Ammonia (NH3) is one of the most important synthetic inorganic commodities. The current industrial NH3 production is dominated by the Haber–Bosch process with high energy cost and CO2 emission as well as the need for large-scale centralized operation. Liquid metals and molten salts have recently emerged as promising catalytic materials for NH3 synthesis. Herein, we present a molten system comprising Li–Zn alloy and eutectic LiCl–KCl salt for effective NH3 synthesis at 400 °C and 1 bar. The 70 mol% Li–Zn liquid alloy activates N2 dissociation more easily than the pure liquid Zn and the 60 mol% Li–Sn liquid alloy. Effective N2 fixation by the liquid Li–Zn alloy is followed by the hydrogenation of Li3N dissolved in the molten salt above. For the first time, this work reports a volcano-type relationship between the Li3N concentration in the molten salt and the NH3 synthesis rate when feeding H2 to the molten salt. Ab initio molecular dynamics simulations suggest that, within this system, both N2 cleavage and Li3N hydrogenation are quite reactive. Through combined experiments and simulations, this work unravels the molecular mechanisms of nitrogen fixation and ammonia synthesis in the liquid alloy–salt catalytic system, and also demonstrates effective strategies for improving the ammonia synthesis rate. Such a hybrid molten catalytic system offers a promising solution for distributed NH3 production with low energy cost and CO2 emission.
H2O2 is a green oxidant, which is widely used in chemical production, environmental remediation, sustainable energy conversion and the medical industry. The traditional anthraquinone method for producing H2O2 is facing issues, such as potential safety hazards and environmental pollution. Therefore, green and sustainable production of H2O2 is desirably investigated. Solar-driven photocatalytic synthesis of H2O2 is a promising method, which requires no additional energy input and will not produce new pollution. g-C3N4 is a kind of nonmetallic photocatalyst, which has the advantages of low cost, environmental friendliness and high stability. However, g-C3N4 still faces the problems of a narrow visible light response range, low photo-generated electron/hole separation efficiency and short carrier lifetime. The polymer properties of g-C3N4 are conducive to introducing foreign atoms into the main body of the tri-s-triazine structure. The electronic structure and optical properties of g-C3N4 can be adjusted by doping, which can significantly improve the photocatalytic performance of g-C3N4. In this work, phosphorus doped g-C3N4 (P/g-C3N4) is prepared by a simple chemical vapor deposition method. The doping process also introduced defects in the bulk phase of g-C3N4, which overcomes drawbacks such as weak visible light capturing ability, low charge separation and transfer efficiency, and a slow mass transfer rate. In addition, the optimized conduction band position further enhances the reduction ability of photo-generated electrons, making its photocatalytic performance magnify by one order of magnitude compared to that of pure g-C3N4. Driven by visible light, P/g-C3N4 produces H2O2 through the photocatalytic oxygen reduction reaction (ORR) in 2 h, reaching a high concentration of 1460.22 μM, and it also maintains good catalytic repeatability in three-cycle catalytic experiments. P/g-C3N4 achieves the goal of efficient, stable and green synthesis of H2O2.
The interest in multi-enzyme cascades for the synthesis of pharmaceutically relevant active ingredients has increased in recent years. Through a smart selection of enzymes, cascades enable multi-step synthesis in a one-pot reaction without the purification of intermediates. In this study, a five-enzyme cascade for the formation of cyclic 2′3′-GMP-AMP (2′3′-cGAMP) from adenosine and guanosine in seven reaction steps was successfully developed. First, the substrate scope of kinases for the phosphorylation of nucleosides and nucleotides was investigated, which were then combined in an enzyme cascade for 2′3′-cGAMP formation from adenosine, guanosine, and polyphosphate. An overall conversion of 57% of the substrates into 2′3′-cGAMP was achieved in relation to the initial guanosine concentration.
