Cationic Oxidative Leaching Engineering Modulated In Situ Self-Reconstruction of Nickel Sulfide for Superior Water Oxidation.

Tuning the electroactive surface species of electrocatalysts remains a significant challenge for achieving highly efficient oxygen evolution reactions. Herein, we propose an innovative in situ leaching strategy, modulated by cationic oxidation, to achieve active self-reconstruction of these catalysts. Vanadium is introduced as a cation into Ni3S2 and oxidized under low oxidative potential, leading to subsequent leaching into the electrolyte and triggering self-reconstruction. The structural evolution from V-Ni3S2 to Ni(OH)2 and subsequently to NiOOH is identified by operando Raman as a three-step transition. In contrast, V-free Ni3S2 is unable to bypass the thermodynamically predicted nickel oxysulfide products to transform into active NiOOH. As a result, the self-restructured V-Ni3S2 only needs an ultralow overpotential of 155 mV at 10 mA cm-2, outperforming V-free Ni3S2 and many other advanced catalysts. This work provides new guidelines for manipulating in situ leaching to modulate the self-reconstruction of catalysts.

Size-Tunable Olive-Like Anatase TiO2 Coated with Carbon as Superior Anode for Sodium-Ion Batteries.

Olive-shaped anatase TiO2 with tunable sizes in nanoscale are designed employing polyvinyl alcohol (PVA) as structure directing agents to exert dramatic impacts on structure shaping and size manipulation. Notably, the introduced PVA simultaneously serves as carbon sources, bringing about a homogenous carbon layer with intimate coupling interfaces for boosted electronic conductivity. Constructed from tiny crystalline grains, the uniformly dispersed carbon-coated TiO2 nano-olives (TOC) possess subtle loose structure internally for prompt Na+ transportations. When utilized for sodium-ion storage, the size effects are increasingly significant at high charge-discharge rates, leading to the much superior rate performances of TOC with the smallest size. Bestowed by the improved Na+ adsorption and diffusion kinetics together with the promoted electron transfer, it delivers a high specific capacity of 267 mAh g-1 at 0.1 C (33.6 mA g-1 ) and sustains 110 mAh g-1 at a rather high rate of 20 C. Even after cycled at 10 C over 1000 cycles, a considerable capacity of 125 mAh g-1 with a retention of 94.6% is still obtained, highlighting its marvelous long-term cyclability and high-rate capabilities.

Voltage activation induced MoO42- dissolution to enhance performance of iron doped nickel molybdate for oxygen evolution reaction.

Transition metal-based precatalysts are typically voltage-activated before electrochemical testing in the condition of alkaline oxygen evolution reaction. Nevertheless, the impact of voltage on the catalyst and the anion dissolution is frequently disregarded. In this study, Fe-doped NiMoO4 (Fe-NiMoO4) was synthesized as a precursor through a straightforward hydrothermal method, and MoFe-modified Ni (oxygen) hydroxide (MoFe-NiOxHy) was obtained via cyclic voltammetry (CV) activation. The effects of voltage on Fe-NiMoO4 and the dissolved inactive MoO42- ions in the process were examined in relation to OER performance. It has demonstrated that the crystallinity of the catalyst is reduced by voltage, thereby enhancing its electrocatalytic activity. The electron distribution state can be adjusted during the application of voltage, leading to the generation of additional active sites and an acceleration in the reaction rate. Additionally, MoO42- exhibits potential dependence during its dissolution. In the OER process, the dissolution of MoO42- enhances the reconstruction degree of Fe-NiMoO4 into the active substance and expedites the formation of active Ni(Fe)OOH. Hence, the optimized MoFe-NiOxHy exhibited exceptional electrocatalytic performance, with a current density of 100 mA cm-2 achieved at an overpotential of only 256 mV. This discovery contributes to a more comprehensive understanding of alkaline OER performance under the influence of applied voltage and the presence of inactive oxygen ions, offering a promising avenue for the development of efficient electrocatalysts.

Oxyanion Engineering Suppressed Iron Segregation in Nickel-Iron Catalysts Toward Stable Water Oxidation.

Nickel-iron catalysts represent an appealing platform for electrocatalytic oxygen evolution reaction (OER) in alkaline media because of their high adjustability in components and activity. However, their long-term stabilities under high current density still remain unsatisfactory due to undesirable Fe segregation. Herein, a nitrate ion (NO3 - ) tailored strategy is developed to mitigate Fe segregation, and thereby improve the OER stability of nickel-iron catalyst. X-ray absorption spectroscopy combined with theoretical calculations indicate that introducing Ni3 (NO3 )2 (OH)4 with stable NO3 - in the lattice is conducive to constructing the stable interface of FeOOH/Ni3 (NO3 )2 (OH)4 via the strong interaction between Fe and incorporated NO3 - . Time of flight secondary ion mass spectrometry and wavelet transformation analysis demonstrate that the NO3 - tailored nickel-iron catalyst greatly alleviates Fe segregation, exhibiting a considerably enhanced long-term stability with a six-fold improvement over FeOOH/Ni(OH)2 without NO3 - modification. This work represents a momentous step toward regulating Fe segregation for stabilizing the catalytic performances of nickel-iron catalysts.

