Construction of unique NiCoP/FeNiCoP hollow heterostructured ellipsoids with modulated electronic structure for enhanced overall water splitting.

Transition metal phosphides have been demonstrated to be promising non-noble catalysts for water splitting, yet their electrocatalytic performance is impeded by unfavorable free energies of adsorbed intermediates. The achievement of nanoscale modulation in morphology and electronic states is imperative for enhancing their intrinsic electrocatalytic activity. Herein, we propose a strategy to expedite the water splitting process over NiCoP/FeNiCoP hollow ellipsoids by modulating the electronic structure and d-band center. These unique phosphorus (P) vacancies-rich ellipsoids are synthesized through an ion-exchange reaction between uniform NiCo-nanoprisms and K3[Fe(CN)6], followed by NaH2PO2-assisted phosphorization under N2 atmosphere. Various characterizations reveals that the titled catalyst possesses high specific surface area, abundant porosity, and accessible inner surfaces, all of which are beneficial for efficient mass transfer and gas diffusion. Moreover, density functional theory (DFT) calculations further confirms that the NiCoP/FeNiCoP heterojunction associated with P vacancies regulate the electronic structures of d-electrons and p-electrons of Co and P atoms, respectively, resulting in a higher desorption efficiency of adsorbed H* intermediates with a lower energy barrier for water splitting. Due to the aforementioned advantages, the resultant NiCoP/FeNiCoP hollow ellipsoids exhibit remarkably low overpotentials of 45 and 266 mV for hydrogen and oxygen evolution reaction to achieve the current densities of 10 and 50 mA cm-2, respectively. This work not only reports the synthesis of a hollow double-shell structure of NiCoP/FeNiCoP but also introduces a novel strategy for constructing a multifunctional electrocatalyst for water splitting.

P-doped Co3S4/NiS2 heterostructures embedded in N-doped carbon nanoboxes: Synergistical electronic structure regulation for overall water splitting.

Water splitting using transition metal sulfides as electrocatalysts has gained considerable attention in the field of renewable energy. However, their electrocatalytic activity is often hindered by unfavorable free energies of adsorbed hydrogen and oxygen-containing intermediates. Herein, phosphorus (P)-doped Co3S4/NiS2 heterostructures embedded in N-doped carbon nanoboxes were rationally synthesized via a pyrolysis-sulfidation-phosphorization strategy. The hollow structure of the carbon matrix and the nanoparticles contained within it not only result in a high specific surface area, but also protects them from corrosion and acts as a conductive pathway for efficient electron transfer. Density functional theory (DFT) calculations indicate that the introduction of P dopants improves the conductivity of NiS2 and Co3S4, promotes the charge transfer process, and creates new electrocatalytic sites. Additionally, the NiS2-Co3S4 heterojunctions can enhance the adsorption efficiency of hydrogen intermediates (H*) and lower the energy barrier of water splitting via a synergistic effect with P-doping. These characteristics collectively enable the titled catalyst to exhibit excellent electrocatalytic activity for water splitting in alkaline medium, requiring only small overpotentials of 150 and 257 mV to achieve a current density of 10 mA cm-2 for hydrogen and oxygen evolution reactions, respectively. This work sheds light on the design and optimization of efficient electrocatalysts for water splitting, with potential implications for renewable energy production.

Assessment of the Bioaccessibility of Carotenoids in Goji Berry (Lycium barbarum L.) in Three Forms: In Vitro Digestion Model and Metabolomics Approach.

Goji berry (Lycium barbarum L., LBL) is a good source of carotenoids, while the bioaccessibility of various types of LBL carotenoids has not been explored. In the study, eight carotenoids, three carotenoid esters and two carotenoid glycosylated derivatives were identified by a non−targeted metabolomics approach. The dried LBL (DRI), LBL in water (WAT), and LBL in "Baijiu" (WIN) were used to recreate the three regularly chosen types of utilization, and the in vitro digestion model showed that the bioaccessibility of the carotenoids increased significantly from the oral to the gastric and intestinal phase (p < 0.05). The bioaccessibility of LBL carotenoids was the most elevated for DRI (at 28.2%), followed by WIN and WAT (at 24.9% and 20.3%, respectively). Among the three carotenoids, zeaxanthin dipalmitate showed the highest bioaccessibility (51.8−57.1%), followed by ß−carotene (51.1−55.6%) and zeaxanthin (45.2−56.3%). However, the zeaxanthin from DRI exhibited significantly higher bioaccessibility (up to 58.3%) than WAT and WIN in both the gastric and intestinal phases (p < 0.05). Results of antioxidant activity tests based on DPPH, FRAP, and ABTS showed that the addition of lipids improved the bioaccessibility of the carotenoids. (p < 0.05).