Reduced graphene oxide composite Ni3S2 microspheres grown directly on nickel foam as an efficient electrocatalyst for OER

The development of cheap, high-efficiency, and stable oxygen evolution reaction (OER) electrocatalysts is a current research hotspot. In this work, reduced graphene oxide (rGO) composite Ni₃S₂ microspheres grown directly on nickel foam (Ni₃S₂-rGO/NF) were prepared by tube furnace calcination and hydrothermal method. The Ni₃S₂-rGO/NF had excellent OER catalytic activity and stability with an overpotential of 303 mV at the current density of 100 mA cm⁻², which was 100 mV lower than that of Ni₃S₂/NF, and its Tafel slope was as low as 23 mV·dec⁻¹. The main reason for enhancing OER activity of the Ni₃S₂-rGO/NF is due to synergistic effect of Ni₃S₂ microspheres and rGO, which inhibited the production of NiS and refined the micron size of Ni₃S₂. This work offers a new method for developing stable and efficient OER catalysts.     

One-step preparation of Fe-doped Ni3S2/rGO@NF electrode and its superior OER performances

In order to improve the OER performance, Ni₃S₂-based catalysts were directly grown on Ni substrate by simultaneously doping of Fe and compositing with reduced graphene oxide (rGO). Synthesis and loading of Ni₃S₂/rGO were completed during a one-step hydrothermal process, in which Ni foam acted as support and Ni source of Ni₃S₂, as well as the subsequent current collector. It is found that either GO or Fe salt tuned Ni₃S₂ nanosheets into thinner and smaller interconnected nanosheets anchored on rGO, which enhanced the charge transfer resistance and improved the active sites. Hence, as-synthesized Fe-doped Ni₃S₂/rGO composite at 120 °C (Fe-2-Ni₃S₂/rGO@NF-120) exhibited an enhancement on OER performances: An overpotential of 247 mV at 20 mA cm⁻², and a small Tafel slope of 63 mV dec⁻¹, as well as an excellent stability of: 20 h maintaining at 20 mA cm⁻² or 50 mA cm⁻².     

Enhanced photoelectrochemical water splitting in hierarchical porous ZnO/Reduced graphene oxide nanocomposite synthesized by sol-gel method

Today the utilization of solar energy to split water and its conversion to hydrogen and oxygen has been considered as a powerful way to solve the environmental crisis. Hierarchical porous nanostructured ZnO and ZnO/reduced graphene oxide (rGO) composite photoanodes are synthesized by innovated sol-gel method using triethylenetetramine (TETA) as a stabilizer. The hierarchical porous ZnO structure containing large agglomerates each consisting of tiny nanoparticles are formed. The X-ray diffraction analysis and Raman spectroscopy confirm the in-situ reduction of graphene oxide sheets during synthesis and formation of ZnO/rGO nanocomposite. Although the band gap and transmittance of the porous nanocomposites do not dramatically change by rGO addition, the main photoluminescence peak quenches entirely showing prolonging exciton lifetime. The ZnO/rGO porous structure achieved remarkably improved current density (1.02 mA cm^?2 at 1.5 V vs. Ag/AgCl) in 1 wt% rGO, up to 12 times higher compared to the bare ZnO (0.09 mA cm^?2 at 1.5 V vs. Ag/AgCl), which attributes to positive role of ZnO hierarchical porous structure and rGO electron separation/transportation. These findings provide new insights into the broad applicability of this methodology for promising future semiconductor/graphene composite in the field of photoelectrochemical water splitting.     

Preparation and electrocatalytic characteristics of the Pt-based anode catalysts for ethanol oxidation in acid and alkaline media

The current study reports the preparation and investigation of several Pt-based anode catalysts loaded on reduced graphene oxide (rGO) as electrocatalysts in both acid and alkaline media for ethanol electrooxidation. The synthesized catalysts are evaluated by the method of XRD, Raman spectroscopy, XPS and TEM. Electrocatalytic properties of these catalysts for ethanol oxidation were investigated by cyclic voltammetry and chronoamperometry. It was found that the as-prepared nanocatalysts doped by metals and oxide metals showed the improvement of catalytic performance compared to Pt-only supported on graphene catalyst. The results indicated that the presence of Al favoured Pt nanoparticles dispersing on the surface of rGO sheets. Indeed, the PAG catalyst exhibits the highest mass activity for the ethanol oxidation of 1194 mA mg^?1_Pt in acid medium and 3691 mA mg^?1_Pt in alkaline medium. In addition, the PAG catalyst also shows good antipoisoning ability for ethanol electrooxidation in both media. This catalyst could be a potential catalyst for direct ethanol fuel cell (DEFC).     

