Efficient ammonia synthesis from the air using tandem non-thermal plasma and electrocatalysis at ambient conditions.

While electrochemical N2 reduction presents a sustainable approach to NH3 synthesis, addressing the emission- and energy-intensive limitations of the Haber-Bosch process, it grapples with challenges in N2 activation and competing with pronounced hydrogen evolution reaction. Here we present a tandem air-NOx-NOx--NH3 system that combines non-thermal plasma-enabled N2 oxidation with Ni(OH)x/Cu-catalyzed electrochemical NOx- reduction. It delivers a high NH3 yield rate of 3 mmol h-1 cm-2 and a corresponding Faradaic efficiency of 92% at -0.25 V versus reversible hydrogen electrode in batch experiments, outperforming previously reported ones. Furthermore, in a flow mode concurrently operating the non-thermal plasma and the NOx- electrolyzer, a stable NH3 yield rate of approximately 1.25 mmol h-1 cm-2 is sustained over 100 h using pure air as the intake. Mechanistic studies indicate that amorphous Ni(OH)x on Cu interacts with hydrated K+ in the double layer through noncovalent interactions and accelerates the activation of water, enriching adsorbed hydrogen species that can readily react with N-containing intermediates. In situ spectroscopies and density functional theory (DFT) results reveal that NOx- adsorption and their hydrogenation process are optimized over the Ni(OH)x/Cu surface. This work provides new insights into electricity-driven distributed NH3 production using natural air at ambient conditions.

Heme and Cu2+-induced vasoactive intestinal peptide (VIP) tyrosine nitration: A possible molecular mechanism for the attenuated anti-inflammatory effect of VIP in inflammatory diseases.

Vasoactive intestinal peptide (VIP) is a neuropeptide that play an important role in immunoregulation and anti-inflammation. Numerous inflammatory/autoimmune disorders are associated with decreased VIP binding ability to receptors and diminished VIP activation of cAMP generation in immune cells. However, the mechanisms linking oxidative/nitrative stress to VIP immune dysfunction remain unknown. It has been reported that the elevated heme or Cu2+ in inflammatory diseases can cause oxidative and nitrative damage to nearby biological targets under high oxidative stress conditions, which affects the structure and activity of linked peptides or proteins. Thus, the VIP down-regulated immune response may be interfered by redox metal catalyzed VIP tyrosine nitration. To explore this, we systematically investigated the possibility of heme or Cu2+ to catalyze VIP tyrosine nitration. The results showed that Tyr10 and Tyr22 of VIP can both be nitrated in heme/H2O2/NO2- system as well as in Cu2+/H2O2/NO2- system. Then, we used synthetic mutant VIPs with tyrosine residues substituted by 3-nitrotyrosine to study the impact of tyrosine nitration on VIP activity in SHSY-5Y cells. Our findings demonstrated that VIP nitration dramatically decreased the content of its α-helix and random coil, suggesting that VIP nitration might reduce its affinity to the receptor. This was further confirmed in the cAMP assay. The results showed that 10 nM of these tyrosine nitrated VIPs could significantly (p < 0.01) decrease cAMP secretion compared to the wild type VIP. Our data reveal that the attenuation of the neuroprotective effect of VIP in inflammation-related diseases might be attributed to metal-catalyzed VIP tyrosine nitration.

An electron-hole rich dual-site nickel catalyst for efficient photocatalytic overall water splitting.

Photocatalysis offers an attractive strategy to upgrade H2O to renewable fuel H2. However, current photocatalytic hydrogen production technology often relies on additional sacrificial agents and noble metal cocatalysts, and there are limited photocatalysts possessing overall water splitting performance on their own. Here, we successfully construct an efficient catalytic system to realize overall water splitting, where hole-rich nickel phosphides (Ni2P) with polymeric carbon-oxygen semiconductor (PCOS) is the site for oxygen generation and electron-rich Ni2P with nickel sulfide (NiS) serves as the other site for producing H2. The electron-hole rich Ni2P based photocatalyst exhibits fast kinetics and a low thermodynamic energy barrier for overall water splitting with stoichiometric 2:1 hydrogen to oxygen ratio (150.7 µmol h-1 H2 and 70.2 µmol h-1 O2 produced per 100 mg photocatalyst) in a neutral solution. Density functional theory calculations show that the co-loading in Ni2P and its hybridization with PCOS or NiS can effectively regulate the electronic structures of the surface active sites, alter the reaction pathway, reduce the reaction energy barrier, boost the overall water splitting activity. In comparison with reported literatures, such photocatalyst represents the excellent performance among all reported transition-metal oxides and/or transition-metal sulfides and is even superior to noble metal catalyst.

