Palladium Enhanced Iron Active Site - An Efficient Dual-Atom Catalyst for Oxygen Electroreduction.

Metal-nitrogen-carbon (M-C/N) electrocatalysts have been shown to have satisfactory catalytic activity and long-term durability for the oxygen reduction reaction (ORR). Here, a strategy to prepare a new electrocatalyst (Fe&Pd-C/N) using a unique metal-containing ionic liquid (IL) is exploited, in which Fe & Pd ions are positively charged species atomically dispersed by coordination to the N of the N-doped C substrate, C/N. X-ray absorption fine structure, XPS and aberration-corrected transmission electron microscopy results verified a well-defined dual-atom configuration comprising Fe+2.x -N4 coupled Pd2+ -N4 sites and well-defined spatial distribution. Electronic control of a coupled Fe-Pd structure produces an electrocatalyst that exhibits superior performance with enhanced activity and durability for the ORR compared to that of commercial Pt/C (20%, Johnson Matthey) in both alkaline and acid media. Density functional theory calculations indicate that Pd atom can enhance the catalytic activity of the Fe active sites adjacent to Pd sites by changing the electronic orbital structure and Bader charge of the Fe centers. The excellent catalytic performance of the Fe&Pd-C/N electrocatalyst is demonstrated in zinc-air batteries and hydrogen-air fuel cells.

Hydroxyl-/Carboxyl-Rich Graphitic Carbon Nitride/Graphene Oxide Composites for Efficient Photodegradation of Reactive Red 195 and Antibacterial Applications.

In this work, a protonated graphitic carbon nitride (P-g-C3N4)-coated graphene oxide (GO) composite (GO/P-g-C3N4) was prepared via wet-chemistry exfoliation, followed by a freeze-drying process. The GO/P-g-C3N4 composite was found to have an outstanding photodegradation performance effect on the reactive red 195 (RR195) dye and very strong antibacterial properties. Both the GO structure and the dispersed state of P-g-C3N4 were found to play a significant role in enhancing the photocatalytic activity of GO/P-g-C3N4. The GO/P-g-C3N4 obtained via freeze-drying retained a large number of oxygen-containing groups and showed higher catalytic activity and reusability than the reduced GO (rGO)/g-C3N4 obtained via thermal reduction. Characterization of the samples indicates that GO/P-g-C3N4 has a higher specific surface area and photocurrent density than rGO/g-C3N4; it is likely that these properties lead to the superior photocatalytic activity observed in GO/P-g-C3N4. Adsorption energy calculations indicate that O2 can be readily adsorbed onto the GO surface, which results in stronger oxidizing superoxide anion radicals (•O2-) and holes (h+); these active radicals can rapidly degrade RR195 dyes. Moreover, broad-spectrum antibacterial activity (demonstrated against Staphylococcus aureus and Escherichia coli) was observed in the case of the GO/P-g-C3N4 composite irradiated with visible light. This work offers new insights into the design of cost-effective g-C3N4-based photocatalysts for environmental remediation.

Sub-20-nm anatase TiO2 anchored on hollow carbon spheres for enhanced photocatalytic degradation of reactive red 195.

Herein, hollow carbon sphere (HCS)-supported titanium dioxide (TiO2) nanoparticles (sub-20-nm; HCS@TiO2)-based composites are rationally designed and fabricated via a facile wet-chemistry strategy. The introduction of an HCS, which acts as a conductive substrate, improves the separation efficiency of photogenerated hole/electron pairs (h+/e-) from TiO2 because photogenerated electrons are transferred to conductive carbon skeleton. Due to the three-dimensional spherical structure and excellent hydrophilicity of the carbon skeletons, low-density HCS with outstanding conductivity not only accelerate the separation of photogenerated h+/e- pairs from TiO2 but also improve the adsorption performance of the soluble reactive red 195 molecules (RR195) on the surface of TiO2 nanoparticles. These properties of HCS@TiO2 composites enable efficient photocatalytic degradation of RR195. The obtained results indicated that HCS@TiO2 composites (80 wt% TiO2) achieved the best photocatalytic degradation performance with higher photodegradation rate of 97% than pure TiO2 nanoparticles (86%). This study offers a new pathway for the design and preparation of novel photocatalysts to achieve efficient degradation of degrading organic pollutants.

Imidazolium ionic Liquid-Regulated Sub-5-nm Pt(111) with a stable configuration anchored on hollow carbon nanoshells for efficient oxygen reduction.

