A series of ZIF-67-C-IL catalysts were prepared using ZIF-67 and 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] imide ([ BMIM]NTf2) ionic liquid as precursors. The structure of the catalysts was characterized by XRD, TEM, SEM and XPS. The catalytic performance of the catalysts for the oxygen reduction reaction (ORR) was evaluated in a three-electrode system. The results confirmed that the high-temperature treatment of the precursors resulted in the formation of N, S codoped carbon-encapsulated Co9S8 nanoparticles. To create N, S co-doped carbon coated Co9S8 nanoparticle catalysts, ionic liquids are used as sulfur and nitrogen sources. The catalytic activity of ORR can be improved using N, S co-doped carbon to prevent the aggregation of Co9S8 nanoparticles. Graphitized and N, S co-doped carbon shells are optimal for achieving high activity stability. Optimal 600-ZIF-67-C(1:1.5)-30IL catalytic activity was observed for ORR. The half-wave potential of ORR was 0.88 V vs. RHE in 0.1 mol L− 1 KOH, with a limit current density of 4.70 mA cm− 2. Similar ORR electrocatalytic activity was observed between this catalyst and commercial Pt/C (20 wt%).

To fabricate intermetallic nanoparticles with high oxygen reduction reaction activity, a high-temperature heat treatment of 700 to 1,000 °C is required. This heat treatment provides energy sufficient to induce an atomic rearrangement inside the alloy nanoparticles, increasing the mobility of particles, making them structurally unstable and causing a sintering phenomenon where they agglomerate together naturally. These problems cannot be avoided using a typical heat treatment process that only controls the gas atmosphere and temperature. In this study, as a strategy to overcome the limitations of the existing heat treatment process for the fabrication of intermetallic nanoparticles, we propose an interesting approach, to design a catalyst material structure for heat treatment rather than the process itself. In particular, we introduce a technology that first creates an intermetallic compound structure through a primary high-temperature heat treatment using random alloy particles coated with a carbon shell, and then establishes catalytic active sites by etching the carbon shell using a secondary heat treatment process. By using a carbon shell as a template, nanoparticles with an intermetallic structure can be kept very small while effectively controlling the catalytically active area, thereby creating an optimal alloy catalyst structure for fuel cells.

In this paper, we presented a hybrid composite of graphene quantum dots (GQDs)-modified three-dimensional graphene nanoribbons (3D GNRs) composite linked by Fe3O4 and CoO nanoparticles through reflux and ultrasonic treatment with GQDs, denoted as 3D GQDs-Fe3O4/CoO@GNRs (3D GFCG). In this hybrid, the 3D GNRs framework strengthened the electrical conductivity and the synergistic effects between GQDs and 3D GFCG enhanced the oxygen reduction reaction (ORR) activity of the nanocomposite. The results imply that decorating GQDs with other electro-catalysts is an effective strategy to synergistically improve their ORR activity.

The design of non-precious electrocatalysts with low-cost, good stability, and an improved oxygen reduction reaction(ORR) to replace the platinium-based electrocatalyst is significant for application of fuel cells and metal-air batteries with high energy density. In this study, we synthesize iron-carbide(Fe3C) embedded nitrogen(N) doped carbon nanofiber(CNF) as electrocatalysts for ORRs using electrospinning, precursor deposition, and carbonization. To optimize electrochemical performance, we study the three stages according to different amounts of iron precursor. Among them, Fe3C-embedded N doped CNF-1 exhibits the most improved electrochemical performance with a high onset potential of −0.18 V, a high E1/2 of −0.29 V, and a nearly four-electron pathway (n = 3.77). In addition, Fe3C-embedded N doped CNF-1 displays exellent long-term stabillity with the lowest ΔE1/2= 8 mV compared to the other electrocatalysts. The improved electrochemical properties are attributed to synergestic effect of N-doping and well-dispersed iron carbide embedded in CNF. Consequently, Fe3C-embedded N doped CNF is a promising candidate for non-precious electrocatalysts for high-performance ORRs.

In anion exchange membrane fuel cells, Pd nanoparticles are extensively studied as promising non-Pt catalysts due to their electronic structure similar to Pt. In this study, to fabricate Pd nanoparticles well dispersed on carbon support materials, we propose a synthetic strategy using mixed organic ligands with different chemical structures and functions. Simultaneously to control the Pd particle size and dispersion, a ligand mixture composed of oleylamine(OA) and trioctylphosphine(TOP) is utilized during thermal decomposition of Pd precursors. In the ligand mixture, OA serves mainly as a reducing agent rather than a stabilizer since TOP, which has a bulky structure, more strongly interacts with the Pd metal surface as a stabilizer compared to OA. The specific roles of OA and TOP in the Pd nanoparticle synthesis are studied according to the mixture composition, and the oxygen reduction reaction(ORR) activity and durability of highly-dispersed Pd nanocatalysts with different particles sizes are investigated. The results of this study confirm that the Pd nanocatalyst with large particles has high durability compared to the nanocatalyst with small Pd nanoparticles during the accelerated degradation tests although they initially indicated similar ORR performance.

