In-Situ Derived Defective Ru Particles Anchored on Ru-Ni Layered Double Hydroxides for Enhanced Alkaline Hydrogen Evolution.

Developing active, stable, and cost-efficient electrocatalysts to replace platinum for the alkaline hydrogen evolution reaction (HER) is highly desirable yet represents a great challenge. Here, it is reported on a facile one-pot synthesis of RuxNi layered double hydroxides (RuxNi-LDHs) that exhibit remarkable HER activity and stability after an in-situ activation treatment, surpassing most state-of-the-art Ru-based catalysts as well as commercial Ru/C and Pt/C catalysts. The structural and chemical changes triggered by in-situ activation are systematically investigated, and the results clearly show that the pristine, less-active RuxNi-LDHs are transformed into a highly active catalyst characterized by raft-like, defect-rich Ru° particles decorated on the surface of RuxNi-LDHs. Density functional theory (DFT) calculations reveal that the defective Ru sites can effectively optimize the reaction pathway and lower the free energies of the elemental steps involved, leading to enhanced intrinsic activity. This work highlights the importance of the currently understudied strategy of defect engineering in boosting the HER activity of Ru-based catalysts and offers an effective approach involving in-situ electrochemical activation for the development of high-performance alkaline HER catalysts.

Carbon Encapsulation of Supported Metallic Iridium Nanoparticles: An in Situ Transmission Electron Microscopy Study and Implications for Hydrogen Evolution Reaction.

Carbon-supported metal nanoparticles (NPs) comprise an important class of heterogeneous catalysts. The interaction between the metal and carbon support influences the overall material properties, viz., the catalytic performance. Herein we use in situ and ex situ transmission electron microscopy (TEM) in combination with in situ X-ray spectroscopy (XPS) to investigate the encapsulation of metallic iridium NPs by carbon in an Ir/C catalyst. Real-time atomic-scale imaging visualizes particle reshaping and increased graphitization of the carbon support upon heating of Ir/C in vacuum. According to in situ TEM results, carbon overcoating grows over Ir NPs during the heating process, starting from ca. 550 °C. With the carbon overlayers formed, no sintering and migration of Ir NPs is observed at 800 °C, yet the initial Ir NPs sinter at or below 550 °C, i.e., at a temperature associated with an incomplete particle encapsulation. The carbon overlayer corrugates when the temperature is decreased from 800 to 200 °C and this process is associated with the particle surface reconstruction and is reversible, such that the corrugated carbon overlayer can be smoothed out by increasing the temperature back to 800 °C. The catalytic performance (activity and stability) of the encapsulated Ir NPs in the hydrogen evolution reaction (HER) is higher than that of the initial (nonencapsulated) state of Ir/C. Overall, this work highlights microscopic details of the currently understudied phenomenon of the carbon encapsulation of supported noble metal NPs and demonstrates additionally that the encapsulation by carbon is an effective measure for tuning the catalytic performance.

Constructing Cu-C Bonds in a Graphdiyne-Regulated Cu Single-Atom Electrocatalyst for CO2 Reduction to CH4.

Regulating intermediates through elaborate catalyst design to control the reaction direction is crucial for promoting the selectivity of electrocatalytic CO2 -to-CH4 . M-C (M=metal) bonds are particularly important for tuning the multi-electron reaction; however, its construction in nanomaterials is challenging. Here, via rational design of in situ anchoring of Cu SAs (single atoms) on the unique platform graphdiyne, we firstly realize the construction of a chemical bond Cu-C (GDY). In situ Raman spectroelectrochemistry and DFT calculations confirm that due to the fabrication of the Cu-C bond, during CO2 reduction, the formation of *OCHO intermediates is dominant rather than *COOH on Cu atoms, facilitating the formation of CH4 . Therefore, we find that constructing the Cu-C bond in Cu SAs/GDY can supply an efficient charge transfer channel, but most importantly control the reaction intermediates and guide a more facile reaction pathway to CH4 , thereby significantly boosting its catalytic performance. This work provides new insights on enhancing the selectivity for CO2 RR at the atomic level.

Two biologically inspired tetranuclear nickel(II) catalysts: effect of the geometry of Ni4 core on electrocatalytic water oxidation.

Two biologically inspired tetranuclear nickel complexes [Ni4(L-H)4(CH3COO)3]·Cl (1) and [Ni4(L-H)4(CH3COO)4]·2CH3OH (2) (L = di(pyridin-2-yl)methanediol) have been synthesized and investigated by a combination of X-ray crystallography, PXRD, electrochemistry, in-situ UV-Vis spectroelectrochemistry and DLS. Both of the two complexes feature a core composed of four Ni(II) ions with the same peripheral ligation provided by the anionic di(pyridin-2-yl)methanediol and MeCOO- ligands. Whereas, complex 1 possesses one distorted cubane-like [Ni4(µ3-O)4] core, while 2 has one extended butterfly-like [Ni4(µ3-O)2] core. The homogeneous electrocatalytic reactivity of the two water-soluble complexes for water oxidation have been thoroughly studied, which demonstrates that both of them can efficiently electrocatalyze water oxidation with high stability under alkaline conditions, at relatively low over-potentials (η) of 420-790 mV for 1 and 390-780 mV for 2, both in the pH range of 7.67-12.32, with the high TOF of about 139 s-1 (1) and 69 s-1 (2) at pH = 12.32, respectively. By a series of comparative experiments for complexes 1 and 2, we proposed that their crystal geometries play an important role in their electrocatalytic reactivity for water oxidation. We verified that biomimetic cubane geometry could promote OER catalysis with two very similar compounds for the first time. Compared with 2, the biomimetic cubane topology of 1 could promote OER catalysis by facilitating efficient charge delocalization and electron-transfer.

Lily bulbs' polyphenols extract ameliorates oxidative stress and lipid accumulation in vitro and in vivo.

BACKGROUND: Polyphenols have the potential to reduce the risk of many metabolic disorders. Lily bulbs are rich in polyphenols; however, their effects on lipid metabolism remain unclear. This study aimed to explore the effects of lily bulbs' polyphenols (LBPs) on oxidative stress and lipid metabolism. RESULTS: A total of 14 polyphenolic compounds in LBPs were identified by high-performance liquid chromatography equipped with diode-array detection mass spectrometry. Total phenolic compound in LBPs was 53.76 ± 1.12 g kg-1 dry weight. In cellular experiments, LBPs attenuated the disruption of mitochondrial membrane potential, impeded reactive oxygen species production, alleviated oxidative stress, and reduced lipid accumulation in oleic acid induced HepG2 cells. In in vivo studies, LBPs significantly inhibited body weight gain, reduced lipid levels in serum and liver, and improved oxidative damage in a dose-dependent manner in mice fed a high-fat diet. Moreover, LBPs ameliorated hepatic steatosis and suppressed the expression of hepatic-lipogenesis-related genes (SREBP-1c, FAS, ACC1, and SCD-1) and promoted lipolysis genes (SRB1 and HL) and lipid oxidation genes (PPARα and CPT-1) in mice fed a high-fat diet. CONCLUSION: It was concluded that LBPs are a potential complementary therapeutic alternative in the development of functional foods to curb obesity and obesity-related diseases, such as metabolic syndrome. © 2021 Society of Chemical Industry.