Lujie Cao

Multistimuli‐Responsive, Moldable Supramolecular Hydrogels Cross‐Linked by Ultrafast Complexation of Metal Ions and Biopolymers

A new type of multistimuli-responsive hydrogels cross-linked by metal ions and biopolymers is reported. By mixing the biopolymer chitosan (CS) with a variety of metal ions at the appropriate pH values, we obtained a series of transparent and stable hydrogels within a few seconds through supramolecular complexation. In particular, the CS-Ag hydrogel was chosen as the model and the gelation mechanism was revealed by various measurements. It was found that the facile association of Ag(+) ions with amino and hydroxy groups in CS chains promoted rapid gel-network formation. Interestingly, the CS-Ag hydrogel exhibits sharp phase transitions in response to multiple external stimuli, including pH value, chemical redox reactions, cations, anions, and neutral species. Furthermore, this soft matter showed a remarkable moldability to form shape-persistent, free-standing objects by a fast in situ gelation procedure.

Selective and effective adsorption of methyl blue by barium phosphate nano-flake

We report the synthesis of barium phosphate (BP) nano-flake and its adsorption behavior to methyl blue (MB) in aqueous solution. The as-obtained BP nano-flake revealed pure rhombohedral crystal structure. The adsorption capacity of MB onto BP reached 1500 mg g(-1). The adsorption equilibrium results fitted well with the Freundlich isotherm model. The adsorption process took less than 30 min to reach equilibrium. The adsorption kinetics was elucidated by the pseudo-second-order kinetic equation. It followed 2-stage and 3-stage intra-particle diffusion models for the low and high concentration of dye solutions, respectively. The adsorption of MB using the BP nano-flake was highly selective, compared with the adsorption of other dyes. The interactions between MB and BP were mainly the ionic interaction and hydrogen bonds, which were confirmed by the X-ray photoelectron spectroscopic results and the density functional theory calculations. The BP nano-flake revealed less than 5% decrease in adsorption amount when it was recycled and reused five times. The present work shows that the BP nano-flake is promising for practical applications in MB removal from aqueous solutions.

A highly permeable mixed matrix membrane containing CAU-1-NH2 for H2 and CO2 separation.

A thin and compact mixed matrix membrane containing CAU-1-NH2 and the poly(methyl methacrylate) polymer has been originally synthesized. The as-prepared membrane exhibits high permeability of H2 and excellent H2/CO2 selectivity.

Highly durable organic electrode for sodium-ion batteries via a stabilized α-C radical intermediate.

It is a challenge to prepare organic electrodes for sodium-ion batteries with long cycle life and high capacity. The highly reactive radical intermediates generated during the sodiation/desodiation process could be a critical issue because of undesired side reactions. Here we present durable electrodes with a stabilized α-C radical intermediate. Through the resonance effect as well as steric effects, the excessive reactivity of the unpaired electron is successfully suppressed, thus developing an electrode with stable cycling for over 2,000 cycles with 96.8% capacity retention. In addition, the α-radical demonstrates reversible transformation between three states: C=C; α-C·radical; and α-C− anion. Such transformation provides additional Na+ storage equal to more than 0.83 Na+ insertion per α-C radical for the electrodes. The strategy of intermediate radical stabilization could be enlightening in the design of organic electrodes with enhanced cycling life and energy storage capability.

Facile electrodeposition of 3D concentration-gradient Ni-Co hydroxide nanostructures on nickel foam as high performance electrodes for asymmetric supercapacitors

Novel three-dimensional (3D) concentration-gradient Ni-Co hydroxide nanostructures (3DCGNC) have been directly grown on nickel foam by a facile stepwise electrochemical deposition method and intensively investigated as binder- and conductor-free electrode for supercapacitors. Based on a three-electrode electrochemical characterization technique, the obtained 3DCGNC electrodes demonstrated a high specific capacitance of 1,760 F·g−1 and a remarkable rate capability whereby more than 62.5% capacitance was retained when the current density was raised from 1 to 100 A·g−1. More importantly, asymmetric supercapacitors were assembled by using the obtained 3DCGNC as the cathode and Ketjenblack as a conventional activated carbon anode. The fabricated asymmetric supercapacitors exhibited very promising electrochemical performances with an excellent combination of high energy density of 103.0 Wh·kg−1 at a power density of 3.0 kW·kg−1, and excellent rate capability—energy densities of about 70.4 and 26.0 Wh·kg−1 were achieved when the average power densities were increased to 26.2 and 133.4 kW·kg−1, respectively. Moreover, an extremely stable cycling life with only 2.7% capacitance loss after 20,000 cycles at a current density of 5 A·g−1 was achieved, which compares very well with the traditional doublelayer supercapacitors.

