Electronic structure optimizing of Ru nanoclusters via Co single atom and N, S co-doped reduced graphene oxide for accelerating water electrolysis.

The development of efficient and stable electrocatalysts for hydrogen evolution reaction (HER) is impending for the advancement of water-splitting. In this study, we developed a novel electrocatalyst consisting of highly dispersed Ru nanoclusters ameliorated by cobalt single atoms and N, S co-doped reduced graphene oxide (CoSARuNC@NSG). Benefitted from the optimized electronic structure of the Ru nanoclusters induced by the adjacent single atomic Co and N, S co-doped RGO support, the electrocatalyst exhibits exceptional HER performance with overpotentials of 15 mV and 74 mV for achieving a current density of 10 mA cm-2 in alkaline and acidic water. The catalyst outperforms most noble metal-based HER electrocatalysts. Furthermore, the electrolyzer assembled with CoSARuNC@NSG and RuO2 demonstrated an overall voltage of 1.56 V at 10 mA cm-2 and an excellent operational stability for over 25 h with almost no attenuation. Theoretical calculations also deduce its high HER activity demonstrated by the smaller reaction energy barrier due to the optimized electronic structure of Ru nanoclusters. This strategy involving the regulation of metal nanoparticles activity through flexible single atom and GO support could provide valuable insights into the design of high-performance and low-cost HER catalysts.

Carbonate Minerals and Dissimilatory Iron-Reducing Organisms Trigger Synergistic Abiotic and Biotic Chain Reactions under Elevated CO2 Concentration.

Increasing CO2 emission has resulted in pressing climate and environmental issues. While abiotic and biotic processes mediating the fate of CO2 have been studied separately, their interactions and combined effects have been poorly understood. To explore this knowledge gap, an iron-reducing organism, Orenia metallireducens, was cultured under 18 conditions that systematically varied in headspace CO2 concentrations, ferric oxide loading, and dolomite (CaMg(CO3)2) availability. The results showed that abiotic and biotic processes interactively mediate CO2 acidification and sequestration through "chain reactions", with pH being the dominant variable. Specifically, dolomite alleviated CO2 stress on microbial activity, possibly via pH control that transforms the inhibitory CO2 to the more benign bicarbonate species. The microbial iron reduction further impacted pH via the competition between proton (H+) consumption during iron reduction and H+ generation from oxidization of the organic substrate. Under Fe(III)-rich conditions, microbial iron reduction increased pH, driving dissolved CO2 to form bicarbonate. Spectroscopic and microscopic analyses showed enhanced formation of siderite (FeCO3) under elevated CO2, supporting its incorporation into solids. The results of these CO2-microbe-mineral experiments provide insights into the synergistic abiotic and biotic processes that alleviate CO2 acidification and favor its sequestration, which can be instructive for practical applications (e.g., acidification remediation, CO2 sequestration, and modeling of carbon flux).

Self-Templating Synthesis of Hollow Co3O4 Nanoparticles Embedded in N,S-Dual-Doped Reduced Graphene Oxide for Lithium Ion Batteries.

The design and synthesis of hollow-nanostructured transition metal oxide-based anodes is of great importance for long-term operation of lithium ion batteries. Herein, we report a two-step calcination strategy to fabricate hollow Co3O4 nanoparticles embedded in a N,S-co-doped reduced graphene oxide framework. In the first step, core-shell-like Co@Co3O4 embedded in N,S-co-doped reduced graphene oxide is synthesized by pyrolysis of a Co-based metal organic framework/graphene oxide precursor in an inert atmosphere at 800 °C. The designed hollow Co3O4 nanoparticles with an average particle size of 25 nm and wall thickness of about 4-5 nm are formed by a further calcination process in air at 250 °C via the nanoscale Kirkendall effect. Both micropores and mesopores are generated in the HoCo3O4/NS-RGO framework. Benefiting from the hierarchical porous structure of the hollow Co3O4 and the co-doping of nitrogen and sulfur atoms in reduced graphene oxide, the thus-assembled battery exhibits a high specific capacity of 1590 mAh g-1 after 600 charge-discharge cycles at 1 A g-1 and a promising rate performance from 0.2 to 10 A g-1.

Hierarchical Nanostructured Electrocatalysts for Oxygen Reduction Reaction.

Hierarchical nanostructured materials, which possess the porous structure of multiscale porosities on different pore diameters from micro-, meso- to macropores based on International Union of Pure and Applied Chemistry, are much desired to present the synergistic attractive advantages of each scale of hierarchical pores in the development of catalysis, adsorption, separation, energy, and biochemistry. The use of hierarchical nanostructured materials as oxygen reduction reaction (ORR) electrocatalysts is advanced to increase specific surface area for active sites dispersion and exposure as well as enhance reactants/products transfer. However, complex and costly templateincorporated methods and relatively uncontrollable template-free methods motive us to develop novel and efficient preparation methods. Herein, recent developments and synthesis strategies that have been made in the field of hierarchical nanostructured materials as well as their application for ORR electrocatalysts are reviewed.

