Bimetallic platinum–ruthenium nanoparticles immobilized on reduced graphene oxide-TiO2 (RGO-TiO2) support for ethanol electro oxidation in acidic media

The present work addresses the potentialities of Pt–Ru nanoparticles deposited on a graphene oxide (RGO) and TiO₂ composite support towards electrochemical oxidation of ethanol in acidic media relevant for fuel cell applications. To immobilize platinum–ruthenium bimetallic nanoparticles on to an RGO-TiO₂ nanohybrid support a simple solution-phase chemical reduction method is utilized. An examination using electron microscopy and energy dispersive X-ray spectroscopy (EDS) indicated that Pt–Ru particles of 4–8 nm in diameter are dispersed on RGO-TiO₂ composite support. The corresponding Pt–Ru/RGO-TiO₂ nanocomposite electrocatalyst was studied for the electrochemical oxidation of ethanol in acidic media. Compared to the commercial Pt–Ru/C and Pt/C catalysts, Pt–Ru/RGO-TiO₂ nanocomposite yields higher mass-specific activity of about 1.4 and 3.2 times, respectively towards ethanol oxidation reaction (EOR). The synergistic boosting provided by RGO-TiO₂ composite support and Pt–Ru ensemble together contributed to the observed higher EOR activity and stability to Pt–Ru/RGO-TiO₂ nanocomposite compared with other in-house synthesized Pt–Ru/RGO, Pt/RGO and commercial Pt–Ru/C and Pt/C electrocatalysts. Further optimization of RGO-TiO₂ composite support provides opportunity to deposit many other types of metallic nanoparticles onto it for fuel cell electrocatalysis applications.     

CNT-interconnected iron-doped NiP2/Ni2P heterostructural nanoflowers as high-efficiency electrocatalyst for oxygen evolution reaction

Oxygen evolution reaction (OER) plays a decisive role in electrolytic water splitting. However, it is still challengeable to develop low-cost and efficient OER electrocatalysts. Herein, we present a combination strategy via heteroatom doping, hetero-interface engineering and introducing conductive skeleton to synthesize a hybrid OER catalyst of CNT-interconnected iron-doped NiP₂/Ni₂P (Fe-(NiP₂/Ni₂P)@CNT) heterostructural nanoflowers by a simple hydrothermal reaction and subsequent phosphorization process. The optimized Fe-(NiP₂/Ni₂P)@CNT catalyst delivers an ultralow Tafel slope of 46.1 mV dec^?1 and overpotential of 254 mV to obtain 10 mA cm^?2, which are even better than those of commercial OER catalyst RuO₂. The excellent OER performance is mainly attributed to its unique nanoarchitecture and the synergistic effects: the nanoflowers constructed by a 2D-like nanosheets guarantee large specific area and abundant active sites; the highly conductive CNT skeleton and the electronic modulation by the heterostructural NiP₂/Ni₂P interface and the hetero-atom doping can improve the catalytic activity; porous nanostructure benefits electrolyte penetration and gas release; most importantly, the rough surface and rich defects caused by phosphorization process can further enhance the OER performance. This work provides a deep insight to boost catalytic performance by heteroatom doping and interface engineering for water splitting.     

FeCo alloys in-situ formed in Co/Co2P/N-doped carbon as a durable catalyst for boosting bio-electrons-driven oxygen reduction in microbial fuel cells

Non-noble metal catalyst with high catalytic activity and stability towards oxygen reduction reaction (ORR) is critical for durable bioelectricity generation in air-cathode microbial fuel cells (MFCs). Herein, nitrogen-doped (iron-cobalt alloy)/cobalt/cobalt phosphide/partly-graphitized carbon ((FeCo)/Co/Co₂P/NPGC) catalysts are prepared by using cornstalks via a facile method. Carbonization temperature exerts a great effect on catalyst structure and ORR activity. FeCo alloys are in-situ formed in the catalysts above 900 °C, which are considered as the highly-active component in catalyzing ORR. AC-MFC with FeCo/Co/Co₂P/NPGC (950 °C) cathode shows the highest power density of 997.74 ± 5 mW m^?2, which only declines 8.65% after 90 d operation. The highest Coulombic efficiency (23.3%) and the lowest charge transfer resistance (22.89 Ω) are obtained by FeCo/Co/Co₂P/NPGC (950 °C) cathode, indicating that it has a high bio-electrons recycling rate. Highly porous structure (539.50 m² g^?1) can provide the interconnected channels to facilitate the transport of O₂. FeCo alloys promote charge transfer and catalytic decomposition of H₂O₂ to ?OH and ?O₂^?, which inhibits cathodic biofilm growth to improve ORR durability. Synergies between metallic components (FeCo/Co/Co₂P) and N-doped carbon energetically improve the ORR catalytic activity of (FeCo)/Co/Co₂P/NPGC catalysts, which have the potential to be widely used as catalysts in MFCs.     