Nitrogen (N)-doped protein-based carbon as platinum (Pt) catalyst supports from tofu for oxygen reduction reactions are synthesized using a carbonization and reduction method. We successfully prepare 5 wt% Pt@N-doped protein-based carbon, 10 wt% Pt@N-doped protein-based carbon, and 20 wt% Pt@N-doped protein-based carbon. The morphology and structure of the samples are characterized by field emission scanning electron microscopy and transmission electron micro scopy, and crystllinities and chemical bonding are identified using X-ray diffraction and X-ray photoelectron spectroscopy. The oxygen reduction reaction are measured using a linear sweep voltammogram and cyclic voltammetry. Among the samples, 10 wt% Pt@N-doped protein-based carbon exhibits exellent electrochemical performance with a high onset potential of 0.62 V, a high E1/2 of 0.55 V, and a low ΔE1/2= 0.32 mV. Specifically, as compared to the commercial Pt/C, the 10 wt% Pt@N-doped proteinbased carbon had a similar oxygen reduction reaction perfomance and improved electrochemical stability.

N-doped carbon nanofibers as catalysts for oxygen-reduction reactions are synthesized using electrospinning and carbonization. Their morphologies, structures, chemical bonding states, and electrochemical performance are characterized. The optimized N-doped carbon nanofibers exhibit graphitization of carbon nanofibers and an increased nitrogen doping as well as a uniform network structure. In particular, the optimized N-doped carbon nanofibers show outstanding catalytic activity for oxygen-reduction reactions, such as a half-wave potential (E1/2) of 0.43 V, kinetic limiting current density of 6.2 mA cm-2, electron reduction pathways (n = 3.1), and excellent long-term stability after 2000 cycles, resulting in a lower E1/2 potential degradation of 13 mV. The improvement in the electrochemical performance results from the synergistic effect of the graphitization of carbon nanofibers and the increased amount of nitrogen doping.

Nitrogen (N)-doped ordered mesoporous carbons (OMCs) with a dual transition metal system were synthesized as non-Pt catalysts for the ORR. The highly nitrogen doped OMCs were prepared by the precursor of ionic liquid (3-methyl-1-butylpyridine dicyanamide) for N/C species and a mesoporous silica template for the physical structure. Mostly, N-doped carbons are promoted by a single transition metal to improve catalytic activity for ORR in PEMFCs. In this study, our N-doped mesoporous carbons were promoted by the dual transition metals of iron and cobalt (Fe, Co), which were incorporated into the N-doped carbons lattice by subsequently heat treatments. All the prepared carbons were characterized by via transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). To evaluate the activities of synthesized doped carbons, linear sweep was recorded in an acidic solution to compare the ORR catalytic activities values for the use in the PEMFC system. The dual transition metal promotion improved the ORR activity compared with the single transition metal promotion, due to the increase in the quaternary nitrogen species from the structural change by the dual metals. The effect of different ratio of the dual metals into the N doped carbon were examined to evaluate the activities of the oxygen reduction reaction.

The electrocatalytic characteristics of oxygen reduction reaction of the PtxM(1-x) (M = Co, Cu, Ni) supported on multi-walled carbon nanotubes (MWNTs) have been evaluated in a Polymer Electrolyte Membrane Fuel Cell (PEMFC). The PtxM(1-x)/MWNTs catalysts with a Pt : M atomic ratio of about 3 : 1 were synthesized and applied to the cathode of PEMFC. The crystalline structure and morphology images of the PtxM(1-x) particles were characterized by X-ray diffraction and transmission electron microscopy, respectively. The results showed that the crystalline structure of the Pt alloy particles in Pt/MWNTs and PtxM(1-x)/MWNTs catalysts are seen as FCC, and synthesized PtxM(1-x) crystals have lattice parameters smaller than the pure Pt crystal. According to the electrochemical surface area (ESA) calculated with cyclic voltammetry analysis, Pt0.77Co0.23/MWNTs catalyst has higher ESA than the other catalysts. The evaluation of a unit cell test using Pt/MWNTs or PtxM(1-x)/MWNTs as the cathode catalysts demonstrated higher cell performance than did a commercial Pt/C catalyst. Among the MWNTs-supported Pt and PtxM(1-x) (M = Co, Cu, Ni) catalysts, the Pt0.77Co0.23/MWNTs shows the highest performance with the cathode catalyst of PEMFC because they had the largest ESA.