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Binder-free Integration of Bismuth Nanoflakes onto Nickel Foams for Sodium-ion Batteries

A new type of bismuth-based electrode material for sodium-ion batteries has been synthesized. This electrode consists of bismuth metal nanoflakes seamlessly integrated onto nickel foams. The electrode contains no polymer binders, a crucial component required to retain the structural integrity of most battery electrodes. This binder-free feature improves the amount of charge being stored (i.e. capacity) at fast charging rates.

Sodium-ion batteries are attracting worldwide research efforts as electric energy storage devices, in addition to the prevalent lithium-ion batteries, due to the abundance of sodium. Similar to the preparation of other battery electrodes, fabricating sodium-ion battery electrodes generally requires binders, e.g. polyvinylidene fluoride (PVDF), to hold powdered electrode materials together and glue them to metal supporting substrates. However, the electrically insulating nature of the binders impedes fast electron transport between electrode materials and supporting substrates, consequently degrading the capacity of the batteries at fast charging rates.

Now in ChemComm, researchers from Nankai University & the Collaborative Innovation Center of Chemical Science and Engineering in China demonstrate a bismuth-based electrode material that does not involve a binder. This characteristic is realized by the in-situ growth of bismuth nanoflakes onto nickel foams through a solution-based replacement reaction (Figure 1). Because the nanoflakes grow directly from the nickel foam surface and firmly anchor onto nickel (Figure 2a), the resultant Bi/Ni composite can be directly used as an electrode. Specifically, the bismuth nanoflakes and nickel foam serve as the active material and supporting substrate, respectively.

The Bi/Ni composite exhibited excellent electrochemical performance. It achieved a high capacity of 377.1 mAh/g at a current density of 20 mA/g. Significantly, when the current density increased 100-fold, its capacity could still retain 206.4 mAh/g, which is more than half of the capacity obtained at 20 mA/g (Figure 2b). This outstanding capacity retention is a benefit of the binder-free characteristic that reduces the resistance of electron transport.

The authors then elucidated the working mechanism of the bismuth nanoflakes by in-situ Raman spectroscopy. They concluded that a two-step alloying process was responsible for the charge storage activity.

Figure 1. A schematic illustration showing the synthetic process of the binder-free Bi/Ni electrode. By inserting a piece of nickel foam into an ethylene glycol (EG) solution containing bismuth(III) nitrate, Bi3+ can replace Ni metal, be reduced to Bi metal and deposit on the Ni metal surface.

 

Figure 2. (a) A scanning electron microscopy image of the bismuth nanoflakes. (b) A plot showing the capacity of the Bi/Ni electrode at different current densities.

 

The successful synthesis of the binder-free electrode is expected to encourage future works on the design and synthesis of integrated electrode materials to advance the performance of sodium-ion batteries.

 

To find out more please read:

In situ Synthesis of Bi Nanoflakes on Ni Foam for Sodium-ion Batteries

Liubin Wang, Chenchen Wang, Fujun Li, Fangyi Cheng and Jun Chen

Chem. Commun. 2017, DOI: 10.1039/c7cc08341f

About the blogger:

Tianyu Liu obtained his Ph.D. in Physical Chemistry from University of California, Santa Cruz in United States. He is passionate about scientific communication to introduce cutting-edge research to both the general public and scientists with diverse research expertise. He is a web blog writer for Chem. Commun. and Chem. Sci. More information about him can be found at http://liutianyuresearch.weebly.com/.

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Creating Defects to Enhance Oxygen Evolution Activity: A Case Study using CoFe Layered Double Hydroxides

A group of scientists recently made a breakthrough in promoting the oxygen evolution activity of metal hydroxides. They developed a simple yet efficient strategy of immersing the metal hydroxides in diluted acid solutions.

The oxygen evolution reaction (OER) is a critical component for solar-driven water splitting that can sustainably acquire a clean fuel hydrogen gas by solar energy. Certain noble metal oxides, such as iridium dioxide (IrO2) and ruthenium dioxide (RuO2), work extremely well for catalyzing OERs. However, their scarcity restricts their potential for large-scale applications. To address the cost bottleneck, inexpensive alternatives such as metal hydroxides are being investigated worldwide. Unfortunately, their performance cannot compete with IrO2 or RuO2, partly due to their limited active sites for oxygen evolution. As such, there is a current need to develop strategies to promote the oxygen evolution activity of these metal hydroxides.

