) and procyanidine (PA) on the properties of the electrospun gelatin membranes was compared. The water-resistant ability of the membranes could be significantly improved after being crosslinked with PA at T > 40 °C. In contrast with GTA and GIP, the PA-crosslinking process did not apparently affect the fibrous structure, and induced the lowest shrinkage of the membranes. At the concentration of 5% of PA, the ultimate tensile strength and elongation of the hydrated membrane were 0.87 MPa and 148%, respectively, which were higher than those of the GIP-crosslinked counterparts. In addition, the PA-crosslinked membranes displayed the highest resistance to pepsin degradation, and fibroblast cells could migrate deeper into the interior of the membranes due to the good preservation of the fibrous structure during the cell culture process.