Cooperative Ni(Co)-Ru-P Sites Activate Dehydrogenation for Hydrazine Oxidation Assisting Self-powered H2 Production

Water electrolysis for H₂ production is restricted by the sluggish oxygen evolution reaction (OER). Using the thermodynamically more favorable hydrazine oxidation reaction (HzOR) to replace OER has attracted ever-growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru₁−NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen evolution reaction (HER), realizing an ultralow working potential of −60 mV and overpotential of 32 mV for a current density of 10 mA cm⁻², respectively. Inspiringly, two-electrode electrolyzer based on overall hydrazine splitting (OHzS) demonstrates outstanding activity with a record-high current density of 522 mA cm⁻² at cell voltage of 0.3 V. DFT calculations elucidate the cooperative Ni(Co)−Ru−P sites in Ru₁−NiCoP optimize H* adsorption, and enhance adsorption of *N₂H₂ to significantly lower the energy barrier for hydrazine dehydrogenation. Moreover, a self-powered H₂ production system utilizing OHzS device driven by direct hydrazine fuel cell (DHzFC) achieve a satisfactory rate of 24.0 mol h⁻¹ m⁻².     

Effi cient synthesis of fused pyrazoles via simple cyclization of o-alkynylchalcones with hydrazine

The synthesis of pyrazole derivatives from o-alkynylchalcones and hydrazine via simple cyclization is described. This greener syntheticmethodology provides a straightforward approach to the synthesis of a variety of pyrazole derivatives under mild reaction condition.     

Electrode Modification Using Alkynyl Substituted Fe(II) Phthalocyanine via Electrografting and Click Chemistry for Electrocatalysis

In this work, tetrakis(5‐hexyn‐oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4‐azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne‐azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM^?1 and a limit of detection of 1.09 µM.     

Kinetics and Mechanism of Catalytic Reduction of U(VI) with Hydrazine on Platinum Catalysts in Nitric Acid Media

The kinetics of U(IV) produced by hydrazine reduction of U(VI) with platinum as a catalyst in nitric acid media was studied to reveal the reaction mechanism and optimize the reaction process. Electron spin resonance (ESR) was used to determine the influence of nitric acid oxidation. The effects of nitric acid, hydrazine, U(VI) concentration, catalyst dosage and temperature on the reaction rate were also studied. In addition, the simulation of the reaction process was performed using density functional theory. The results show that the influence of oxidation on the main reaction is limited when the concentration of nitric acid is below 0.5 mol/L. The reaction kinetics equation below the concentration of 0.5 mol/L is found as: -dc(UO₂²⁺)/dt)=kc^0.5323(UO₂²⁺)c^0.2074(N₂H₅⁺)c^-0.2009(H⁺). When the temperature is 50 ℃, and the solid/liquid ratio r is 0.0667 g/mL, the reaction kinetics constant is k=0.00199 (mol/L)^0.4712/min. Between 20 ℃ and 80 ℃, the reaction rate gradually increases with the increase of temperature, and changes from chemically controlled to diffusion-controlled. The simulations of density functional theory give further insight into the influence of various factors on the reaction process, with which the reaction mechanisms are determined according to the reaction kinetics and the simulation results.     

Creating the Ideal Push-Pull System for Electrocatalysis: A Comparative Study on Symmetrical and Asymmetrical Cardanol-based Cobalt Phthalocyanines

A symmetrical cardanol-based cobalt phthalocyanine (Pc) along with its asymmetrical acid-based derivatives were synthesized and applied in the electrocatalysis of hydrazine. Despite the inhibition of electron movement by the bulky cardanol-based substituent throughout the series of molecules, an ideal combination of substituents was established in GCE- 3 (2,9,16-tris(3-pentadecylphenoxy)-23-mono propionic acid phthalocyanato cobalt (II)) where a limit of detection (LoD) value of 5.10 μM (signal to noise ratio=5) was recorded for the detection of hydrazine. The results obtained serve as an illustration that the combination of electron-donating and electron-withdrawing substituents has a significant influence on the complete functioning of the phthalocyanine molecule(s) being investigated.     

A highly selective HBT-based “turn-on” fluorescent probe for hydrazine detection and its application

As one of the important industrial chemicals, hydrazine (N₂H₄) can be inhaled through the skin, leading to many serious health issues. In this paper, we constructed a novel turn-on fluorescent probe HBTM for N₂H₄ detection based on ESIPT and ICT mechanism by incorporating the methyl dicyanvinyl group to 2-(2′-hydroxylphenyl) benzothiazole (HBT) fluorophore. The probe showed the following advantages: high sensitivity with detection limit of 2.9 × 10^?7 M, high selectivity over other related interfering species, wide linear range of 0–140 μM and pH value adaptation. Moreover, the probe could detect N₂H₄ on paper strips and image N₂H₄ in living cells.     

Synthesis of 2‐Aryl‐5‐oxo‐4‐[2‐(phenylmethylidene)hydrazino]‐2,5‐dihydro‐1H‐pyrrole‐3‐carboxylates by the Reaction between Hydrazones,Acetylenedicarboxylates, and 1‐Aryl‐N,N′‐bis(arylmethylidene)methanediamines

An efficient approach for the preparation of functionalized 2‐aryl‐2,5‐dihydro‐5‐oxo‐4‐[2‐(phenylmethylidene)hydrazino]‐1H‐pyrroles is described. The four‐component reaction between aldehydes, NH₂NH₂?H₂O, dialkyl acetylenedicarboxylates, and 1‐aryl‐N,N′‐bis(arylmethylidene)methanediamines proceeds in EtOH under reflux in good‐to‐excellent yields (Scheme 1). The structures of 4 were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS, and, in the case of 4f , by X‐ray crystallography). A plausible mechanism for this type of reaction is proposed (Scheme 2).     

Oxidative Deoximation with Sodium Perborate1

An efficient and convenient conversion of oximes to corresponding carbonyl compounds with sodium perborate in glacial acetic acid is reported.     

A cinnamoyl substituted Nile Red-based probe to detect hydrazine

Herein we discovered that a Nile Red-based probe with a cinnamoyl unit was highly selective and sensitive to N₂H₄. Hydrazinolysis by N₂H₄ would release a hydroxyl substituted Nile Red and result in remarkable fluorescence quench. Importantly, Cys/Hcy would not interrupt the N₂H₄ recognition. This is because, for this probe, the combination of the π-π conjugate system can stabilize the ethylene union, which results in the nucleophilic addition of the thiol group of Cys/Hcy becomes non-effective.     

Synthesis of 4‐Alkyl‐1(2H)‐phthalazinones and 4‐Alkyl‐2,3‐benzoxazin‐1‐ones via Ring Cleavage of 3‐Substituted N‐Alkylated‐3‐hydroxyisoindolin‐1‐ones

Abstract

N‐Alkyl (Me, Et, i‐Pr, t‐Bu)‐substituted phthalimdes 5a–d were easily transformed to 1(2H)‐phthalazinones 8d–i and 2,3‐benzoxazin‐1‐ones 9d, f, and j via a one‐pot addition–decyclization–cyclocondensation process.