Figure 1. A schematic illustration showing the structural change of CoFe layered double hydroxide after being immersed in diluted nitric acid. Acid soaking creates Fe, Co and O defects (represented by VFe, VCo, and VO in the illustration, respectively) as well as separating the hydroxide layers.

Recently, Zhou et al. from Hunan University and Shenzhen University in China, demonstrated an easy acid-etching method that is capable of significantly improving the oxygen evolution activity of CoFe layered double hydroxide. When the hydroxide comes into contact with the nitric acid, protons remove some Co, Fe and O atoms and leave behind vacancies. These vacancies are named defects (Figure 2). Oxygen gas prefers to evolve at these defects and thus the defective hydroxide exhibits improved oxygen evolution activity. In addition, the nitrate anions can intercalate in between the metal hydroxide layers and break adjacent layers apart, exposing a large number of defect-containing surfaces and thus further boosting the oxygen evolution activity (Figure 1).

Figure 2. Transmission electron microscopy images of untreated CoFe layered double hydroxide (a, b) and acid-etched CoFe layered double hydroxide (c, d). After etching, the hydroxide nanoplates crack (due to layer separation) and surfaces become rough (due to creation of defects).

This method is expected to be applicable for a wide range of other metal hydroxides. The simplicity and efficiency of this method could make oxygen evolution catalysts cost-effective for commercialization.

 

To find out more please read:

Acid-etched Layered Double Hydroxides with Rich Defects for Enhancing the Oxygen Evolution Reaction

Peng Zhou, Yanyong Wang, Chao Xie, Chen Chen, Hanwen Liu, Ru Chen, Jia Huo and Shuangyin Wang

Chem. Commun. 2017, 53, 11778-11781

About the blogger:

Tianyu Liu obtained his Ph.D. in Physical Chemistry from University of California, Santa Cruz in United States. He is passionate about scientific communication to introduce cutting-edge research to both the general public and scientists with diverse research expertise. He is an online blog writer for Chem. Commun. and Chem. Sci. More information about him can be found at http://liutianyuresearch.weebly.com/.

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Desalinating Seawater with Carbon “Sandwiches”

A joint group of scientists from China, Japan and Australia recently made a breakthrough in water desalination. They designed and synthesized a multilayered electrode consisting of a graphene nanosheet sandwiched between two porous carbon particle layers. This “sandwich” electrode can be used for capacitive desalination to produce fresh water from seawater, and exhibited the highest desalination capacity among the reported graphene sheet-based electrodes.

Capacitive desalination is an emerging water desalination technique. It removes water-soluble salts, mostly sodium chloride, by applying an electric field to move the salts to the surface of electrodes. Because the amount of ions being removed is directly proportional to the surface area of the electrodes, using electrodes with abundant surface to electro-adsorb ions is critical for excellent desalination performance.

The researchers utilized graphene oxide (GO) and zeolitic imidazolate framework-8 (ZIF-8, a metal organic framework) as the two components (Figure 1a). When dissolved in water, ZIF-8 nanocrystals became attached to the surface of GO and completely covered both sides of the GO nanosheets. This process was driven by the coordination interaction between the two species. The formed ZIF-8/GO/ZIF-8 “sandwiches” were then annealed at near 1000 oC in nitrogen gas. The annealing step converted GO nanosheets and ZIF-8 nanocrystals into graphene nanosheets and porous carbon particle layers, respectively. Owing to the presence of pores on the surface of the yielded carbon particles, the carbon “sandwiches” had a high surface area of 1360 m2/g, much higher than that of the graphene sheets alone (150 m2/g).

Figure 1. (a) A schematic diagram displaying the key steps for the synthesis of the carbon “sandwiched” electrodes. 2-MeIM = 2-methylimidazole, a building block for ZIF-8. (b) The change of NaCl concentration collected for a “sandwiched” electrode (NC/rGO) and a graphene sheet electrode (rGO). When an electric field is applied, the concentration of NaCl starts to drop and reaches a plateau; When the electric field dissipates, the concentration of NaCl returns to its initial level. The salt concentration decreased to a much lower level with NC/rGO (red curve) than rGO (black curve).