Co(OH)2 nanoparticles deposited on reduced graphene oxide nanoflake as a suitable electrode material for supercapacitor and oxygen evolution reaction in alkaline media

In this work, cobalt hydroxide nanoparticles are simply synthesized (size is about 50 nm) and deposited on the reduced graphene oxide nanoflake by the hydrothermal method. Then, the ability of glassy carbon electrode modified with this low-cost nanocomposite is examined as a supercapacitor and oxygen evolution electrocatalysts in 2.0 mol L^?1 KOH by a three-electrode system. The modified electrode as a pseudocapacitor with potential windows of 0.35 V, exhibits a powerful specific capacitance (235.20 F g^?1 at 0.1 A g^?1 current density), energy density, stability (about 90% of the initial capacitance value maintain after 2000 cycles at 1.0 A g^?1) and fast charge/discharge ability. Furthermore, the modified electrode displays a good electrocatalytic activity for oxygen evolution reaction with a current density of 10.0 mA cm^?2 at 1.647 V, small Tafel slope of 56.5 mV dec^?1, good onset potential of 1.521 V vs. RHE and suitable durability.     

ZIF-L-Co@carbon fiber paper composite derived Co/Co3O4@C electrocatalyst for ORR in alkali/acidic media and overall seawater splitting

Green and clean energy technologies, including fuel cells, metal-air batteries, water splitting et al., are becoming more significant for our lives. Oxygen reduction reaction (ORR), hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are key reaction processes for fuel cells, metal-air batteries and water splitting. Therefore, it is highly desirable to design a multifunctional catalyst, which owns catalytic performance under a widely applied range. Herein, we demonstrate a novel multifunctional catalyst (Co/Co₃O₄@C) by carbonizing a composite material constructed of zeolite imidazolate framework and carbon fiber paper (ZIF-L-Co@CP). It is a carbon-based material containing metallic Co and Co₃O₄ as a low-cost and effective catalyst toward the ORR and overall water splitting. For ORR, the Co/Co₃O₄@C catalyst shows high half-wave potential in both alkaline and acidic media, 0.823 V for 0.1 M KOH and 0.672 V for 0.1 M HClO₄. More importantly, it exhibits good catalytic activities of hydrogen and oxygen evolutions to perform overall splitting in actual seawater.     

Nickel-polyaniline composite electrodes for hydrogen evolution reaction in alkaline media

In this work, nickel-based electrodes were prepared using a composite electrodeposition technique in a nickel bath containing suspended polyaniline (PAni) particles. The electrodes were characterized by Raman spectroscopy and scanning electron microscopy. The catalytic activity of the composite electrodes for the hydrogen evolution reaction (HER) was measured by cathodic polarization and electrochemical impedance spectroscopy in KOH and KOH with 1 M sucrose at room temperature. The Ni–PAni electrodes showed a high active surface area that contributed to the increase in the current density of HER and to the decrease in overpotential value as compared to Ni electrodes.     

Nickel foam-supported Fe,Ni-Polyporphyrin microparticles: Efficient bifunctional catalysts for overall water splitting in alkaline media

Developing highly active, stable and sustainable electrocatalysts for overall water splitting is of great importance to generate renewable H₂ for fuel cells. Herein, we report the synthesis of electrocatalytically active, nickel foam-supported, spherical core-shell Fe-poly(tetraphenylporphyrin)/Ni-poly(tetraphenylporphyrin) microparticles (FeTPP@NiTPP/NF). We also show that FeTPP@NiTPP/NF exhibits efficient bifunctional electrocatalytic properties toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Electrochemical tests in KOH solution (1 M) reveal that FeTPP@NiTPP/NF electrocatalyzes the OER with 100 mA cm⁻² at an overpotential of 302 mV and the HER with 10 mA cm⁻² at an overpotential of 170 mV. Notably also, its catalytic performance for OER is better than that of RuO₂, the benchmark OER catalyst. Although its catalytic activity for HER is slightly lower than that of Pt/C (the benchmark HER electrocatalyst), it shows greater stability than the latter during the reaction. The material also exhibits electrocatalytic activity for overall water splitting reaction at a current density of 10 mA cm⁻² with a cell voltage of 1.58 V, along with a good recovery property. Additionally, the work demonstrates a new synthetic strategy to an efficient, noble metal-free-coordinated covalent organic framework (COF)-based, bifunctional electrocatalyst for water splitting.     

Excellent electro-oxidation of methanol and ethanol in alkaline media: Electrodeposition of the NiMoP metallic nano-particles on/in the ERGO layers/CE

Here, the Ni-based metallic nano-particles (Ni, NiMo and NiMoP) were electrodeposited on/in the surface of ERGO/CE substrate from a citrate-based electrolyte and their catalytic activities investigated towards methanol and ethanol electro-oxidation. The physicochemical characterizations of all prepared electrocatalysts were investigated by different electrochemical and non-electrochemical techniques. The electrocatalytic activities of the modified electrodes towards the electro-oxidation of methanol and ethanol were studied in 0.1 M NaOH solution by conventional electrochemical methods such as cyclic voltammetry and chronoamperometry. In the optimized electrodeposition conditions, the obtained electrochemical results indicate that the NiMoP/ERGO/CE displays dramatically improved electrocatalytic activity [J_pf (mA.cm⁻²) = 263.14 for methanol and J_pf (mA.cm⁻²) = 253.35 for ethanol], stability and poisoning tolerance towards the electro-oxidation of these fuels in alkaline solution. Finally, for comparison, the Ni (alone) and NiMo (binary) electrodeposited on/in the ERGO/CE (without P) and also studying the influence of the ERGO layers on the surface of CE, the NiMoP/CE (without ERGO) were prepared and applied as electrocatalysts.     

