Defect engineering with N-doped carbon hybrid cobalt-molybdenum phosphide nanosheets wrapped molybdenum oxide nanorods for alkaline hydrogen evolution reaction.

Regulating the electrocatalytic hydrogen evolution reaction (HER) performance through defect engineering of the surface of the catalysts is an effective pathway. Herein, cobalt-molybdenum phosphide (CoMoP) nanosheets wrapped molybdenum oxide (MoO3) core-shell nanorods (MoO3@CoMoP), as alkaline electrocatalysts with ligand-derived N-doped carbon hybrid and oxygen-vacancies, were synthesized via solvothermal approaches and followed by phosphorization. As expected, the MoO3@MoCoP affords efficient HER with a low overpotential (η) of 84.2 ± 0.4 mV at 10 mA cm-2. After phosphorization, not only the MoCoP active species are incorporated into the catalyst, but also the defects sites are achieved. Impressively, the metal-ligand-derived MoCoP are distributed uniformly in the N-doped carbon hybrid matrix, exhibiting well-exposed active sites. Benefiting from the synergy effect of MoCoP active species and oxygen-vacancy, the MoO3@MoCoP showed increased conductivity and stability, which can deliver a current density of 10 mA cm-2 over 40 h. MoO3@MoCoP exhibits an optimal electronic structure on the surface by charge redistribution at the interface, thereby optimizing the hydrogen adsorption energy and accelerating the hydrogen evolution kinetics. This work paves the way for the design of transition metal electrocatalysts with desirable properties through a promising strategy in the field of energy conversion.

Nitrogen-doped hollow mesoporous carbon spheres for efficient oxygen reduction.

Extensive investigations have been devoted to nitrogen-doped carbon materials as catalysts for the oxygen reduction reaction (ORR) in various conversion technologies. In this study, we introduce nitrogen-doped carbon materials with hollow spherical structures. These materials demonstrate significant potential in ORR activity within alkaline media, showing a half-wave potential of 0.87 V versus the reversible hydrogen electrode (RHE). Nitrogen-doped hollow carbon spheres (N-CHS) exhibit unique characteristics such as a thin carbon shell layer, hollow structure, large surface area, and distinct pore features. These features collectively create an optimal environment for facilitating the diffusion of reactants, thereby enhancing the exposure of active sites and improving catalytic performance. Building upon the promising qualities of N-CHS as a catalyst support, we employ heme chloride (1 wt%) as the source of iron for Fe doping. Through the carbonization process, Fe-N active sites are effectively formed, displaying a half-wave potential of 0.9 V versus RHE. Notably, when implemented as a cathode catalyst in zinc-air batteries, this catalyst exhibits an impressive power density of 162.6 mW cm-2.

Fe-N-C catalysts decorated with oxygen vacancies-rich CeOx to increase oxygen reduction performance for Zn-air batteries.

Platinum group metal (PGM)-free catalysts represented by nitrogen and iron co-doped carbon (Fe-N-C) catalysts are desirable and critical for metal-air batteries, but challenges still exist in performance and stability. Here, cerium oxides (CeOx) are incorporated into a two-dimensional Fe-N-C catalyst (FeNC-Ce-950) via a host-guest strategy. The Ce4+/Ce3+ redox system creates a large number of oxygen vacancies for rapid O2 adsorption to accelerate the kinetics of oxygen reduction reaction (ORR). Consequently, the as-synthesized FeNC-Ce-950 catalyst exhibits a half-wave potential (E1/2) of 0.921 V and negligible decay (<2 mV for ΔE1/2) after 5,000 accelerated durability cycles, significantly outperforming most of ORR catalysts reported in recent years and precious metal counterparts. When applied in a zinc-air battery, it demonstrates a peak power density of 175 mW cm-2 and a specific capacity of 757 mAh gZn-1. This study also provides a reference for the exploration of Fe-N-C catalysts decorated with variable valence metal oxides.