The desalination capacity of the carbon “sandwich” reaches 17.52 mg/g, meaning 1 gram of the electrode can remove 17.52 mg of sodium chloride. Consistent with the enhanced surface area, the capacity of the “sandwich” is much higher than that of the graphene alone (Figure 1b). More significantly, the “sandwich” electrode outperforms all other previously reported graphene sheet-based electrodes in terms of the desalination capacity.

This work has greatly advanced the development of capacitive desalination, a promising and affordable technique to mass produce fresh water by desalting seawater.

To find out more please read:

High Performance Capacitive Deionization Electrodes Based on Ultrathin Nitrogen-doped Carbon/graphene Nano-Sandwiches

Miao Wang, Xingtao Xu, Jing Tang, Shujin Hou, Md. Shahriar A. Hossain, Likun Pan and Yusuke Yamauchi

Chem. Commun. 2017, 53, 10784-10787

About the blogger:

Tianyu Liu is a Ph.D. in chemistry graduated from University of California, Santa Cruz in United States. He is passionate about scientific communication to introduce cutting-edge researches to both the general public and the scientists with diverse research expertise. He is a web blogger for the Chem. Commun. and Chem. Sci. blog websites. More information about him can be found at http://liutianyuresearch.weebly.com/.

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Synthesis of Tin Dioxide Nanotubes for Lithium-ion Batteries with “A Grain of Oxalate Salt”

Preparation of tube-shaped electrode materials for lithium-ion batteries is a trending topic. Tubes with hollow cylindrical bodies allow exposure of the electrodes’ interior surface and can accommodate the large volumetric expansion commonly observed when lithium ions diffuse (either via intercalation or alloying) into the electrodes. The aforementioned two characteristics improve the specific capacity (a measure of how much electric energy one electrode can hold) and lifetime of electrodes.

Recently, the Mai research group from Wuhan University of Technology, China demonstrated a straightforward method for the synthesis of tin dioxide nanotubes as high-performance anodes for lithium-ion batteries. They adopted manganese(III) oxyhydroxide (MnOOH) nanowires as the sacrificial templates and immersed them in a batch of aqueous solutions containing tin(II) cations and oxalate anions (C2O42-). Afterwards, they warmed the mixture at 60 oC under constant magnetic stirring for 4 h and collected a white precipitate consisting of tin dioxide nanotubes. These nanotubes were then washed and coated with carbon thin films to improve their electrical conductivity and structural stability before being subjected to performance evaluations.

The presence of oxalate anions was crucial for producing the nanotubes with a well-defined shape. The function of these anions was revealed through a series of experiments. Oxalate anions first reduced MnOOH to manganese(II) cations and consumed protons in the vicinity of the MnOOH surface. The consumption of local protons increased the local pH and triggered precipitation and oxidation (by dissolved oxygen) of Sn2+ to tin dioxide. The two reactions proceeded, and eventually the MnOOH nanowires disappeared but tubes of tin dioxide formed around their surfaces (Figure 1). Samples obtained without oxalate salts were irregularly shaped.

Figure 1. (a) The schematic illustration of the synthesis steps of the tin dioxide nanotubes. (b) Scanning electron microscopy and (c) transmission electron microscopy images of the as-prepared tin dioxide nanotubes.

The carbon-coated tin dioxide nanotubes showed superior stability performance to bare tin dioxide nanotubes, as shown from the slower capacity-fading rate depicted in Figure 2a. In addition, carbon coating did not significantly sacrifice nanotubes’ charge-storage performance as both electrodes with and without a coating exhibited comparable capacity at all tested current densities (Figure 2b).

Figure 2. Performance comparison between carbon-coated tin dioxide nanotubes (SnO2@C NTs) and bare tin dioxide nanotubes (SnO2 NTs): (a) long-term stability and (b) capacity achieved at different current densities and charge-discharge cycle numbers.

To find out more please read:

Oxalate-assisted Formation of Uniform Carbon-confined SnO2 Nanotubes with Enhanced Lithium Storage

Chunhua Han, Baoxuan Zhang, Kangning Zhao, Jiashen Meng, Qiu He, Pan He, Wei Yang, Qi Li and Liqiang Mai

DOI: 10.1039/c7cc05406h

About the blogger:

Tianyu Liu is a Ph.D. in chemistry graduated from University of California, Santa Cruz in United States. He is passionate about scientific communication to introduce cutting-edge researches to both the general public and the scientists with diverse research expertise. He is a web blogger for the Chem. Commun. and Chem. Sci. blog websites. More information about him can be found at http://liutianyuresearch.weebly.com/.

