Reduced Graphene Oxide-Supported Iron-Cobalt Alloys as High-Performance Catalysts for Oxygen Reduction Reaction.

Exploring non-precious metal-based catalysts for oxygen reduction reactions (ORR) as a substitute for precious metal catalysts has attracted great attention in recent times. In this paper, we report a general methodology for preparing nitrogen-doped reduced graphene oxide (N-rGO)-supported, FeCo alloy (FeCo@N-rGO)-based catalysts for ORR. The structure of the FeCo@N-rGO based catalysts is investigated using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and transition electron microscopy, etc. Results show that the FeCo alloy is supported by the rGO and carbon that derives from the organic ligand of Fe and Co ions. The eletrocatalytic performance is examined by cyclic voltammetry, linear scanning voltammetry, Tafel, electrochemical spectroscopy impedance, rotate disc electrode, and rotate ring disc electrode, etc. Results show that FeCo@N-rGO based catalysts exhibit an onset potential of 0.98 V (vs. RHE) and a half-wave potential of 0.93 V (vs. RHE). The excellent catalytic performance of FeCo@N-rGO is ascribed to its large surface area and the synergistic effect between FeCo alloy and N-rGO, which provides a large number of active sites and a sufficient surface area.

Effect of different introduction methods of cerium and tin on the properties of titanium-based catalysts for the selective catalytic reduction of NO by NH3.

This work investigated the influence of introduction methods of cerium and tin on the physicochemical properties as well as the activity and durability of titanium-based catalysts for the selective catalytic reduction of NO by NH3 (NH3-SCR). Precipitation and impregnation methods were adopted to synthesize a series of cerium-tin-titanium catalysts. These catalysts were characterized by XRD, Raman, N2 adsorption-desorption, HRTEM, EDS mapping, XPS, H2-TPR, NH3-TPD and in situ DRIFT. Notably, Ce/Sn/Ti(imp) catalyst prepared by stepwise-impregnation method could provide an interface between Ce and Sn for more facile electron transfer than Sn/Ce-Ti(co), Ce/Sn-Ti(co) and Sn/Ce/Ti(imp) catalysts. It promoted the redox equilibrium of Ce4+ + Sn2+ ↔ Ce3+ + Sn4+ shifting to right to produce adequate Ce3+ and surface adsorbed oxygen, resulting in optimal reducibility and surface acidity of Ce/Sn/Ti(imp) catalyst. Besides, the activation of NH3 and desorption of NOx readily occurred on the surface of Ce/Sn/Ti(imp), which were favorable for the proceeding of subsequent reactions and excellent performance of NH3-SCR.

Dimethylglyoxime Clathrate as Ligand Derived Nitrogen-Doped Carbon-Supported Nano-Metal Particles as Catalysts for Oxygen Reduction Reaction.

Nitrogen-doped carbon-supported metal nano-particles show great promise as high-performance catalysts for novel energies, organic synthesis, environmental protection, and other fields. The synergistic effect between nitrogen-doped carbon and metal nano-particles enhances the catalytic properties. Thus, how to effectively combine nitrogen-doped carbon with metal nano-particles is a crucial factor for the synthesis of novel catalysts. In this paper, we report on a facile method to prepare nitrogen-doped carbon-supported metal nano-particles by using dimethylgly-oxime as ligand. The nano-particles of Pd, Ni, Cu, and Fe were successfully prepared by the pyrolysis of the corresponding clathrate of ions and dimethylglyoxime. The ligand of dimethylglyoxime is adopted as the source for the nitrogen-doped carbon. The nano-structure of the prepared Pd, Ni, Cu, and Fe particles are confirmed by X-ray diffraction, scanning electron microscopy, and trans-mission electron microscopy tests. The catalytic performances of the obtained metal nano-particles for oxygen reduction reaction (ORR) are investigated by cyclic voltammetry, Tafel, linear sweeping voltammetry, rotating disc electrode, rotating ring disc electrode, and other technologies. Results show that the nitrogen-doped carbon-supported metal nano-particles can be highly efficient catalysts for ORR. The results of the paper exhibit a facile methodology to prepare nitrogen-doped carbon-supported metal nano-particles.

V2O3 Nanoparticles Confined in High-Conductivity and High-Throughput Carbon Nanofiber Nanohybrids for Advanced Sodium-Ion Capacitors.

Electrode materials with high conductivity and high mass transport rate are highly desirable for a variety of electrochemical energy devices but face a grand challenge to be readily prepared yet. Here, we propose the design and preparation of a nanohybrid of V2O3 nanoparticles embedded in a multichannel carbon nanofiber (V2O3@MCNF) network with high conductivity and high mass transport. We demonstrate the V2O3@MCNF shows superior capability for sodium storage with an excellent capacity of 214.3 mA h g-1 even at 5 A g-1, thanks to its high conductivity for electron transfer and facilitated mass transportation endowed by the one-dimensional conductive multichannel fiber structure. Such favorable structures and properties in V2O3@MCNFs enable them to be applied as high-performance anodes of sodium-ion hybrid capacitors (SIHCs), successfully addressing the critical kinetics imbalance between Faradaic anodes and capacitive cathodes for application of SIHCs, which show impressively high energy/power densities along with impressive cycling performance over 10,000 cycles.

