Interfacial Electronic Modulation of Dual-Monodispersed Pt–Ni_(3)S_(2) as Efficacious Bi-Functional Electrocatalysts for Concurrent H_(2) Evolution and Methanol Selective Oxidation

Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.

Vapour and Solution Uptake Properties of Starch and Cellulose Biopolymers

This study was aimed at gaining further insight on the role of hydration in adsorption processes of biopolymer/adsorbate systems using complementary methods (electromagnetic interference (EMI) shielding, calorimetry, and solvent/vapour adsorption isotherms). Cellulose and starch-based materials were used as the adsorbents, whereas water (liquid and vapour), ethanol and p-nitrophenol (PNP) in aqueous solution were the adsorbate systems. The biopolymer/water systems had higher uptake capacity overall, where starch materials showed higher uptake capacity than cellulose among the various solvents. The secondary and tertiary structure of the biopolymers was a key factor affecting their uptake capacity, as evidenced by the enhanced adsorption properties of starch over cellulose, along with higher uptake of amylose (AM) versus amylopectin (AP) in starch biopolymers. EMI results also confirmed that AM starch had higher adsorption toward water than ethanol. The textural properties and surface chemistry of the biopolymers were probed using dye adsorption (PNP at pH 8.5) in aqueous solution that showed parallel trends with water vapour adsorption isotherms. Isothermal Titration Calorimetry (ITC) revealed that the heat of adsorption in AP differed from that of AM since the biopolymer tertiary structure governs the accessibility of biopolymer adsorption sites. The role of branching in AP and amorphous domains in AM/AP composites are inferred to play a key role in hydration-driven allosterism known for such biopolymer/water vapour adsorption processes.