Large scale synthesis of high-efficiency bifunctional electrocatalyst based on cost-effective and earth-abundant transition metal for overall water splitting in the alkaline environment is indispensable for renewable energy conversion. In this regard, meticulous design of active sites and probing their catalytic mechanism on both cathode and anode with different reaction environment at molecular-scale are vitally necessary. Herein, a coordination environment inheriting strategy is presented for designing low-coordination Ni2+ octahedra (L-Ni-8) atomic interface at a high concentration (4.6 at.%). Advanced spectroscopic techniques and theoretical calculations reveal that the self-matching electron delocalization and localization state at L-Ni-8 atomic interface enable an ideal reaction environment at both cathode and anode. To improve the efficiency of using the self-modification reaction environment at L-Ni-8, all of the structural features, including high atom economy, mass transfer, and electron transfer, are integrated together from atomic-scale to macro-scale. At high current density of 500 mA/cm2, the samples synthesized at gram-scale can deliver low hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) overpotentials of 262 and 348 mV, respectively.
ABSTRACT In recent years, the exploration of a practical strategy for novel energetic molecules with high energy and low sensitivity is very desirable but highly challenging. Novel ionic energetic molecules have attracted much attention in this area due to their prominent advantages including low sensitivities, high thermal stability, and excellent energy performances. Herein, five different ionic energetic molecules based on new monovalent and divalent 4-oxyl-3,5-dinitropyrazolate moieties with enhanced oxygen balance have been synthesized, characterized and evaluated as potential high-energy materials. Thermal stability, sensitivities and energy output test were measured and studied in detail. The heats of formation and energetic parameters were calculated by using Gaussian 09 suite of programs and EXPLO 5 code. The results suggest that all as-prepared new molecules exhibit good thermal stability with high decomposition temperature (3, 231°C; 5, 160°C; 6, 185°C; 7, 180°C; 8, 213°C), and relative low sensitivity (IS > 20 J, FS = 324 N). Inheriting the significant oxygen content of monovalent and divalent 4-oxyl-3,5-dinitropyrazolate moieties, they also possess good energy properties (vD = 8238 ~ 9208 m s?1, P = 26.8 ~ 36.7 GPa, Vo = 481.8 ~ 959.4 L kg?1), which make them competitive high-energy materials. 相似文献
Carbon-carbon (C-C) coupling reactions represent one of the most powerful tools for the synthesis of complex natural products, bioactive molecules developed as drugs and agrochemicals. In this work, a multifunctional nanoreactor for C-C coupling reaction was successfully fabricated via encapsulating the core-shell Cu@Ni nanocubes into ZIF-8 (Cu@Ni@ZIF-8). In this nanoreactor, Ni shell of the core-shell Cu@Ni nanocubes was the catalytical active center, and Cu core was in situ heating source for the catalyst by absorbing the visible light. Moreover, benefiting from the plasmonic resonance effect between Cu@Ni nanocubes encapsulated in ZIF-8, the absorption range of nanoreactor was widened and the utilization rate of visible light was enhanced. Most importantly, the microporous structure of ZIF-8 provided shape-selective of reactant. This composite was used for the highly shape-selective and stable photocatalysed C-C coupling reaction of boric acid under visible light irradiation. After five cycles, the nanoreactor still remained high catalytical activity. This Cu@Ni@ZIF-8 nanoreactor opens a way for photocatalytic C-C coupling reactions with shape-selectivity.