Influences of Multilayer Graphene and Boron Decoration on the Structure and Combustion Heat of Al3Mg2 Alloy.

To improve the engine-driven performance of propellants, high-energy alloys such as Al and Mg are usually adopted as annexing agents. However, there is still room for improvement in the potential full utilization of alloy energy. In this study, we investigated how to improve combustion efficiency by decorating Al3Mg2 alloy with multilayer graphene and amorphous boron. Scanning electron microscopy and Raman tests showed that decorating with multilayer graphene and amorphous boron promoted the dispersion of Al3Mg2 alloy. The results showed that decorating with 1% boron and 2% multilayer graphene improved the combustion heat of Al3Mg2 alloy to 32.8 and 30.5 MJ/kg, respectively. The coexistence of two phases improved the combustion efficiency of the matrix Al3Mg2 alloy.

Getting insight into the effect of CuO on red mud for the selective catalytic reduction of NO by NH3.

A series of copper-modified red mud catalysts (CuO/PRM) with different copper oxide contents were synthesized by wet impregnation method and investigated for selective catalytic reduction of NO by NH3 (NH3-SCR). The catalytic results demonstrated that the red mud catalyst with 7 wt% CuO content exhibited the excellent catalytic performance as well as resistance to water and sulfur poisoning. The red mud support and copper-containing catalysts were characterized by XRF, XRD, N2 adsorption-desorption, HRTEM, EDS mapping, XPS, H2-TPR, NH3-TPD and in situ DRIFT. The obtained results revealed that well dispersed copper oxide originating from 1 to 7 wt% CuO contents was more facile for the redox equilibrium of Cu2+ + Fe2+ ↔ Cu+ + Fe3+ shifting to right to form Cu+ and surface oxygen species than crystalline CuO generating from high CuO loading (9 wt% CuO), which was beneficial to the enhancement of reducibility and the formation of Lewis acid sites on the catalyst surface. All these factors made significant contributions to the improvement of NH3-SCR activities for CuO/PRM catalysts. Moreover, in situ DRIFT analysis combined with DFT calculated results confirmed that the finely dispersed copper species not only enhanced the NH3 activation but also promoted the NOx desorption, which synergistically facilitated the NH3-SCR process via the Eley-Rideal mechanism.

A Hybrid Material Combined Copper Oxide with Graphene for an Oxygen Reduction Reaction in an Alkaline Medium.

In this work, an electrode material based on CuO nanoparticles (NPs)/graphene (G) is developed for ORR in alkaline medium. According to the characterization of scanning electron microscope and transmission electron microscope, CuO NPs are uniformly distributed on the wrinkled G sheets. The X-ray diffraction test reveals that the phase of CuO is monoclinic. The CuO/G hybrid electrode exhibits a positive onset potential (0.8 V), high cathodic current density (3.79 × 10-5 mA/cm²) and high electron transfer number (four-electron from O2 to H2O) for ORR in alkaline media. Compared with commercial Pt/C electrocatalyst, the CuO/G electrode also shows superior fuel durability. The high electrocatalytic activity and durability are attribute to the strong coupling between CuO NPs and G nanosheets.

Electrochemical impacts of sheet-like hafnium phosphide and hafnium disulfide catalysts bonded with reduced graphene oxide sheets for bifunctional oxygen reactions in alkaline electrolytes.

Non-noble metal-based catalysts with efficient catalytic activities for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are critical for energy conversion devices, including fuel cells and metal-air batteries. In this work, novel hafnium phosphide-reduced graphene oxide nanosheets (HfP-rGO NS) and hafnium disulfide-reduced graphene oxide nanosheets (HfS2-rGO NS) were synthesized and investigated as bifunctional electrocatalysts for OER and ORR. The prepared HfP-rGO NS and HfS2-rGO NS catalysts showed nanosheet structures, where the HfP or HfS2 nanosheet was closely packed with rGO. A unique methodology was adopted to lodge the non-metal oxide catalytic sheets (i.e., HfP and HfS2) over the rGO sheets, which positioned the oxide layer on the catalytic sheet surface for instant oxygen evolution. Low intensity X-ray diffraction patterns and Raman spectra confirmed the sheet-like structure of HfP-rGO NS and HfS2-rGO NS. Scanning electron microscope mapping images revealed that all elements (i.e., Hf, P, C and O for HfP-rGO NS and Hf, S, C and O for HfS2-rGO NS) were equally distributed in the synthesized heteroatomic nanosheets. Moreover, both the HfP-rGO NS and HfS2-rGO NS demonstrated excellent durability for both ORR and OER. This outperforms the most state-of-the-art non-precious-metal-based bifunctional catalysts, which is attributed to the synergistic effect of rGO and Hf-based catalysts. The different ORR and OER reaction potentials in HfP-rGO NS and HfS2-rGO NS likely result from the influence of HfP and HfS2.