There are few reports on the direct epoxidation of propylene catalyzed by LaCoO3 perovskite to form propylene oxide (PO) (both experimental and theoretical studies), especially the promoting effect of Cu doping. Herein, we report a comprehensive mechanistic study using both DFT calculations and microkinetic simulations for undoped and Cu-doped LaCoO3(110)–Cl to explore the effects of Cu doping in LaCoO3 perovskite towards PO selectivity. The propylene oxidation process consists of two parallel pathways, i.e., allylic hydrogen stripping and propylene oxametalcycle (OOMMP) intermediate mechanisms. Our results indicated that doping Cu has little effect on the selectivity for PO on LaCoO3 without Cl due to its very low reactivity. Alternatively, in the presence of Cl, copper doping not only lowers the strength of the Brønsted base of molecular
In this study, we successfully synthesized a carbon-coated nickel phosphide composite catalyst (Ni2P@C) through a strategy of polyvinylpyrrolidone (PVP)-assisted pyrolysis and phosphidation of Ni-MOF. Thorough structural characterization revealed that the assistance of PVP significantly decreased the size of the nickel nanoparticles during pyrolysis, and the subsequent gas phosphidation transformed the metallic nickel into the Ni2P phase with strengthened Ni–P synergy. The resulting core–shell structured Ni2P@C possessed a substantial number of surface Niδ + sites with electron deficiency, which served as both a metal center to dissociate hydrogen and a Lewis acid to activate the C–O bond. Remarkably, under mild reaction conditions (120 °C and pH 2 of 2.0 MPa), the Ni2P@C composite demonstrated exceptional activity for hydrodeoxygenation of furfuryl alcohol, achieving an impressive 2-methylfuran productivity of 1.7 g2-MF gCata−1 h−1. These results surpass the performance of most non-noble metal catalysts currently reported. This study could provide valuable insights for the rational design of advanced carbon-coated Ni2P composite catalysts for hydrogenative biomass upgrading.
Sulfur undergoes various changes from solid S8 to soluble lithium polysulfides (Li2S8–Li2S4) and insoluble Li2S2 and Li2S during charge–discharge cycling of lithium sulfur (Li–S) batteries. The dissolution of sulfur-containing compounds in battery electrolytes and their movement between electrodes, known as the polysulfide shuttle effect, decreases the battery performance. In addition, the kinetics of sulfur redox reactions are sluggish. Different host materials have been explored to address these issues. Herein, nanofibres of conjugated polymers have been synthesised that have multiple electron transport pathways. The cross-linker is nickel phthalocyanine tetrasulfonic acid tetrasodium salt (NPTS). Sulfur is situated in the voids of cross-linked nanofibres of the polymer and Ni2+ present in NPTS attracts the negative charge-bearing polysulfides. Due to the confinement and polyvalent electrostatic attraction, the solubility of sulfur and polysulfide is suppressed. Density functional theory calculations revealed that S2− interacts with Ni2+ and Li+ interacts with the pyrrolic nitrogens of PPy-NPTS. The overlap of the p-orbitals of sulfur and nickel is determined from the density of states calculations. The bond length of Li2S is ideal for this interaction, hence this molecule showed the highest adsorption energy with the cross-linked polymeric host. The adsorption energy decreased upon an increase in the number of sulfur atoms in the polysulfide chain due to the bond length mismatch. However, due to electrostatic polyvalent interaction, the adsorption energy is sufficient to suppress polysulfide dissolution. Thus, the structure of this host material with nickel cations and pyrrolic nitrogens is suitable to adsorb lithium polysulfides irrespective of their length, unlike neutral hosts. This efficient binding also improved the electrocatalysis of the sulfur redox reaction. Hence, the Li–S battery containing these nanofibres showed a specific capacity of 1326 mA h g−1 at 0.2C. Batteries fabricated considering practical parameters, such as low electrolyte to sulfur ratio of 5.0 μL mg−1 with sulfur loading of 4.0 mg cm−2, showed impressive performance.