RESUMEN
A dynamic-regulated Pd-Fe-N electrocatalyst was effectively constructed with electron-donating and back-donating effects, which serves as an efficient engineering strategy to optimize the electrocatalytic activity. The designed PdFe3/FeN features a comprehensive electrocatalytic performance toward the nitrogen reduction reaction (NRR, yield rate of 29.94 µg h-1 mgcat-1 and FE of 38.43% at -0.2 V vs RHE) and oxygen evolution reaction (OER, 308 mV at 100 mA cm-2). Combining in situ ATR-FTIR, XAS, and DFT results, the role of the interstitial-N-dopant-induced electron sponge effect has been significantly elucidated in strengthening the electrocatalytic NRR process. Specifically, the introduction of a N dopant, an electron acceptor, initiates the generation of robust Lewis-acidic Fe sites, facilitating free N2 capture and bonding. Simultaneously, after NH3 adsorption, the N dopant can back-donate electrons to Fe sites, strengthening the NH3 deportation through weakening the Lewis acidity of Fe centers. Besides, the electron-deficient Fe sites contribute to the reconstruction of FeOOH, the real active species during the OER, which accelerates the four-electron reaction kinetics. This research offers a perspective on electrocatalyst design, potentially facilitating the evolution of advanced material engineering for efficient electrocatalytic synthesis and energy storage.
RESUMEN
Ammonia, a vital component in the synthesis of fertilizers, plastics, and explosives, is traditionally produced via the energy-intensive and environmentally detrimental Haber-Bosch process. Given its considerable energy consumption and significant greenhouse gas emissions, there is a growing shift toward electrocatalytic ammonia synthesis as an eco-friendly alternative. However, developing efficient electrocatalysts capable of achieving high selectivity, Faraday efficiency, and yield under ambient conditions remains a significant challenge. This review delves into the decades-long research into electrocatalytic ammonia synthesis, highlighting the evolution of fundamental principles, theoretical descriptors, and reaction mechanisms. An in-depth analysis of the nitrogen reduction reaction (NRR) and nitrate reduction reaction (NitRR) is provided, with a focus on their electrocatalysts. Additionally, the theories behind electrocatalyst design for ammonia synthesis are examined, including the Gibbs free energy approach, Sabatier principle, d-band center theory, and orbital spin states. The review culminates in a comprehensive overview of the current challenges and prospective future directions in electrocatalyst development for NRR and NitRR, paving the way for more sustainable methods of ammonia production.
RESUMEN
Manganese (Mn)-based layer-structured transition metal oxides are considered as excellent cathode materials for potassium ion batteries (KIBs) owing to their low theoretical cost and high voltage plateau. The energy density and cycling lifetime, however, cannot simultaneously satisfy the basic requirements of the market for energy storage systems. One of the primary causes results from the complex structural transformation and transition metal migration during the ion intercalation and deintercalation process. The orbital and electronic structure of the octahedral center metal element plays an important role for maintaining the octahedral structural integrity and improving the K+ diffusivity by the introduced heterogeneous [Me-O] chemical bonding. A multitransition metal oxide, P3-type K0.5Mn0.85Co0.05Fe0.05Al0.05O2 (KMCFAO), was synthesized and employed as a cathode material for KIBs. Beneficial from the larger layer spacing for K+ to better accommodate and effectively preventing the irreversible structural transformation in the insertion/extraction process, it can reach a superior capacity retention up to 96.8% after 300 cycles at a current density of 500 mA g-1. The full cell of KMCFAO//hard carbon exhibits an encouraging promising energy density of 113.8 W h kg-1 at 100 mA g-1 and a capacity retention of 72.6% for 500 cycles.