Synthesis and Characterizations of Zinc Oxide on Reduced Graphene Oxide for High Performance Electrocatalytic Reduction of Oxygen.

Electrocatalysts for the oxygen reduction (ORR) reaction play an important role in renewable energy technologies, including fuel cells and metal-air batteries. However, development of cost effective catalyst with high activity remains a great challenge. In this feature article, a hybrid material combining ZnO nanoparticles (NPs) with reduced graphene oxide (rGO) is applied as an efficient oxygen reduction electrocatalyst. It is fabricated through a facile one-step hydrothermal method, in which the formation of ZnO NPs and the reduction of graphene oxide are accomplished simultaneously. Transmission electron microscopy and scanning electron microscopy profiles reveal the uniform distribution of ZnO NPs on rGO sheets. Cyclic voltammograms, rotating disk electrode and rotating ring disk electrode measurements demonstrate that the hierarchical ZnO/rGO hybrid nanomaterial exhibits excellent electrocatalytic activity for ORR in alkaline medium, due to the high cathodic current density (9.21 × 10-5 mA/cm²), positive onset potential (-0.22 V), low H2O2 yield (less than 3%), and high electron transfer numbers (4e from O2 to H2O). The proposed catalyst is also compared with commercial Pt/C catalyst, comparable catalytic performance and better stability are obtained. It is expected that the ZnO/rGO hybrid could be used as promising non-precious metal cathode in alkaline fuel cells.

Enhanced kinetics of polysulfide redox reactions on Mo2C/CNT in lithium-sulfur batteries.

Among different energy storage devices, the lithium-sulfur (Li-S) battery is the subject of recent attention. However, the capacity decay caused by polysulfide shuttle leading to sluggish kinetics of polysulfide redox reactions is the main hindrance for its practical application in Li-S batteries. Herein, molybdenum carbide nanoparticles anchored on carbon nanotubes (Mo2C/CNT) are reported to serve as an efficient cathode material to enhance the electrochemical kinetics of polysulfide conversion in Li-S batteries. Mo2C/CNT shows strong adsorption and activation of polar polysulfides and therefore accelerates the redox kinetics of polysulfides, reduces the energy barrier, effectively mitigates the polarization and polysulfide shuttle, thus improving the electrochemical performance. The S-Mo2C/CNT composite with 70 wt% sulfur loading exhibits high specific discharge capacity (1206 mA h g-1 at 0.5 C), excellent high-rate performance, long cycle life (900 cycles), and outstanding Coulombic efficiency (∼100%) at a high rate (2 C) corresponding to a capacity decay of only 0.05%. Remarkably, the S-Mo2C/CNT cathode with high areal sulfur loading of 2.5 mg cm-2 exhibits high-rate capacities and stable cycling performance over 100 cycles, offering the potential for use in high energy Li-S batteries.

Recent Advance on Polyaniline or Polypyrrole-Derived Electrocatalysts for Oxygen Reduction Reaction.

The fuel cell, as one of the most promising electrochemical devices, is sustainable, clean, and environmentally benign. The sluggish oxygen reduction reaction (ORR) is an important fuel cell cathodic reaction that decides the efficiency of the overall energy conversion. In order to improve ORR efficiency, many efficient catalysts have been developed, in which the N-doped material is most popular. Polyaniline and polypyrrole as common aromatic polymers containing nitrogen were widely applied in the N-doped material. The shape-controlled N-doped carbon material can be prepared from the pyrolysis of the polyaniline or polypyrrole, which is effective to catalyze the ORR. This review is focused on the recent advance of polyaniline or polypyrrole-based ORR electrocatalysts.

Coralline-Like N-Doped Hierarchically Porous Carbon Derived from Enteromorpha as a Host Matrix for Lithium-Sulfur Battery.