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Janus Particle Chains that Can Rotate, Dissipate and Recombine

Janus is a god in ancient Roman mythology with two opposing faces. Its name has been brought to materials science to label particles with two or more distinct faces as “Janus particles”. Integrating multiple functions into one physical entity, Janus particles with various properties are extensively adopted as catalysts, electronic components and other applications.

Reporting in Chemical Communications, Bart Jan Ravoo and co-workers from Westfälische Wilhelms-Universität Münster in Germany developed a Janus particle colloidal assembly using a sandwich micro-contact printing method, a strategy reported previously by the same group. The Janus particle assembly consists of Janus particle chains, with the structure of one chain illustrated in Figure 1b. The authors first capped a batch of silica micro-beads with tri-block co-polymers on opposing ends (green parts shown in Figure 1). These copolymers serve as arms that extend and attach to functionalized magnetite (Fe3O4) nanoparticles. Two Janus particles will become magnetically glued together if they connect to the same nanoparticle at the two caps. This connection propagates and eventually forms Janus particle chains mainly consisting of two to four particles.

Figure 1. The schematic illustration depicting the structure of a Janus particle chain.

The artificial chains are responsive to an external magnetic field and photons with different wavelengths. Owing to the magnetic nanoparticles, the chains tend to arrange themselves according to the direction of the applied magnetic field. As shown in Figure 2a, the authors successfully rotated a chain by moving around a magnet.

Moreover, radiating the chains using UV light and green visible light will alter the chain configuration. The light sensitivity is rooted in a light-induced isomerization reaction of the co-polymer linkers: green light yields adhesive trans-isomers, whereas UV light produces cis-isomers that detach from magnetite. Hence, dissipation of the chains into individual Janus particles and then rejoining the particles together can be readily accomplished (Figure 2b).

Figure 2. Optical microscopy images showing (a) the magnetic and (b) the photo-switching properties of one Janus particle chain. All scale bars are 10 µm.

The demonstrated assembly is just the tip of the iceberg for Janus particle assemblies. As claimed by the authors, any acrylate in principal can be used to build the co-polymer linkers, resulting in colloidal assemblies with versatile features.

To find out more please read:

Self-assembly of Colloidal Molecules that Respond to Light and a Magnetic Field

Sven Sagebiel, Lucas Stricker, Sabrina Engel and Bart Jan Ravoo

DOI: 10.1039/c7cc04594h

About the blogger:

Tianyu Liu is a Ph.D. in chemistry graduated from University of California-Santa Cruz. He is passionate about scientific communication to introduce cutting-edge researches to both the general public and the scientists with diverse research expertise. He is a web writer for the Chem. Commun. and Chem. Sci. blog websites. More information about him can be found here.

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Elucidating the Stability of Two Metal-Organic Frameworks toward Carbon Dioxide Sorption: A Comparative Study

Metal-organic frameworks (MOFs) are coordination networks consisting of organic ligands and metal cores. They possess crystalline structures with metal complexes as the basic building blocks. These complexes assemble together and extend periodically to form the MOF structures. MOFs represent a family of highly porous materials with ultrahigh surface area (typically >1000 m2 g-1). Other attractive characteristics for MOFs are abundant active metal cores and unique porous structures with tunable pore width, useful for gas storage applications.

Capturing carbon dioxide has evolved into an intriguing research area, mainly due to environmental concerns triggered by high levels of greenhouse gas emissions. Some MOFs have already been explored as carbon dioxide storage materials and exhibited storage capability exceeding that of conventional absorbents (e.g. amines). Aside from the absorption capacity of carbon dioxide, the performance stability over prolonged operation periods is another figure of merit for MOF-based absorbents. However, there are limited studies in this area. Now for the first time, research groups led by Zeng and Zhao from National University of Singapore compared the performance stability of two representative MOFs, HKUST-1 and UiO-66(Zr). The unit cell of the two MOFs are shown in the inset of Figure a.