Anodic corrosion of heteroatom doped graphene oxide supports and its influence on the electrocatalytic oxygen evolution reaction

Transition metal-based electrocatalysts supported on carbon substrates face the challenges of anodic corrosion of carbon during oxygen evolution reaction at high oxidation potential. The role of electrophilic functional groups (carbonyl, pyridinic, thiol, etc.) incorporated in graphene oxide has been studied towards the anodic corrosion resistance. Heteroatom functionalized carbon supports possess modified electronic properties, surface oxygen content, and hydrophilicity, which are crucial in governing electrochemical corrosion in the alkaline oxidative environment. Evidently, electron-withdrawing groups in NGO support (pyridinic, cyano, nitro, etc) and its lower oxygen content impart maximum corrosion resistance and anodic stability in comparison to the other sulfur-doped and co-doped graphene oxide support. In this report, we establish the baseline evaluation of carbon-supported OER electrocatalysts by a systematic analysis of activity and substrate corrosion resistance. The result of this study establishes the role of surface composition of the doped supports while for designing a stable, corrosion-resistant OER electrocatalyst.     

Electrochemical performance of in situ LiFePO4 modified by N-doped graphene for Li-ion batteries

LiFePO₄ modified by N-doped graphene (NG) with a three-dimensional conductive network structure was synthesized via a one-step in situ hydrothermal method. The effects of N amount of NG on the phase structure, morphology, and electrochemical properties of LiFePO₄ are investigated in this study. X-ray diffraction (XRD) results show that doping suitable N amounts in NG do not alter the crystal structure of LiFePO_4, and scanning electron microscopy (SEM) images show that NG can slightly reduce the particle size of LiFePO₄. The high-resolution transmission electron microscopy (HRTEM) results show that the LiFePO₄ particles are well covered and connected by NG. The electrochemical performance confirms that LiFePO₄ modified by 20% N-doped graphene (named LFP/NG-4) displays a perfect specific capacity of 166.6 mAh·g^?1 at a rate of 0.2C and can reach 125 mAh·g^?1 at a rate of 5 C. Electrochemical impedance spectroscopy (EIS) results illustrate that the charge transfer resistance value of the LFP/NG-4 composite is only 58.6 Ω, which is very low compared with LiFePO₄. Cyclic voltammetry (CV) tests indicate that the addition of 20% N-doped graphene can effectively reduce electrode polarization and improve reversibility. The LFP/NG-4 composite with a three-dimensional conductive network structure can be regarded as a promising cathode material for Li-ion batteries.     

Synthesis of a Fe3O4-rGO-ZnO-catalyzed photo-Fenton system with enhanced photocatalytic performance

In this work, we designed a magnetically-separable Fe₃O₄-rGO-ZnO ternary catalyst, ZnO anchored on the surface of reduced graphene oxide (rGO)-wrapped Fe₃O₄ magnetic nanoparticles, where rGO, as an effective interlayer, can enhance the synergistic effect between ZnO and Fe₃O₄. The effects of three operational parameters, namely irradiation time, hydrogen peroxide dosage, and the catalyst dosage, on the photo-Fenton degradation of methylene blue and methyl orange were investigated. The results showed that the Fe₃O₄-rGO-ZnO had great potential for the destruction of organic compounds from wastewater using the Fenton chemical oxidation method at neutral pH. Repeatability of the photocatalytic activity after 5 cycles showed only a tiny drop in the catalytic efficiency.     