Here, N-doped hollow carbon sphere (NHCS)-supported (111)-plane-engineered sub-5-nm Pt (Pt-NHCS) catalysts regulated precisely by imidazolium ionic liquids were synthesized successfully and used to catalyze oxygen reduction. The (111)-plane engineered Pt nanocrystals with a diameter of 4.5 ± 0.5 nm were homogeneously deposited on the 3-dimensional spherical nanoshells. The resulting Pt nanocrystals anchored on the carbon skeleton exhibit a stable configuration in both alkaline and acid electrolytes with the help of imidazolium cations and pyrolysis. Among all as-prepared catalysts, the optimized Pt-NHCS shows remarkable long-term durability. Specifically, Pt-NHCS maintains 95.3% of the original current density after 10,000 potential cycles, while Pt/C benchmarks exhibit a retention of 78.5%. Accelerated durability test results indicate that Pt-NHCS exhibits a high efficiency of 96 % in comparison with initial current density, while a value of 86% for Pt/C. Density functional theory calculations demonstrate that reactive Pt(111) planes with well-defined Schottky defects and vacancies adsorb and activate oxygen molecule rapidly while desorbing the reaction intermediates.

Single Co Atoms Implanted into N-Doped Hollow Carbon Nanoshells with Non-Planar Co-N4-1-O2 Sites for Efficient Oxygen Electrochemistry.

Facile synthesis of cost-effective carbon-supported Co single atoms (Co-SAs) exhibits huge potential applications in energy storage and conversion devices. We here report the implantation of Co-SAs into hollow carbon spheres (Co-SAs-HCS) via a facile wet-chemistry strategy followed by controlled pyrolysis. Electron-rich histidine acted as a Lewis base effectively immobilizing Co2+ (Lewis acid) via the electrostatic effect and hydrogen bonds, thus achieving the scalable synthesis of Co-SAs-HCS. We constructed a series of histidine-Co2+ structure models to elucidate the formation of histidine-Co2+ complexes by analyzing their binding energy. X-ray absorption fine-structure results verify that central Co atoms with four N coordination atoms possess a non-planar Co-N4 structure. Electrochemical results indicate that the as-prepared Co-SAs-HCS catalyst shows a low potential difference (0.809 V) between the oxygen evolution reaction potential at 10 mA cm-2 and the oxygen reduction reaction half-wave potential, outperforming the commercial Pt/C catalysts (0.996 V). Moreover, an assembled Zn-air battery based on Co-SAs-HCS exhibits an unexpected long-term durability. We have demonstrated that non-planar Co-N4-1-O2 sites are the source for highly efficient adsorption and dissociation of O2 molecules and then reduction of the free energy of desorption of the intermediates by density functional theory. Our findings provide a new design insight into the exploration of advanced electrocatalysts, which will be applied in the design of green energy devices in the future.

Amino-1H-tetrazole-regulated high-density nitrogen-doped hollow carbon nanospheres for long-life Zn-air batteries.

High-density nitrogen-doped porous carbon catalysts have been regarded as promising alternatives to precious metals in proton-exchange membrane fuel cells (PEMFC) and metal-air batteries based on the oxygen reduction reaction (ORR). We herein synthesized high-density pyridinic and graphitic N-doped hollow carbon nanospheres (G&P N-HCS) using a high-yield amino-1H-tetrazole (ATTZ) via a self-sacrificial-template method. The synthesized G&P N-HCS shows a high N content (15.2 at%), in which pyridinic (Pr) and graphitic (Gr) N are highly reactive for the ORR catalysis. We found that the half-wave potential and limiting current density of G&P N-HCS are comparable to the state-of-the-art Pt/C, whereas its cyclic durability is much superior to that of Pt/C. Experimental results indicate that an optimal ratio (1 : 1) between Gr N and Pr N in G&P N-HCS exhibits the highest ORR performances, rather than Gr N-dominated N-HCS or Pr N-dominated N-HCS. Notably, N-HCS containing only Gr N and Pr N has poor catalytic performance for ORR in alkaline electrolytes. Density functional theory (DFT) simulations untangle the catalytic nature of Pr and Gr N and decipher the relations between the N type(s) and total N content required for the ORR catalysis. This study provides a new way to design efficient N-doped porous carbon-enriched active sites, and solves the cathode catalyst in the commercialization of PEMFC and metal-air batteries.