The two aforementioned MOFs were subjected to 500 carbon dioxide absorbing and desorbing cycles (Figure a). The carbon dioxide uptake amount of the two MOFs was gauged at specific cycle numbers (Figure b). Whilst HKUST-1 displayed a consistent decreasing storage capacity with increasing cycle number, the capacity of UiO-66(Zr) fluctuated but remained relatively constant. The results clearly indicate that HKUST-1 is more vulnerable and instable than UiO-66(Zr) during long-term working cycles.

The authors then investigated the mechanisms associated with the different stability performances. They first observed that the surface area of HKUST-1 decreased 24% to 1270 m2 g-1 after the stability test, whereas that of UiO-66(Zr) remained relatively intact. Moisture-induced structural collapse was excluded as a possible reason by carrying out a control experiment with ultra-pure and dry hydrogen gas. The authors then exploited multi-frequency atomic force microscopy and concluded that the difference in elastic modulus of the two MOF crystals played an important role in determining the corresponding MOF durability. UiO-66(Zr) has an elastic modulus (ca. 28 GPa) much higher than that of HKUST-1 (ca. 19 GPa), meaning that the former is more elastic than the latter. The high elasticity of UiO-66(Zr) can efficiently buffer the volumetric deformation caused by carbon dioxide absorption and desorption, preventing UiO-66(Zr) crystals from structural failure.

Figure. (a) Illustration of one cycle of the carbon dioxide absorption-desorption test. The inset shows where one carbon dioxide molecule resides in the corresponding MOFs. (b) The evolution of carbon dioxide uptake capacity (blue) and surface area (black) of HKUST-1 and UiO-66(Zr).

This work is expected to provide general guidelines on studying the structural stability of other MOFs with applications associated with gas storage and separation.

 

To find out more please read:

Structure Failure Resistance of Metal-organic Frameworks toward Multiple-cycle CO2 Sorption

Zhigang Hu, Yao Sun, Kaiyang Zeng, and Dan Zhao

DOI: 10.1039/c7cc04313a

About the author:

Tianyu Liu is a Ph.D. in chemistry graduated from University of California-Santa Cruz. He is passionate about scientific communication to introduce cutting-edge researches to both the general public and the scientists with diverse research expertise. He is a web writer for the Chem. Commun. and Chem. Sci. blog websites. More information about him can be found at http://liutianyuresearch.weebly.com/.

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Dissolving and Stabilizing the Precursor of Graphene in Organic Solvents

Graphene, a two-dimensional single-layer graphite sheet, has aroused worldwide attention since the last decade. Its ultrahigh electrical and thermal conductivities, high mechanical stiffness and unique band structure have attracted extensive research efforts to develop graphene-based electronics, photonics, printing materials etc. Currently, among various strategies, the wet-chemical method still remains the most practical protocol for large-scale production of graphene in laboratories. This process in general involves two steps: the oxidative exfoliation of graphite, a.k.a. Hummers’ method, followed by reduction of the oxidized graphite sheets. Graphite oxide (GO), possessing a layered structure analogous to graphite but with rich oxygen functionalities (such as hydroxyl and carboxyl groups) anchored on each layer, is the product of the first step and thus serves as a precursor of graphene.

As the aforementioned wet chemical method is usually carried out in water, GO is primarily stored as aqueous-based colloidal dispersions. However, GO is reported to be chemically unstable in water since water molecules can react with electropositive carbons of GO. Though the reaction is not rapid, it partially removes the oxygen functionalities and breaks the carbon matrix, which eventually forces GO to precipitate and reduces the shelf life of the GO precursor.

Recently, Shi and coworkers from Tsinghua University have successfully prolonged the lifetime of GO by dispersing it in organic solvents. During the last purification step of the Hummers’ method, instead of using de-ionized water, anhydrous ethanol was utilized to rinse the GO product and obtain ethanol-wetted GO. X-ray diffraction revealed that ethanol molecules existed in the inter-layer space between adjacent layers. The ethanol-wetted GO could be readily dissolved in propylene carbonate, an organic solvent, for concentrations ranging from 0.1 mg mL-1 to 40 mg mL-1 (Figures a and b). More importantly, GO could be stored in propylene carbonate for at least a month without a colour change, whilst the colour of aqueous GO dispersion discernibly darkened (Figure c). Spectroscopic studies indicated that the colour change was attributed to the loss of oxygen functionalities. The results unambiguously prove that GO in propylene carbonate is much more stable than GO in water.