Tuning of shear thickening behavior and elastic strength of polyvinylidene fluoride via doping of ZnO-graphene

ZnO rice like nonarchitects are grafted on the graphene carbon core via a rapid microwave synthesis route. The prepared grafted systems are characterized via XRD, SEM, RAMAN, and XPS to examined the structural and morphological parameters. Zinc oxide grafted graphene sheets (ZnO-G) are further doped in β-phase of polyvinylidene fluoride (PVDF) to prepare the polymer nanocomposites (PNCs) via mixed solvent approach (THF/DMF). β-phase confirmation of PVDF PNCs is done by FTIR studies. It is observed that ZnO-G filler enhances the β-phase content in the PNCs. Non-doped PVDF and PNCs are further studied for rheological behavior under the shear rate of 1–100 s⁻¹. Doping of ZnO-G dopant to the PVDF matrix changes its discontinuous shear thickening (DST) behavior to continues shear thickening behavior (CST). Hydrocluster formation and their interaction with the dopant could be the reason for this striking DST to CST behavioral change. Strain amplitude sweep (10⁻³% -10%) oscillatory test reveals that the PNCs shows extended linear viscoelastic region with high elastic modulus and lower viscous modulus. Effective shear thickening behavior and strong elastic strength of these PNCs present their candidature for various fields including mechanical and soft body armor applications.     

On the Catalytic Activity of Sn Monomers and Dimers at Graphene Edges and the Synchronized Edge Dependence of Diffusing Atoms in Sn Dimers

In this study, in situ transmission electron microscopy is performed to study the interaction between single (monomer) and paired (dimer) Sn atoms at graphene edges. The results reveal that a single Sn atom can catalyze both the growth and etching of graphene by the addition and removal of C atoms respectively. Additionally, the frequencies of the energetically favorable configurations of an Sn atom at a graphene edge, calculated using density functional theory calculations, are compared with experimental observations and are found to be in good agreement. The remarkable dynamic processes of binary atoms (dimers) are also investigated and is the first such study to the best of the knowledge. Dimer diffusion along the graphene edges depends on the graphene edge termination. Atom pairs (dimers) involving an armchair configuration tend to diffuse with a synchronized shuffling (step-wise shift) action, while dimer diffusion at zigzag edge terminations show a strong propensity to collapse the dimer with each atom diffusing in opposite directions (monomer formation). Moreover, the data reveals the role of C feedstock availability on the choice a single Sn atom makes in terms of graphene growth or etching. This study advances the understanding single atom catalytic activity at graphene edges.     

Novel energy-saving window coating based on F doped TiO2 nanocrystals with enhanced NIR shielding performance

To reduce the energy consumption of cooling in the hot summer days, searching for novel NIR shielding materials for buildings is of great value. In this report, monodispersed F doped TiO₂ nanocrystals with an average size of 8.6 nm were synthesized as novel solar shielding materials for energy-saving windows. All the products adopted an anatase TiO₂ structure. After doping of F ions, the morphology of TiO₂ was transformed from an irregular shape to a pseudospherical shape. The Raman shift and XPS depth analysis confirmed the successful doping of F⁻ ions into the lattice oxygen sites in the TiO₂ structure. The introduction of F⁻ ions generated free electrons and bulk Ti³⁺ in TiO₂ crystals, which activated a localized surface plasmon resonance (LSPR) absorption in the NIR region. Correspondingly, the NIR shielding performance of the TiO₂ films improved with increasing F doping amounts. The NIR shielding value of the films increased from 1.3% to 43.2% when the molar ratio of F to Ti increased from 0 to 0.3. The reason can be attributed to the enhanced NIR absorption induced by the increased electron concentration after doping of fluorine ions. The F–TiO₂ films showed superior visible transmittance (90.1–96.7%). Moreover, the F–TiO₂ films lowered the indoor temperature of the heat box by 5.3 °C in the thermal tests. Overall, the prepared F–TiO₂ nanocrystals show a great potential to be used for energy-saving windows.     

Synthesis and plasma treatment of nitrogen-doped graphene fibers for high-performance supercapacitors

Graphene fiber-based supercapacitor has aroused great interest as a flexible power source in future wearable electronics. However, the low electrochemical performance of graphene fibers (GFs) usually causes the serious limitation of use in practical applications due to the material stacking, hydrophobicity and fabrication process complexity. In this work, a facile and effective plasma-assisted strategy is put forward to increase specific surface area, tune hierarchically porous structure and promote wettability of nitrogen-doped graphene fibers (NGFs), resulting in the improvement of electrochemical performance. The supercapacitor assembled from plasma-treated NGFs shows superior capacitance (878 mF/cm² at 0.1 mA/cm² current density) and high energy density (19.5 μW h/cm² at 40 mW/cm² power density), which is 23.7% and 131.4% higher than that of NGFs and GFs, respectively. Additionally, the fiber-based supercapacitor based on plasma-treated NGFs exhibits high rate capability of 59.8% and excellent cyclic performance (95.8% retention over 10,000 cycles). These plasma-treated NGFs can be promising candidates for high-performance and flexible power sources in future wearable electronics.