Spontaneous polarization enhanced bismuth ferrate photoelectrode: fabrication and boosted photoelectrochemical water splitting property

In this paper, the fabrication of a highly orientated Bi₂Fe₄O₉ (BFO) photoelectrode in the presence of two-dimensional (2D) graphene oxide (GO) was reported. It was found that the GO can be used as a template for controlling the growth of BFO, and the nanoplate composites of BFO/reduced graphene oxide (RGO) with a high orientation can be fabricated. The thickness of the nanoplates became thinner as the ratio of GO increased. As a result, the ferroelectric spontaneous polarization unit arranges itself in the space in a periodic manner, leading to the formation of a polarization field along a special direction. Therefore, the created built-in electric field of the nanoplate composites of BFO/RGO is improved upon the increase of the amount of RGO. As expected, carrier separation is enhanced by the built-in electric field, therefore substantially enhancing the photoelectrochemical (PEC) activity of water splitting compared to pure BFO under the irradiation of visible-light.     

Pd electrodeposition on a novel substrate of reduced graphene oxide/ poly(melem-formaldehyde) nanocomposite as an active and stable catalyst for ethanol electrooxidation in alkaline media

Palladium nanoparticles (Pd NPs) were successfully electrodeposited on a reduced graphene oxide/poly(melem-formaldehyde) nanocomposite (rGO/PMF) NC as a catalyst for ethanol electrooxidation in alkaline media; melem was used as a nitrogen-rich source in the substrate structure for the first time. The specific surface area and average pore diameter of (rGO/PMF) NC were 481.61 m² gr^?1 and 10.23 nm, respectively. High nitrogen doping and structural defects improved the dispersion and anchoring of Pd NPs on (rGO/PMF) NC. The onset potential (E_onset) of Pd/(rGO/PMF) NC was shifted negatively to 110 mV, in comparison to Pd/rGO. Also, the current density and electrochemical active surface area (EASA) of Pd/(rGO/PMF) NC were enhanced to 44 mA cm^?2 and 67.58 m² gr^?1, respectively, as compared to Pd/rGO. Furthermore, the stability of Pd/(rGO/PMF)NC was indicated against ethanol oxidation intermediates during 7000 s. This work also produced a superior graphene-based material for direct ethanol fuel cell anode catalysts applications.     

Spectrally selective coating of nanoparticles (Co3O4:Cr2O3) incorporated in carbon to captivate solar energy

Innovatory nanocomposite comprising nanomaterials Co₃O₄:Cr₂O₃ and carbon (fuel ash) was designed to absorb solar energy. Different concentration ratios of Co₃O₄ and Cr₂O₃ nanoparticles were utilized as a dopant for fuel thin films synthesis via spin and casting methods on glass and aluminum substrates. The optical properties of the modified films demonstrated in the range of 250 to 1300 nm. The data were interpreted in terms of a phonon‐assisted theory. Energy gap (E_g) of doped C was calculated with different concentration ratios of Co₃O₄:Cr₂O₃ (0.5:2.5, 1:2, 1.5:1.5, 2:1, 2.5:0.5) wt%, and fixed concentration of C in 7wt%. The results showed E_g of the doped samples in the range of 2.9 to 3.9 eV. In addition, the intensity of the solar radiation was measured. The absorptivity was in the range of 88 to 93.6%. The above results are comparable to those of semiconductors and have high absorptivity values when the nanocomposite was utilized on a flat plate collector as a coating to trap and absorb solar energy.     

A melamine formaldehyderesin route to in situ encapsulate Co2O3 into carbon black for enhanced oxygen reduction in alkaline media

Enhancing the activity and stability of the non-precious metal catalyst (NPMC) for oxygen reduction reaction (ORR) is vital for the commercialization of fuel cells. Herein, we put forward a method in which the melamine formaldehyderesin was used as a precursor to encapsulate in situ Co₂O₃ into carbon black to form Co₂O₃@MF-C catalysts. The prepared catalysts were characterized by TEM, XRD, XPS, BET, and Raman spectroscopy. The electrocatalytic activity was measured by using rotating disk electrode (RDE) voltammetry. The Co₂O₃@MF-Cs shows outstanding electrocatalytic activity in alkaline solution compared with the commercial Pt/C catalyst. The 20%Co₂O₃@MF-C-650 shows the highest activity for ORR and its initial reduction potential and half-wave potential reach 1.01 V and 0.94 V, respectively, in 0.1 M KOH solution. The prepared catalysts also follow the 4-electron pathway ORR process both in alkaline and in acid conditions.