High-performance atomic Co/N co-doped porous carbon catalysts derived from Co-doped metal-organic frameworks for oxygen reduction.

Improving the activity and durability of carbon-based catalysts is a key challenge for their application in fuel cells. Herein, we report a highly active and durable Co/N co-doped carbon (CoNC) catalyst prepared via pyrolysis of Co-doped zeolitic-imidazolate framework-8 (ZIF-8), which was synthesized by controlling the feeding sequence to enable Co to replace Zn in the metal-organic framework (MOF). The catalyst exhibited excellent oxygen reduction reaction (ORR) performance, while the half-wave potential decreased by only 8 mV after 5,000 accelerated stress test (AST) cycles in an acidic solution. Furthermore, the catalyst exhibited satisfactory cathodic catalytic performance when utilized in a hydrogen/oxygen single proton exchange membrane (PEM) fuel cell and a Zn-air battery, yielding maximum power densities of 530 and 164 mW cm-2, respectively. X-ray absorption spectroscopy (XAS) and high-angle annular dark field-scanning transmission electron microscopy (HAAD-STEM) analyses revealed that Co was present in the catalyst as single atoms coordinated with N to form Co-N moieties, which results in the high catalytic performance. These results show that the reported catalyst is a promising material for inclusion into future fuel cell designs.

Construction of Confined Bifunctional 2D Material for Efficient Sulfur Resource Recovery and Hg2+ Adsorption in Desulfurization.

Substantial energy penalty of valuable sulfate recovery restricts the efficiency of wet desulfurization and increases the risk of Hg0 reemission. Although the enhanced sulfite oxidation rate with cobalt-based materials can increase the energy efficiency, inactivation and poisoning of catalyst due to the competition of reactant must be addressed. Here we obtained a superwetting two-dimensional cobalt-nitrogen-doped carbon (2D Co-N-C) nanosheet featuring confined catalysis/adsorption sites for the energy-efficient sulfite oxidation and Hg2+ adsorption. The designed structure exhibits enhanced surface polarity, availability and short reactant diffusion path, thus enabling the significant catalytic TOF value of 0.085 s-1 and simultaneous mercury removal ability of 143.26 mg·g-1. The catalyst nanosheets present regenerating stabilities to improve cost-efficiency. By deployment of the Co-N-C catalysts, a marked reduction of heat penalty up to 69% can be achieved, which makes this catalytic pathway for sulfur resource recovery economically feasible in real industry scenario.

Non-PGM Electrocatalysts for PEM Fuel Cells: A DFT Study on the Effects of Fluorination of FeNx-Doped and N-Doped Carbon Catalysts.

Fluorination is considered as a means of reducing the degradation of Fe/N/C, a highly active FeNx-doped disorganized carbon catalyst for the oxygen reduction reaction (ORR) in PEM fuel cells. Our recent experiments have, however, revealed that fluorination poisons the FeNx moiety of the Fe/N/C catalytic site, considerably reducing the activity of the resulting catalyst to that of carbon only doped with nitrogen. Using the density functional theory (DFT), we clarify in this work the mechanisms by which fluorine interacts with the catalyst. We studied 10 possible FeNx site configurations as well as 2 metal-free sites in the absence or presence of fluorine molecules and atoms. When the FeNx moiety is located on a single graphene layer accessible on both sides, we found that fluorine binds strongly to Fe but that two F atoms, one on each side of the FeNx plane, are necessary to completely inhibit the catalytic activity of the FeNx sites. When considering the more realistic model of a stack of graphene layers, only one F atom is needed to poison the FeNx moiety on the top layer since ORR hardly takes place between carbon layers. We also found that metal-free catalytic N-sites are immune to poisoning by fluorination, in accordance with our experiments. Finally, we explain how most of the catalytic activity can be recovered by heating to 900 °C after fluorination. This research helps to clarify the role of metallic sites compared to non-metallic ones upon the fluorination of FeNx-doped disorganized carbon catalysts.