A pseudo-Double-Network Hydrogel Built upon Layered Double Hydroxides with Self-Strengthening Properties.

While great achievements have been made in the development of mechanically robust nanocomposite hydrogels, incorporating multiple interactions on the bases of two demensional inorganic cross-linkers to construct self-strengthening hydrogels has rarely been investigated. To this end, we propose here a new method for the coupling the dynamic covalent bonds and non-covalent interactions within a pseudo double-network system. The pseudo first network, formed through the Schiff Base reation between Tris-modified layered double hydroxides (Tris-LDHs) and oxidized dextran (ODex), is linked to the second network built upon non-covalent interactions between Tris-LDHs and poly(acrylamide-co-2-acrylamido-2-methyl-propanesulfonate) (p-(AM-co-AMPS). The swelling and mechanical properties of the resulting hydrogels have been investigated as a function of the ODex and AMPS contents. The as-prepared hydrogel can swell to 420 times of its original size and retain more than 99.9 wt.% of water. Mechanical tests show that the hydrogel can bear 90 % of compression and is able to be stretched to near 30 times of its original length. Cyclic tensile tests reveal that the hydrogels are capable of self-strengthening after mechanical training. The unique energy dissipation mechanism based on the dynamic covalent and non-covalent interactions is considered to be responsible for the outstanding swelling and mechanical performances.

Regulating Hollow Carbon Cage Supported NiCo Alloy Nanoparticles for Efficient Electrocatalytic Hydrogen Evolution Reaction.

The NiCo alloy is one of the most promising alternatives to the noble-metal electrocatalysts for the hydrogen evolution reaction (HER); however, its performance is largely restricted by insufficient active sites and low surface area. Here, we fabricated a hierarchical hollow carbon cage supported NiCo alloy (denoted as HC NiCo/C) and a bulk NiCo alloy (denoted as NiCo) by reduction of a partially ZIF-67 etched ZIF-67@NiCo-LDH (LDH = layered double hydroxide) precursor and a fully ZIF-67 etched NiCo-LDH precursor, respectively. The as-prepared HC NiCo/C, in which the Ni29Co71 alloy nanocrystals with an average 6 nm size were encapsulated in graphitic carbon layers, provided a vastly increased electrochemically active surface area (ca. 13 times than the NiCo) and abundant catalytic active sites, which resulted in a higher HER performance with an overpotential of 99 mV than the 198 mV for NiCo at 10 mA cm-2. Detailed experimental results suggested that only the HC NiCo/C possessed the active alloy surface composed of unsaturated Ni0 and Co0 atoms, and both the metal-support interaction and alloying effect influenced the electronic structure of Co and Ni in HC NiCo/C, whereas the NiCo exhibited pure Ni surface. Theoretical calculations further revealed the Ni29Co71 alloy surface in HC NiCo/C possessed the appropriate adsorption energy of the intermediate state (adsorbed H*). This work provided new insight into the construction of the stable small-sized bimetallic alloy nanocatalysts by regulating the reduction precursors.