Coralline-like N-doped hierarchically porous carbon (CNHPC) was prepared through a hydrothermal carbonization process using a sea pollutant enteromorpha as the starting material. The addition of a small amount of glucose during carbonization improved the yield of carbon, and the inherent N contents, especially for pyrrolic N and pyridinic N atoms. After loading 40 wt. % sulfur, the CNHPC/S composite, as a cathode in a Li-S battery, exhibited an initial discharge capacity of 1617 mAh g-1 (96.5 % of theoretical capacity) at 0.1 C and a capacity loss of 0.05 % per charge-discharge cycle after 500 cycles at 0.5 C with a stable Coulombic efficiency of 100 % in carbonate based electrolyte. Such a great performance can be attributed to the coralline-like hierarchically porous infrastructure and inherently abundant N doping. Given the conversion of waste pollutants into valuable energy-storage materials and the easy process, this work features a promising approach to prepare C/S cathodes for Li-S batteries. The special structural and textural characteristics of CNHPC might be attractive to other practical applications such as supercapacitors and catalysis.

Facile and Mild Strategy to Construct Mesoporous CeO2-CuO Nanorods with Enhanced Catalytic Activity toward CO Oxidation.

CeO2-CuO nanorods with mesoporous structure were synthesized by a facile and mild strategy, which involves an interfacial reaction between Ce2(SO4)3 precursor and NaOH ethanol solution at room temperature to obtain mesoporous CeO2 nanorods, followed by a solvothermal treatment of as-prepared CeO2 and Cu(CH3COO)2. Upon solvothermal treatment, CuO species is highly dispersed onto the CeO2 nanorod surface to form CeO2-CuO composites, which still maintain the mesoporous feature. A preliminary CO catalytic oxidation study demonstrated that the CeO2-CuO samples exhibited strikingly high catalytic activity, and a high CO conversion rate was observed without obvious loss in activity even after thermal treatment at a high temperature of 500 °C. Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H2-TPR) analysis revealed that there is a strong interaction between CeO2 and CuO. Moreover, it was found that the introduction of CuO species into CeO2 generates oxygen vacancies, which is highly likely to be responsible for high catalytic activity toward CO oxidation of the mesoporous CeO2-CuO nanorods.

Synergistic effect of N- and F-codoping on the structure and photocatalytic performance of TiO2.

Three types of TiO2 nanostructures were synthesized via a facile hydrolysis method at 195°C. Effects of the preparation method and doping with N and F on the crystal structure and photocatalytic performance of TiO2 were investigated. The nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller porosimetry, ultraviolet-visible diffuse reflectance spectroscopy and fluorescent emission spectra. Their photo-catalytic activity was examined by the photodegradation of methylene blue in aqueous solution under both ultra-violet and visible light irradiation. The results show that nitrogen and fluorine co-doped anatase TiO2 had the characteristics of a smaller crystalline size, broader light absorption spectrum and lower charge recombination than pure TiO2. Most importantly, more efficient photocatalytic activity under both ultra-violet and visible light was observed. The obtained N-F-TiO2 nanomaterial shows considerable potential for water treatment under sunlight irradiation.

A high-performance catalyst support for methanol oxidation with graphene and vanadium carbonitride.

In this study, a graphene-vanadium carbonitride (G-V(C, N)) hybrid is reported as a novel support for the Pt catalyst in methanol oxidation. The catalytic activity of the Pt/G-V(C, N) hybrid for methanol oxidation is greatly enhanced compared with that of a commercial Pt/C catalyst with carbon black as the catalyst support. The outstanding catalytic activity of the Pt/G-V(C, N) catalyst suggests the potential of using graphene-metal carbonitride as the catalyst support in fuel cells.

Hydrothermal synthesis of vanadium nitride and modulation of its catalytic performance for oxygen reduction reaction.

A creative hydrothermal synthesis method followed by calcination for vanadium nitride (VN) is reported. The oxygen reduction reaction (ORR) study of the catalyst shows that VN possesses a comparable catalytic performance to commercial Pt/C catalyst. The ORR catalytic activity study of vanadium nitride, vanadium carbonitride, and vanadium carbide reveals that tuning anions offers a promising route for the activity enhancement of the non-precious metal catalysts.

Nickel oxide hollow microsphere for non-enzyme glucose detection.

A facile strategy has been developed to fabricate nickel oxide hollow microspheres (NiO-HMSs) through a solvothermal method by using a mixed solvent of ethanol and water with the assistance of sodium dodecyl sulfate (SDS). Various techniques, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), and powder X-ray diffraction (XRD), were used to characterize the morphology and the structure of as-prepared samples. It was confirmed that the products possess a hollow microsphere structure that is constructed by interconnecting porous nanoplate framework. Electrochemical studies indicate that the NiO-HMS exhibits excellent stability and high catalytic activity for electrocatalytic oxidation of glucose in alkaline solutions, which enables the NiO-HMS to be used in enzyme-free amperometric sensors for glucose determination. It was demonstrated that the NiO-HMS-based glucose biosensor offers a variety of merits, such as a wide linear response window for glucose concentrations of 1.67 µM-6.87 mM, short response time (3 s), a lower detection limit of 0.53 µM (S/N=3), high sensitivity (~2.39 mA mM(-1) cm(-2)) as well as good stability and repeatability.