POSS-Derived Synthesis and Full Life Structural Analysis of Si@C as Anode Material in Lithium Ion Battery.

Polyhedral oligomeric silsesquioxane (POSS)-derived Si@C anode material is prepared by the copolymerization of octavinyl-polyhedral oligomeric silsesquioxane (octavinyl-POSS) and styrene. Octavinyl-polyhedral oligomeric silsesquioxane has an inorganic core (-Si8O12) and an organic vinyl shell. Carbonization of the core-shell structured organic-inorganic hybrid precursor results in the formation of carbon protected Si-based anode material applicable for lithium ion battery. The initial discharge capacity of the battery based on the as-obtained Si@C material Si reaches 1500 mAh g-1. After 550 charge-discharge cycles, a high capacity of 1430 mAh g-1 was maintained. A combined XRD, XPS and TEM analysis was performed to investigate the variation of the discharge performance during the cycling experiments. The results show that the decrease in discharge capacity in the first few cycles is related to the formation of solid electrolyte interphase (SEI). The subsequent rise in the capacity can be ascribed to the gradual morphology evolution of the anode material and the loss of capacity after long-term cycles is due to the structural pulverization of silicon within the electrode. Our results not only show the high potential of the novel electrode material but also provide insight into the dynamic features of the material during battery cycling, which is useful for the future design of high-performance electrode material.

In-Situ Synthesized Si@C Materials for the Lithium Ion Battery: A Mini Review.

As an important component, the anode determines the property and development of lithium ion batteries. The synthetic method and the structure design of the negative electrode materials play decisive roles in improving the property of the thus-assembled batteries. Si@C compound materials have been widely used based on their excellent lithium ion intercalation capacity and cyclic stability, in which the in-situ synthetic method can make full use of the structural advantages of the monomer itself, thus improving the electrochemical performance of the anode material. In this paper, the different preparation technologies and composite structures of Si@C compound materials by in-situ synthesis are introduced. The research progress of Si@C compound materials by in-situ synthesis is reviewed, and the prospect of future development of Si@C compound materials has been tentatively commented.

Bi-metallic boride electrocatalysts with enhanced activity for the oxygen evolution reaction.

Rational design and understanding of the intrinsic mechanism are critical to develop highly active and durable electrocatalysts. In this study, a series of bi-metallic boride catalysts based on Ni and Co were prepared, and their activities were evaluated. The synthesised Co-10Ni-B catalyst exhibited excellent activity for water splitting in a 1 M KOH electrolyte. The overpotential was 330 mV at a current density of 10 mA cm-2, better than previously reported mono-metallic borides and even IrO2. The synergistic effect of Co and Ni was proved by X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy. The facile formation of critical intermediates CoOOH and NiOOH during the catalytic processes and a significant increase in surface area owing to the introduction of a second metal into mono-metallic boride were attributed to the superior catalytic performance of catalysts for the oxygen evolution reaction. A Co-10Ni-B-sp catalyst with a higher surface area than the Co-10Ni-B catalyst was also synthesised to evaluate the effect of a high surface area on the catalytic activity. A lower overpotential of 310 mV at a current density of 10 mA cm-2 was achieved.

Transforming waste biomass with an intrinsically porous network structure into porous nitrogen-doped graphene for highly efficient oxygen reduction.

Porous nitrogen-doped graphene with a very high surface area (1152 m(2) g(-1)) is synthesized by a novel strategy using intrinsically porous biomass (soybean shells) as a carbon and nitrogen source via calcination and KOH activation. To redouble the oxygen reduction reaction (ORR) activity by tuning the doped-nitrogen content and type, ammonia (NH3) is injected during thermal treatment. Interestingly, this biomass-derived graphene catalyst exhibits the unique properties of mesoporosity and high pyridine-nitrogen content, which contribute to the excellent oxygen reduction performance. As a result, the onset and half-wave potentials of the new metal-free non-platinum catalyst reach -0.009 V and -0.202 V (vs. SCE), respectively, which is very close to the catalytic activity of the commercial Pt/C catalyst in alkaline media. Moreover, our catalyst has a higher ORR stability and stronger CO and CH3OH tolerance than Pt/C in alkaline media. Importantly, in acidic media, the catalyst also exhibits good ORR performance and higher ORR stability compared to Pt/C.

Photoregenerative I⁻/I3⁻ couple as a liquid cathode for proton exchange membrane fuel cell.

A photoassisted oxygen reduction reaction (ORR) through I(-)/I3(-) redox couple was investigated for proton exchange membrane (PEM) fuel cell cathode reaction. The I(-)/I3(-)-based liquid cathode was used to replace conventional oxygen cathode, and its discharge product I(-) was regenerated to I3(-) by photocatalytic oxidation with the participation of oxygen. This new and innovative approach may provide a strategy to eliminate the usage of challenging ORR electrocatalysts, resulting in an avenue for developing low-cost and high-efficiency PEM fuel cells.