Figure. (a) Dissolution of ethanol-wetted GO in propylene carbonate. (b) GO colloidal dispersions with various concentrations. (c) Color evolution of GO dispersions (1 mg mL-1) with water and propylene carbonate as solvents before and after storing for 28 days under ambient conditions.

Aside from propylene carbonate, dimethyl sulfoxide, ethylene glycol and N,N-dimethylformamide are solvents that can dissolve the ethanol-wetted GO. The successful stabilization of GO colloidal dispersions could ensure the steady production of graphene in laboratories, as well as reveal new opportunities to develop GO-based devices.

To find out more please read:

Organic Dispersions of Graphene Oxide with Arbitrary Concentrations and Improved Chemical Stability

Wencheng Du, Mingmao Wu, Miao Zhang, Guochuang Xu, Tiantian Gao, Liu Qian, Xiaowen Yu, Fengyao Chi, Chun Li and Gaoquan Shi

DOI: 10.1039/c7cc04584k

About the author:

Tianyu Liu is a Ph.D. in chemistry graduated from University of California-Santa Cruz. He is passionate about scientific communication to introduce cutting-edge researches to both the general public and the scientists with diverse research expertise. He is a web blog writer for the Chem. Commun. and Chem. Sci. blog websites. More information about him can be found at http://liutianyuresearch.weebly.com/.

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Releasing A Pungent Anti-cancer Reagent with A Trisulfide Linker Inspired by Garlic

People who love the taste of garlic are often annoyed by its lingering smell. While there are various tips to get rid of this unpleasant odor, have you ever thought that this garlic aroma brings you chemical compounds that are potent anti-cancer reagents?

Diallyl trisulfide, one of the natural occurring components rendering the flavor of garlic, is able to release hydrogen sulfide (H2S) upon contacting with thiol compounds (i.e., organic molecules with –SH functional groups). H2S is a pungent gas that one might never forget after sniffing a rotten egg. However, this “notorious” gas, when at low concentrations, is reported to be friendly to our bodies. It relaxes vascular smooth muscle, reduces blood pressure, lowers risk associated with cancer as well as protects gastrointestinal, nervous and immune systems. All the aforementioned benefits of H2S have aroused worldwide efforts in developing H2S-releasing and bio-compatible materials that mimic the natural products for pharmaceutical applications.

Davis, Quinn and co-workers from Monash University, Australia and University of Warwick, United Kingdom, recently published a paper in Chemical Communications that reports a trisulfide-linked organic polymer capable of releasing H2S when meets –SH groups. As shown in the scheme below, the synthesized polymer is composed of three parts: a polyethylene glycol (PEG) unit on the left (in blue), a cholesterol (CHOL) group on the right (in orange), and a linker (in black) joining the two ends. PEG and CHOL are chosen mainly due to their bio-compatibility. By changing the structure of the middle linker, the authors obtained three types of polymers that behave differently when mixing with thiol compounds. The trisulfide linker (denoted as T) enables release of H2S gas and initiates polymer degradation. The disulfide linker (denoted as D) allows polymer degradation only. The amide linker (denoted as C) containing no sulfide atoms is inert to the thiol exposure.

Scheme. The chemical structure of the synthesized polymers with different linkers.

Experiments showed that the T-linked polymers are capable of releasing H2S both in vitro and in vivo.

A fluorescent probe, which can be reduced by H2S and becomes fluorescent, is applied to detect the existence of H2S. As shown in Figure a, the trisulfide linked polymers tested in vitro exhibited the highest fluorescence when mixing with L-cysteine (a thiol compound to trigger H2S generation). For the in vivo measurements, the authors incubated HEK293 cells with the polymers and the probe. Similar as the in vitro results, the fluorescence intensity of the cells containing the T-linked polymers is the highest (Figure b). Both the in vitro and in vivo results unambiguously proved that the presence of the T-linker was responsible for generating H2S. Additionally, another set of tests using Nile Red confirmed the biodegradability of the T-linked polymers.

