2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO2 to Formic Acid.

Efficiently transforming CO2 into renewable energy sources is crucial for decarbonization efforts. Formic acid (HCOOH) holds great promise as a hydrogen storage compound due to its high hydrogen density, non-toxicity, and stability under ambient conditions. However, the electrochemical reduction of CO2 (CO2 RR) on conventional carbon black-supported metal catalysts faces challenges such as low stability through dissolution and agglomeration, as well as suffering from high overpotentials and the necessity to overcome the competitive hydrogen evolution reaction (HER). In this study, we modify the physical/chemical properties of metal surfaces by depositing metal monolayers on graphene (M/G) to create highly active and stable electrocatalysts. Strong covalent bonding between graphene and metal is induced by the hybridization of sp and d orbitals, especially the sharp d z 2 ${{d}_{{z}^{2}}}$ , d y z ${{d}_{yz}}$ , and d x z ${{d}_{xz}}$ orbitals of metals near the Fermi level, playing a decisive role. Moreover, charge polarization on graphene in M/G enables the deposition of another thin metallic film, forming metal/graphene/metal (M/G/M) structures. Finally, evaluating overpotentials required for CO2 reduction to HCOOH, CO, and HER, we find that Pd/G, Pt/G/Ag, and Pt/G/Au exhibit excellent activity and selectivity toward HCOOH production. Our novel 2D hybrid catalyst design methodology may offer insights into enhanced electrochemical reactions through the electronic mixing of metal and other p-block elements.

Iron Phosphide Confined in Carbon Nanofibers as a Free-Standing Flexible Anode for High-Performance Lithium-Ion Batteries.

Iron phosphide with high specific capacity has emerged as an appealing candidate for next-generation lithium-ion battery anodes. However, iron phosphide could undergo conversion reactions and generally suffer from a rapid capacity degradation upon cycling due to its structure pulverization. Chemomechanical breakdown of iron phosphide due to its rigidity has been a challenge to fully realizing its electrochemical performance. To address this challenge, we report here on an enticing opportunity: a flexible, free-standing iron phosphide anode with Fe2P nanoparticles confined in carbon nanofibers may overcome existing challenges. For the synthesis, we introduce a facile electrospinning strategy that enables in situ formation of Fe2P within a carbon matrix. Such a carbon matrix can effectively minimize the structure change of Fe2P particles and protect them from pulverization, allowing the electrodes to retain a free-standing structure after long-term cycling. The produced electrodes showed excellent electrochemical performance in lithium-ion half and full cells, as well as in flexible pouch cells. These results demonstrate the successful development of iron phosphide materials toward high capacity, light weight, and flexible energy storage.

Novel N-p-carboxy benzyl chitosan/poly (vinyl alcohol/functionalized zeolite mixed matrix membranes for DMFC applications.

The novel N-p-carboxy benzyl chitosan (CBC)/ poly (vinyl alcohol) (PVA) based mixed matrix membranes (MMMs) filled with surface-modified zeolite have been prepared using the dissolution casting technique. The applicability of prepared MMMs for direct methanol fuel cell (DMFC) was investigated in terms of water uptake, methanol permeation, and proton conductivity by changing filler content (10-50 wt. %). The zeolite was modified by silane coupling agent, 3-mercaptopropyltrimethoxysilane (MPTMS). The resultant modified zeolite (MZ) was incorporated into CBC/PVA blend to obtain mixed matrix PEMs. The functional group, structural properties, morphological and topographical investigation of MMMs were examined using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and Scanning electron microscopy (SEM) respectively. The prepared MMMs exhibited a remarkable decrease in methanol permeability of 2.3 × 10-7  cm2/s with C-CPMZ50. The maximum value of proton conductivity of 0.0527 Scm-1, was shown by C-CMPZ10. The prepared PEMs also displayed good stability during long term operating time.

Atomic Structure and Dynamics of Epitaxial Platinum Bilayers on Graphene.

Platinum atomic layers grown on graphene were investigated by atomic resolution transmission electron microscopy (TEM). These TEM images reveal the epitaxial relationship between the atomically thin platinum layers and graphene, with two optimal epitaxies observed. The energetics of these epitaxies influences the grain structure of the platinum film, facilitating grain growth via in-plane rotation and assimilation of neighbor grains, rather than grain coarsening from the movement of grain boundaries. This growth process was enabled due to the availability of several possible low-energy intermediate states for the rotating grains, the Pt-Gr epitaxies, which are minima in surface energy, and coincident site lattice grain boundaries, which are minima in grain boundary energy. Density functional theory calculations reveal a complex interplay of considerations for minimizing the platinum grain energy, with free platinum edges also having an effect on the relative energetics. We thus find that the platinum atomic layer grains undergo significant reorientation to minimize interface energy (via epitaxy), grain boundary energy (via low-energy orientations), and free edge energy. These results will be important for the design of two-dimensional graphene-supported platinum catalysts and obtaining large-area uniform platinum atomic layer films and also provide fundamental experimental insight into the growth of heteroepitaxial thin films.