Microbial synthesis of efficient palladium electrocatalyst with high loadings for oxygen reduction reaction in acidic medium.

Whereas limited amount of precious metal adsorbed by bacteria conflicting the needs of high loadings for better catalytic performances, cell disruption technology was adopted to smash Shewanella cells in this work, releasing abundant oxygen functional groups inside the cells for better adsorption of palladium ion. Then palladium catalysts were synthesized in two ways: 1) Pd catalyst supported on carbonized-broken-bacterial (Pd/FHNC) was obtained after direct carbonization and reduction; 2) Electrospinning technology was used to spin the broken Shewanella into fibers, and Pd nanoparticles supported on nitrogen-doped carbon nanofiber (Pd/NCNF) was prepared following carbonization and hydrogen reduction. The as-prepared catalysts exhibit excellent oxygen reduction reaction (ORR) electrocatalytic performance in the acid medium. The mass specific activities at 0.7 V of Pd/FHNC and Pd/NCNF were 0.213 A mg-1 and 0.121 A mg-1 which were 5.92 and 3.36 times than those of commercial Pd/C(0.036 A mg-1) respectively, and they also displayed higher stability than Pd/C. Furthermore, the Pd loadings of Pd/FHNC and Pd/NCNF were 21.52% and 17.13% respectively. An explanation for the improved performance is the co-doping of nitrogen and phosphorus, also the tight integration of Pd and broken-bacterial. Herein, we propose a novel and effective method for synthesis of ORR electrocatalysts.

Investigating the active sites in molybdenum anchored nitrogen-doped carbon for alkaline oxygen evolution reaction.

Developing durable and efficient non-precious-metal based catalysts for oxygen evolution reaction (OER) is highly desirable in the field of electrocatalysis. In this work, a series of novel Mo anchored N-doped carbon catalysts (denoted as Mo/NC-T) were prepared starting from the zeolitic imidazolate framework 8 (ZIF-8) precursor. Firstly, Mo doped ZIF-8 precursor (Mo/ZIF-8) with a regular polyhedron structure was formed through a simple ion-exchange method process between molybdenum pentachloride (MoCl5) and ZIF-8. Afterward, Mo/ZIF-8 was converted to Mo/NC-T through a two-step calcination process in nitrogen (N2) and ammonia (NH3). The as-synthesized Mo/NC-T samples exhibited superior electrocatalytic OER properties. The optimal sample at 650 °C (Mo/NC-650) presented a low overpotential of 320 mV at 10 mA cm-2, a Tafel slope of 71 mV dec-1, and an outstanding long-term stability for 30 h in 1 M KOH solution. The remarkable OER activity of Mo/NC-T could be ascribed to the structural stability of carbon matrix and the synergistic effect between Mo3+ (derived from Mo-C bonds) and pyridinic N. This work provides a novel perspective on the roles of Mo species in the N-doped carbon electrocatalysts for OER.

Insight into the amorphous nickel-iron (oxy)hydroxide catalyst for efficient oxygen evolution reaction.

The specific roles of Ni and Fe in nickel-iron (oxy)hydroxide catalyst (NiFeOx(OH)y) are extensively discussed during oxygen evolution reaction (OER). However, there still remains controversy about whether Ni or Fe species as the dominate active site. In this work, we reported the NiFeOx(OH)y catalysts with varied atomic ratio of nickel and iron for OER to explore the dominate active site during OER processes. From the electrochemical performances, the similar Tafel slopes of catalysts with Fe species can achieve at a level of 40 mV dec-1, outperforming the Tafel slopes of catalysts without Fe species. Thus, it can be concluded that the present Fe site can serve as the dominant active site in NiFeOx(OH)y for OER. Meanwhile, the Ni species is proved as the OH- adsorption site, which is beneficial to the Fe site to deliver a better OER performance. As a result, the catalyst with an optimal Ni/Fe interface (atomic ratio of 1 : 1.18) displays outstanding OER performances. It only requires a low overpotential of 250 mV to deliver current density of 10 mA cm-2 and exhibits a small Tafel slope of 39 mV dec-1. This catalyst also shows remarkable stability with negligible potential decay after 50 h at a current density of 50 mA cm-2. This work offers a new sight into the specific roles of Ni and Fe in NiFeOx(OH)y for OER.

Palladium-Catalyzed Thioetherification of Quinolone Derivatives via Decarboxylative C-S Cross-Couplings.

A highly efficient and practical procedure for palladium-catalyzed direct thioetherification of quinolone derivatives with diaryl disulfides through decarboxylative C-S coupling has been established. The reaction could proceed smoothly under air in the presence of Pd(OAc)2 and Ag2 CO3 in DMSO. This protocol provides an appealing alternative to existing approaches to construct aryl sulfides of quinolone derivatives, which may be used as key intermediates in the synthesis of drug candidates.