Large-scale fabrication of porous carbon-decorated iron oxide microcuboids from Fe–MOF as high-performance anode materials for lithium-ion batteries

A facile, cost-effective and environmentally friendly route has been developed to synthesise porous carbon-decorated iron oxides on a large scale via annealing iron metal–organic framework (MOF) precursors. The as-prepared C–Fe3O4 particles exhibit microcuboid-like morphologies that are actually composed of ultrafine nanoparticles and show a greatly enhanced lithium storage performance with high specific capacity, excellent cycling stability and good rate capability. The C–Fe3O4 electrodes demonstrate a high reversible capacity of 975 mA h g−1 after 50 cycles at a current density of 100 mA g−1 and a remarkable rate performance, with capacities of 1124, 1042, 886 and 695 mA h g−1 at current densities of 100, 200, 500 and 1000 mA g−1, respectively. The satisfactory electrochemical performance was attributed to the hierarchical architecture, which benefitted from the synergistic effects of the high conductivity of the carbon matrix, the cuboid-like secondary particles on the microscale, and the ultrafine primary nanoparticles on the nanoscale. This low-cost and simple method provides the possibility to prepare anode materials on a large scale and hence may have great potential applications in energy storage and conversion.

A hollow ceramic fiber supported ZIF-8 membrane with enhanced gas separation performance prepared by hot dip-coating seeding

A hollow ceramic fiber supported ZIF-8 membrane has been prepared by a hot dip-coating seeding method followed by secondary growth. The obtained membrane exhibits excellent H2 permselectivity.

Catalyzed activation of CO2 by a Lewis-base site in W–Cu–BTC hybrid metal organic frameworks

A metal–organic framework (MOF)-based catalyst W–Cu–BTC is designed by hybridizing highly active W ions into Cu3(BTC)2(H2O)3 (also known as Cu–BTC or HKUST-1, BTC = 1,3,5-tricarboxylate benzene) frameworks based on density functional (DFT) calculations. We show that the hybrid W–Cu node plays a pivotal role in activating CO2 according to frontier molecular orbital theory. In contrast to the Lewis-acid nature of open metal sites in most MOFs, the exposed W ion in W–Cu–BTC is identified as a Lewis-base site, evidenced by the substantial electron donation from W ion to CO2. Kinetically, the linear CO2 molecule can be readily bent by forming a CO2–W complex after overcoming a negligible activation barrier of 0.09 eV. In addition, we present calculated infrared spectra (IR) and X-Ray spectra (XPS) for reference in future experimental studies.

Enhanced hydrolytic stability of sulfonated polyimide ionomers using bis(naphthalic anhydrides) with low electron affinity.

In the pursuit of hydrolytically stable sulfonated polyimide (SPI) membranes as promising candidates for proton exchange membranes, usable at elevated temperature, a series of novel SPI ionomers based on the low electron affinity bis(naphthalic anhydrides), 4,4′-sulfide-bis(naphthalic anhydride) (SBNA) and benzophenone-4,4′-bis(4-thio-1,8-naphthalic anhydride) (BPBTNA), were prepared. Tough, flexible, and transparent membranes were obtained from these polymers, although their inherent viscosities ranged from 0.41 to 0.59 dL g−1. The SPI membranes were thermally stable with the decomposition of sulfonic acid groups over 300 °C, and exhibited good mechanical properties with 65 MPa of tensile strength at 25 °C and 50% RH. The proton conductivities of the SPI membranes increases with increasing temperature and ion exchange capability (IEC), and the S–O(80) with 2.23 mequiv. g−1 of IEC showed a higher proton conductivity than Nafion® 212 at 100% RH. For the high IEC membranes, microscopic analyses revealed the hydrophilic clusters were well-dispersed and connected to each other. The accelerated water stability tests demonstrated that the SPI ionomers based on SBNA and BPBTNA maintained a high mechanical strength after being aged in water for 24 h at 140 °C, which was much more stable than the SPI membranes based on 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA). The improved hydrolytic stability of polymers could be well correlated with the results of the electron affinity (Ea) of the dianhydride calculated by the theoretical calculation. This investigation illustrated that this strategy will benefit the further development of hydrolytically stable SPIs applied to high temperature PEFCs.

Low-Cost and Novel Si-Based Gel for Li-Ion Batteries

Si-based nanostructure composites have been intensively investigated as anode materials for next-generation lithium-ion batteries because of their ultra-high-energy storage capacity. However, it is still a great challenge to fabricate a perfect structure satisfying all the requirements of good electrical conductivity, robust matrix for buffering large volume expansion, and intact linkage of Si particles upon long-term cycling. Here, we report a novel design of Si-based multicomponent three-dimensional (3D) networks in which the Si core is capped with phytic acid shell layers through a facile high-energy ball-milling method. By mixing the functional Si with graphene oxide and functionalized carbon nanotube, we successfully obtained a homogeneous and conductive rigid silicon-based gel through complexation. Interestingly, this Si-based gel with a fancy 3D cross-linking structure could be writable and printable. In particular, this Si-based gel composite delivers a moderate specific capacity of 2711 mA h g-1 at a current density of 420 mA g-1 and retained a competitive discharge capacity of more than 800.00 mA h g-1 at the current density of 420 mA g-1 after 700 cycles. We provide a new method to fabricate durable Si-based anode material for next-generation high-performance lithium-ion batteries.