Reviving Oxygen Evolution Electrocatalysis of Bulk La–Ni Intermetallics via Gaseous Hydrogen Engineering

A hydrogen processing strategy is developed to enable bulk LaNi5 to attain high activity and long-term stability toward the electrocatalytic oxygen evolution reaction (OER). By a combination of in situ Raman and quasi in situ X-ray absorption (XAS) spectra, secondary-electron-excited scanning transmission electron microscopy (STEM) patterns as well as the Rietveld method and density functional theory (DFT) calculations, it is discovered that hydrogen-induced lattice distortion, grain refinement, and particle cracks dictate the effective reconstruction of the LaNi5 surface into a porous hetero-nanoarchitecture composed of uniformly confined active γ-NiOOH nanocrystals by La(OH)3 layer in the alkaline OER process. This significantly optimizes the charge transfer, structural integrity, active-site exposure, and adsorption energy toward the reaction intermediates. Benefiting from these merits, the overpotential (322 mV) at 100 mA cm−2 for the hydrogen-processed OER catalyst deposited on nickel foam is reduced by 104 mV as compared to the original phase. Notably, it exhibits remarkable stability for 10 days at an industrial-grade current density of more than 560 mA cm−2 in alkaline media

Carbon quantum dots coated BiVO4 inverse opals for enhanced photoelectrochemical hydrogen generation

Carbon quantum dots (CQDs) coated BiVO4 inverse opal (io-BiVO4) structure that shows dramatic improvement of photoelectrochemical hydrogen generation has been fabricated using electrodeposition with a template. The io-BiVO4 maximizes photon trapping through slow light effect, while maintaining adequate surface area for effective redox reactions. CQDs are then incorporated to the io-BiVO4 to further improve the photoconversion efficiency. Due to the strong visible light absorption property of CQDs and enhanced separation of the photoexcited electrons, the CQDs coated io-BiVO4 exhibit a maximum photo-to-hydrogen conversion efficiency of 0.35%, which is 6 times higher than that of the pure BiVO4 thin films. This work is a good example of designing composite photoelectrode by combining quantum dots and photonic crystal.Published versio

Coupling surface plasmon resonance of gold nanoparticles with slow-photon-effect of TiO2 photonic crystals for synergistically enhanced photoelectrochemical water splitting

The slow photon effect of a photonic crystal (PC) is a promising characteristic for tuning light-matter interactions through material structure designing. A TiO2 bi-layer structure photoanode was constructed by fabricating a TiO2 PC layer through a template-assisted sol-gel process on a TiO2 nanorod array (NR) layer. Gold nanoparticles (Au NPs) with an average size of about 10 nm were deposited in situ into the TiO2 bi-layer structure. The extended photoelectrochemical (PEC) water splitting activity in visible light was ascribed to the energetic hot electrons and holes that were generated in the Au NPs through the excitation and decay of surface plasmons. By alternating the characteristic pore size of the TiO2 PC layer, the slow photon region at the red edge of the photonic band gap could be purposely tuned to overlap with the strong localized surface plasmon resonance (SPR) region of Au NPs. The matching slow photon effect of TiO2 PC (with a characteristic pore size of 250 nm) intensified the SPR responses (central at 536 nm) of Au NPs. Consequently, more hot electrons were generated in the Au NPs and injected into the conduction band of TiO2, resulting in improved PEC water splitting efficiency in the visible light region. Under simulated sunlight illumination, the photoconversion efficiency of the well matching Au/TiO2 photoanode approached 0.71%, which is one of the highest values ever reported in Au/TiO2 PEC systems. The work reported here provides support for designing coupling plasmonic nanostructures with PC-based materials to synergistically enhance PEC water splitting efficiency

Super-Branched PdCu Alloy for Efficiently Converting Carbon Dioxide to Carbon Monoxide

The alloying of noble metals with Cu is one of the most effective strategies for improving catalytic performance and reducing cost in electrocatalytic carbon dioxide reduction reactions (CO2RR). Previous works usually focused on the influence of morphology and composition on the catalytic activity, but lacked the study of the valence state ratio of metals and the electron transfer behavior on alloys. In this work, PdCu−2 alloy (Pd/Cu molar ratio is 1:2) was obtained by a simple one-step solvothermal method, which can effectively convert CO2 to CO with a maximum Faradaic efficiency (FE) of 85% at −0.9 V (vs. RHE). Then, the effect of the chemical state of Pd and Cu on the catalytic performance was investigated. The X-ray photoelectron spectroscopy (XPS) shows that the binding energy of Pd in PdCu alloy has a negative shift, which has affected the adsorption of key intermediates. When the proportion of oxidized state and zero-valent metal in the alloy is about 1:2, the PdCu alloy shows the best catalytic activity. In addition, the transient photovoltage (TPV) measurements further demonstrate that due to the introduction of Cu, the electron transfer rate of PdCu−2 becomes the slowest, which helps the accumulation of electrons on PdCu−2 and leads to the improvement of catalytic performance for electrocatalytic CO2RR. This work can provide more insights into the alloy catalysts of electrocatalytic CO2RR

C3N nanodots inhibits Aβ peptides aggregation pathogenic path in Alzheimer’s disease

Abstract Despite the accumulating evidence linking the development of Alzheimer’s disease (AD) to the aggregation of Aβ peptides and the emergence of Aβ oligomers, the FDA has approved very few anti-aggregation-based therapies over the past several decades. Here, we report the discovery of an Aβ peptide aggregation inhibitor: an ultra-small nanodot called C3N. C3N nanodots alleviate aggregation-induced neuron cytotoxicity, rescue neuronal death, and prevent neurite damage in vitro. Importantly, they reduce the global cerebral Aβ peptides levels, particularly in fibrillar amyloid plaques, and restore synaptic loss in AD mice. Consequently, these C3N nanodots significantly ameliorate behavioral deficits of APP/PS1 double transgenic male AD mice. Moreover, analysis of critical tissues (e.g., heart, liver, spleen, lung, and kidney) display no obvious pathological damage, suggesting C3N nanodots are biologically safe. Finally, molecular dynamics simulations also reveal the inhibitory mechanisms of C3N nanodots in Aβ peptides aggregation and its potential application against AD

Enhanced mechanical properties of nanocrystalline B4C–SiC composites by in-situ high pressure reactive sintering

A unique optimized of core–shell structural B4C nanopowder, sintering aid additive of Si, and high-pressure sintering technique has been used to process nanocrystalline B4C–SiC ceramics with enhanced mechanical properties. C-coated B4C nanopowder was initially uniformly mixed with micron Si of different content by ball-milling. B4C–SiC composites with a homogenous distribution of SiC in B4C matrix were subsequently obtained by sintering the mixed powders at 6 GPa and 1600 °C. The added Si reacted with submicron amorphous carbon layer and amorphous carbon nanoshell to form dispersed SiC nanocrystals and Si–C phase filled at B4C grain boundaries and pores, respectively. The prepared composite had the most outstanding mechanical properties when the Si content in the precursor was 15 wt%, with a hardness reaching 37.8 GPa and a fracture toughness reaching 7.3 MPa·m1/2. Microstructural characterizations indicated that the multi deflection of nanoscale crack caused by intergranular fracture, the covalent bonding of Si–C phase at the grain boundary, and the abundant nanotwin substructure were jointly responsible for the superior performance in hardness and fracture toughness