Green hydrogen (H₂) is an import energy carrier due to the zero-carbon emission in the energy cycle. Nevertheless, green H₂ production based on electrolyzer and photovoltaics (EZ/PV) remains limited due to the highly pH-dependant and energy exhausting overall water splitting. Herein, we report a series of Ru-nanocluster-modified mesoporous nanospheres (Ru_x@mONC) as pH-universal electrocatalysts towards both hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR). The optimal catalyst Ru₂₀@mONC realizes remarkable catalytic activity and stability towards both HER and HzOR regardless of electrolytes. As a result, the electrode pair of Ru₂₀@mONC//Ru₂₀@mONC requires low cell-potentials of 39/429, 405/926, and 164/1,141 mV to achieve the current density of 10/100 mA·cm⁻², as well as the long-term stability for HzOR assisted electrochemical water splitting in alkaline, acidic, and neutral media, respectively. Those performances are more promising compared to the state-of-the-art electrocatalysts so far reported. A proof-of-concept test demonstrates an efficient production of green H₂ powered by a single-junction silicon solar cell, which may inspire the use of a cost-effective EZ/PV system. Furthermore, a combined spectroscopic and theoretical study verifies the formation of abundant Ru/NC heterointerfaces in Ru₂₀@mONC, which not only contributes to the balancing of H* adsorption/desorption in HER but also facilitates the *N₂H₂ dehydrogenation in HzOR.

Magneto-luminescent molecules have significant applications in data storage and quantum computing. However, design of these bi-functional molecules coupled with magnetic behavior and photoluminescence is still challenging. In this work, we report a metallofullerene DyErScN@Ⅰ_h-C₈₀ exhibiting single-molecule magnet (SMM) behavior and near-infrared emission. For DyErScN@Ⅰ_h-C₈₀, two functional lanthanide metal ions of Dy³⁺ (SMM function) and Er³⁺ (luminescent function) are integrated inside a fullerene cage using a trimetallic nitride template, and its structure has been unambiguously characterized by single-crystal X-ray diffraction. Magnetic measurements revealed that DyErScN@Ⅰ_h-C₈₀ behaves as a SMM with a blocking temperature up to 9 K resulting from the intramolecular magnetic interaction between Dy³⁺ and Er³⁺ ions. Moreover, DyErScN@Ⅰ_h-C₈₀ exhibits temperature-dependent near-infrared emission around 1.5 µm with multiple splitting peaks from Er³⁺, which arises from the influence of Dy³⁺ ion. This study provides a new strategy to synthesize new magneto-luminescent molecule materials.

A new Gd@C_2v(9)-C₈₂·2.5(S₈)·0.5(CS₂) co-crystal was prepared for the first time and characterized by single-crystal X-ray diffraction (XRD). The analysis clearly showed that, even though the C_2v(9)-C₈₂ cage is fully ordered, the endohedral Gd atoms are highly disordered. This result indicates the presence of highly delocalized endohedral Gd atoms, which has never been reported before. Density functional theory (DFT) calculations were used to rationalize the XRD results. The calculations reveal the presence of two local energy minima, a and b, with the latter existing as four conformers b1–b4. Whereas the energy difference between the two minima is calculated only ~ 10 kcal/mol, their interconversion is almost impossible due to a high energy barrier, of up to 35.98 kcal/mol. This suggests the existence of multiple low-energy positions for the endohedral Gd atom. In addition, a remarkable electron transfer from the C_2v(9)-C₈₂ cage to the S₈ moieties was demonstrated, which might result in a modified endohedral environment and further contribute to the occurrence of delocalized endohedral Gd atoms.