Mussel inspired multifunctional bovine serum albumin (BSA) coatings loaded with Baicalein (BAI) to enhance osteogenesis and resist oxidative stress for potential application on implant.

Oxidative stress is associated with most traumatic or pathological bone defects, and seriously affects the effect of implantation. The construction of antioxidative and osteogenic coatings is of great significance to accelerate the bone regeneration of implants. In this study, baicalein (BAI), a nature flavonoid drug, was loaded in bovine serum albumin (BSA) by desolvent method to prepare BAI-BSA composite protein, and tannic acid (TA)/BAI-BSA coatings were further built via layer by layer self-assembly technology. BAI-BSA possesses good biocompatibility that showed no cytotoxicity to osteoblasts and erythrocytes, and helps to enhance the activity of alkaline phosphatase (ALP) and promote the formation of osteogenic mineralized calcium nodules. After assembled with TA, BAI-BSA coating significantly promoted cell adhesion and in vitro osteogenic mineralization of MC3T3-E1. Moreover, BAI drug loading improved the antioxidative function of BSA coatings effectively. The scavenging rates of (TA/BAI-BSA-10)4 for ABTS+• and DPPH• free radicals were 69.6 ± 16.1 % and 53.4 ± 2.4 %, respectively. At cellular level, the TA/BAI-BSA coating effectively inhibited the impact of oxidative stress on the oxidative damage of osteoblasts. The drug-loaded protein coatings possess both great antioxidative and osteogenic functions, which have important potential in the field of bone repair.

Stretchable V2O5/PEDOT supercapacitors: a modular fabrication process and charging with triboelectric nanogenerators.

Stretchable energy storage devices are of great importance for the viable applications of wearable/stretchable electronics. Studies on stretchable energy storage devices, especially supercapacitors (SCs), have shown encouraging progress. However, challenges still remain in the pursuit of high specific capacitances and facile fabrication methods. Herein, we report a modular materials fabrication and assembly process for stretchable SCs. With a V2O5/PEDOT composite as the active material, the resulting stretchable SCs exhibited high areal specific capacitances up to 240 mF cm-2 and good capacitance retention at a strain of 50%. To demonstrate the facile assembly process, a stretchable wristband was fabricated by simply assembling SC cells in series to deliver a voltage higher than 2 V. Charging the wristband with a triboelectric nanogenerator (TENG) to light an LED was further demonstrated, indicating the potential to integrate our SCs with environmental energy harvesters for self-powered stretchable devices.

Copper(II) tungstate nanoflake array films: sacrificial template synthesis, hydrogen treatment, and their application as photoanodes in solar water splitting.

We report the preparation of CuWO4 nanoflake (NF) array films by using a solid phase reaction method in which WO3 NFs were employed as sacrificial templates. The SEM, TEM and XRD results demonstrated that the obtained CuWO4 films possessed a network structure that was composed of single crystalline NFs intersected with each other. The CuWO4 NF films showed superior photoelectrochemical (PEC) activity to other CuWO4 photoanodes reported recently for the oxygen evolution reaction (OER). We attributed the high activity to the unique morphological and crystalline structure of the CuWO4 film, which enhanced the photoactivity by providing a large specific area, a short hole transport distance from the inside of CuWO4 to the CuWO4/solution interface, and a low grain boundary density. Hydrogen treatment by annealing the CuWO4 NF film in mixed gases of H2 and Ar could further enhance the photoactivity, as hydrogen treatment significantly increased the electron density of CuWO4 by generating oxygen vacancy in the lattice. The photocurrent density for OER obtained on the hydrogen-treated (H-treated) CuWO4 NF film is the largest ever reported on CuWO4 photoanodes in the literature. Moreover, the CuWO4 photoanodes exhibit good stability in weak alkaline solution, while the H-treated CuWO4 photoanodes exhibit acceptable stability. This work not only reveals the potential of CuWO4 as a photoanode material for solar water splitting but also shows that the construction of nanostructured CuWO4 photoanodes is a promising method to achieve high PEC activity toward OER.