Figure. (a) Fluorescence spectra collected from different systems in vitro. The inset shows the chemical reaction between the probe (SF4) and H2S that displays fluorescence. (b) Fluorescence intensity of different polymers over time in HEK293 cells.

The developed tri-sulfide linker may allow the mimicry of endogenous biosynthesis, the initiation of discrete signaling events and the synthesis of next-generation pharmaceutical excipients.

 

To find out more please read:

Garlic-inspired Trisulfide Linkers for Thiol-stimulated H2S Release
Francesca Ercole, Michael R. Whittaker, Michelle L. Halls, Ben J. Boyd, Thomas P. Davis and John F. Quinn
DOI: 10.1039/c7cc03820h

About the author:

Tianyu Liu is a Ph.D. in chemistry graduated from University of California-Santa Cruz. He is passionate about scientific communication to introduce cutting-edge researches to both the general public and the scientists with diverse research expertise. He is a web writer for the Chem. Commun. and Chem. Sci. blog websites. More information about him can be found at http://liutianyuresearch.weebly.com/.

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A Promising Cathode Material for Magnesium-ion Batteries Has Been Identified

Research associated with batteries is gaining increasing attention and extensive efforts in recently decades, partly due to the development of sustainable energy to combat a series of problems including fossil fuel depletion, environmental pollution and global warming. Batteries are indispensable energy storage devices for the utilization of sustainable energy (e.g., solar and wind energy). One of the battery’s cutting-edge research topics is to achieve novel batteries with higher capacity (a figure-of-merit to measure how much electrical energy a battery can store) and better reliability than the lithium-ion batteries that currently dominate the battery market.

In the past decade, batteries based on magnesium ions, termed as magnesium-ion batteries, are emerging. The magnesium-ion batteries possess at least two advantages over lithium-ion batteries. Firstly, their typical anode material, magnesium metal, has a theoretical capacity of 3833 mAh/cm3. This value is much higher than that of graphite, a conventional anode material for lithium-ion batteries. Secondly, the formation of metal dendrite on anode surface can be avoided by replacing lithium metal with magnesium metal. Metal dendrites grow from anodes can eventually touch cathodes, causing electric short circuits and triggering fire and explosion. Therefore, magnesium-ion batteries are safer than lithium-ion batteries. However, nothing can be perfect. The limited mobility of Mg2+ of cathode materials greatly reduces the capacity (particularly at fast charging rates) and practicability of the magnesium-ion batteries.

Now Rong et al. has published an article in Chemical Communications stating that a promising cathode material capable of fast conducting Mg2+ for magnesium-ion batteries has been identified. The material is a molybdenum phosphate compound with a chemical formula of Mo3(PO4)3O. It is composed of several edge-sharing MoO6 octahedra, corner-sharing MoO5 trigonal bipyramids, MoO4 tetrahedra, and PO4 tetrahedra. Using advanced simulation and computation techniques (i.e., the first-principles density functional theory), the authors first proved that Mg2+ can stably reside in some interstitial sites among the aforementioned polyhedra, indicating the identified compound is active for Mg2+ storage. In addition, the authors plotted two possible pathways for Mg2+ diffusion during charge and discharge processes (shown in the Figure). As illustrated in Figure a1, the first one is an inner-channel path along the b-axis. The second one is an inter-channel path along the c-axis.

The most striking feature of the path #1 is its ultra-low activation barrier (i.e., the highest potential energy that a Mg2+ need to overcome when diffusing) of only ~80 meV (Figure a2). Such a low diffusion barrier is expected to allow facile Mg2+ diffusion within the bulk of Mo3(PO4)3O, which can boost the capacity of the magnesium-ion batteries particularly at elevated charging rates. On the contrary, the activation barrier of the path #2 is as high as ~1200 meV. The authors claimed that the Mg2+ diffusion along the path #2 “should be ~1018 times less frequent than” the path #1.

 

 

Figure (a1) schematic of the Mg2+ diffusion path #1 and (a2) its corresponding diffusion potential barrier distribution along the way. (b1) Schematic of the Mg2+ diffusion path #2 and (a2) its corresponding diffusion potential barrier distribution along the way.

 

At last, the authors estimated the theoretical average potential that Mo3(PO4)3O can reach is 1.98 V, corresponding to a promising energy density of 173 Wh/kg. Although the proposed phosphate is hypothetical, the investigation of its stability reveals the possibility that this material can be experimentally synthesized.

To find out more please read:

Fast Mg2+ Diffusion in Mo3(PO4)3O for Mg Batteries
Ziqin Rong, Penghao Xiao, Miao Liu, Wenxuan Huang, Daniel C. Hannah, William Scullin, Kristin A. Persson and Gerbrand Ceder
DOI: 10.1039/c7cc02903a

About the author:

Tianyu Liu is a Ph.D. in chemistry graduated from University of California-Santa Cruz. He is passionate about scientific communication to introduce cutting-edge researches to both the general public and the scientists with diverse research expertise. He is a web writer for the Chem. Commun. and Chem. Sci. blog websites. More information about him can be found at http://liutianyuresearch.weebly.com/.

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A “Cube-in-tube” Carbon-Metal Oxide Lithium-ion Battery Composite Electrode with Outstanding Capacity and Durability

Lithium-ion batteries are indispensable for powering a number of electronics (e.g. cell phones, laptops and even electric vehicles) used in the modern society. The key components of a lithium-ion battery are its two electrodes (anode and cathode) because they largely dictate the amount of electrical energy (measured by a parameter called “capacity”) the battery can hold. Increasing the capacity as well as prolonging the lifetime of lithium-ion batteries are practically desirable. Material scientists worldwide are searching for electrode materials to achieve the goal.

In the past decade, a diverse array of metal oxides has been developed as lithium-ion battery anodes with promising performance. These anodes have exhibited considerably higher capacity (~1000 mAh/g) than the current commercial anode material, graphite (372 mAh/g). However, two major drawbacks of metal oxides, namely the limited electrical conductivity and the short lifetime, impede their feasibility for practical applications. While the poor electrical conductivity is an intrinsic physical property of most metal oxides, their short life time is caused by the large volumetric deformation during charge and discharge processes. The deformation will eventually trigger pulverization of electrodes and lead to loss of capacity. Therefore, developing novel strategies that manage to turn metal oxides to viable electrode candidates with satisfying lifetime becomes necessary.

Now writing in Chemical Communications, a research group led by Professor Liqiang Mai and Professor Qi Li from Wuhan University of Technology, China demonstrated a metal oxide-carbon composite anode that exhibited both high capacity and super-long lifetime. The structure of this composite is a “cube-in-tube” configuration (Figure 1): the manganese oxide nanoparticle-embedded carbon “tubes” encapsulate the CoSnO3 (a binary metal oxide) “cubes”. This unique composite electrode delivered a maximal capacity of 960 mAh/g at a current density of 0.1 A/g (Figure 2a), around three times higher than the theoretical capacity of graphite. More impressively, as shown in Figure 2b, the electrode displayed outstanding stability with ~99% of capacity retained after 1500 consecutive charge and discharge cycles (roughly equivalent to four years’ use), much higher than those of the current commercial products and other laboratory-developed composites.

Figure 1. Schematic of the synthesis strategy and the morphology of the “cube-in-tube” metal oxide-carbon composite lithium-ion battery electrode.

Figure 2. (a) Plot of capacity at different current densities; (b) The stability performance evaluated at 2 A/g.

The authors attributed the electrode’s excellent durability to two reasons. Firstly, the hollow structures (both the “tube” and the “cube”) provide adequate empty space to accommodate volumetric change of metal oxides. Secondly, the soft nature of carbon renders its ability to serve as a mechanical buffer layer. Both aspects reduce the possibility of structural pulverization and promote long lifetime.

To find out more please read:

Facile Electrospinning Formation of Carbon-confined Metal Oxide Cube-in-tube Nanostructures for Stable Lithium Storage

Ziang Liu, Ruiting Guo, Jiashen Meng, Xiong Liu, Xuanpeng Wang, Qi Li, Liqiang Mai

DOI: 10.1039/C7CC0327A

About the author:

Tianyu Liu is a Ph.D. in chemistry graduated from University of California-Santa Cruz, United States. He is passionate about scientific communication to introduce cutting-edge researches to both the general public and the scientists with diverse research expertise. He is a web writer for the Chem. Commun. and Chem. Sci. blog websites. More information about him can be found at http://liutianyuresearch.weebly.com/.

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