A hybrid FeOx/CoOx/Pt ternary nanocatalyst for augmented catalysis of formic acid electro-oxidation.

Platinum-based catalysts that have long been used as the anodes for the formic acid electro-oxidation (FAO) in the direct formic acid fuel cells (DFAFCs) were susceptible to retrogradation in performance due to CO poisoning that impaired the technology transfer in industry. This work is designed to overcome this challenge by amending the Pt surface sequentially with nanosized cobalt (nano-CoOx, fibril texture of ca. 200 nm in particle size) and iron (nano-FeOx, nanorods of particle size and length of 80 and 253 nm, respectively) oxides. This enriched the Pt surface with oxygenated groups that boosted FAO and mitigated the CO poisoning. The unfilled d-orbitals of the transition metals and their tendency to vary their oxidations states presumed their participation in a faster mechanism of FAO. Engineering the Pt surface in this FeOx/CoOx/Pt hierarchy resulted in a remarkable activity toward FAO, that exceeded four times that of the Pt catalyst with up to ca. 2.5 times improvement in the catalytic tolerance against CO poisoning. This associated a ca. - 32 mV shift in the onset potential of FAO which increased to - 40 mV with a post-activation of the same catalyst at - 0.5  in 0.2 mol L-1 NaOH, displaying the catalyst's competitiveness in reducing overpotentials in DFAFCs. It also exhibited a favorable amelioration in the catalytic durability in long-termed chronoamperometric electrolysis. The electrochemical impedance spectroscopy and the CO stripping voltammetry were employed to elucidate the origin of enhancement.

Boosted formic acid electro-oxidation on platinum nanoparticles and "mixed-valence" iron and nickel oxides.

The modification of Pt nanoparticles (nano-Pt, assembled electrochemically onto a glassy carbon (GC) substrate) with hybrid multivalent nickel (nano-NiOx) and iron (nano-FeOx) oxide nanostructures was intended to steer the mechanism of the formic acid electro-oxidation (FAO) in the desirable dehydrogenation pathway. This binary modification with inexpensive oxides succeeded in mediating the reaction mechanism of FAO by boosting reaction kinetics "electron transfer" and amending the surface geometry of the catalyst against poisoning. The sequence of deposition was optimized where the a-FeOx/NiOx/Pt/GC catalyst (where "a" denotes a post-activation step for the catalyst at -0.5 V in 0.5 mol L-1 NaOH) reserved the best hierarchy. Morphologically, while nano-Pt appeared to be spherical (ca. 100 nm in average diameter), nano-NiOx appeared as flowered nanoaggregates (ca. 56 nm in average diameter) and nano-FeOx (after activation) retained a plate-like nanostructure (ca. 38 nm in average diameter and 167 nm in average length). This a-FeOx/NiOx/Pt/GC catalyst demonstrated a remarkable catalytic efficiency (125 mA mgPt-1) for FAO that was ca. 12.5 times that of the pristine Pt/GC catalyst with up to five times improvement in the catalytic tolerance against poisoning and up to -214 mV shift in the FAO's onset potential. Evidences for equipping the a-FeOx/NiOx/Pt/GC catalyst with the least charge transfer resistance and the highest stability among the whole investigated catalysts are provided and discussed.

Potential use of dry powder of Vossia cuspidata (Roxb.) Griff. rhizomes and leaves in methylene blue dye remediation.

Phytoremediation is a promising, cost-effective, and eco-friendly process for wastewater treatment. Herein, the dry biomasses of Vossia cuspidata (Roxb.) Griff. leaves (PL) and rhizomes including aerial stems (PR) were used to effectively remediate methylene blue (MB) dyes. Interestingly, the adsorption uptake and removal efficiency of MB by PR were higher than those of PL; exceeding 97 and 91% in 35 and 25 min for 0.1 and 0.4 g/L MB, respectively. The MB diffusion within the PL and PR was insignificant and the adsorption kinetics was principally controlled by the surface MB-adsorbent interaction, as consistently approved by the pseudo-second order kinetic model. In addition, the adsorption increased rapidly with the plant dosage with high dependence on the initial MB concentration. Moreover, the impact of shaking speed on the adsorption was minor but temperature played a critical role where the highest efficiencies were recorded at 30 and 40 °C on PL (91.9%) and PR (93.3%), respectively. The best removal efficiencies were attained with PR at pH 6, but with PL at pH 8. The Temkin isotherm could perfectly simulate the experimental data (R2 > 0.97); suggesting a linear decrease of the adsorption heat of MB with the plant coverage.

Tailor-designed nanowire-structured iron and nickel oxides on platinum catalyst for formic acid electro-oxidation.

This investigation is concerned with designing efficient catalysts for direct formic acid fuel cells. A ternary catalyst containing iron (nano-FeOx) and nickel (nano-NiOx) nanowire oxides assembled sequentially onto a bare platinum (bare-Pt) substrate was recommended for the formic acid electro-oxidation reaction (FAOR). While nano-NiOx appeared as fibrillar nanowire bundles (ca. 82 nm and 4.2 µm average diameter and length, respectively), nano-FeOx was deposited as intersecting nanowires (ca. 74 nm and 400 nm average diameter and length, respectively). The electrocatalytic activity of the catalyst toward the FAOR depended on its composition and loading sequence. The FeOx/NiOx/Pt catalyst exhibited ca. 4.8 and 1.6 times increases in the catalytic activity and tolerance against CO poisoning, respectively, during the FAOR, relative to the bare-Pt catalyst. Interestingly, with a simple activation of the FeOx/NiOx/Pt catalyst at -0.5 V vs. Ag/AgCl/KCl (sat.) in 0.2 mol L-1 NaOH, a favorable Fe2+/Fe3+ transformation succeeded in mitigating the permanent CO poisoning of the Pt-based catalysts. Interestingly, this activated a-FeOx/NiOx/Pt catalyst had an activity 7 times higher than that of bare-Pt with an ca. -122 mV shift in the onset potential of the FAOR. The presence of nano-FeOx and nano-NiOx enriched the catalyst surface with extra oxygen moieties that counteracted the CO poisoning of the Pt substrate and electronically facilitated the kinetics of the FAOR, as revealed from CO stripping and impedance spectra.

Propitious Dendritic Cu2O-Pt Nanostructured Anodes for Direct Formic Acid Fuel Cells.

This study introduces a novel competent dendritic copper oxide-platinum nanocatalyst (nano-Cu2O-Pt) immobilized onto a glassy carbon (GC) substrate for formic acid (FA) electro-oxidation (FAO); the prime reaction in the anodic compartment of direct formic acid fuel cells (DFAFCs). Interestingly, the proposed catalyst exhibited an outstanding improvement for FAO compared to the traditional platinum nanoparticles (nano-Pt) modified GC (nano-Pt/GC) catalyst. This was evaluated from steering the reaction mechanism toward the desired direct route producing carbon dioxide (CO2); consistently with mitigating the other undesired indirect pathway producing carbon monoxide (CO); the potential poison deteriorating the catalytic activity of typical Pt-based catalysts. Moreover, the developed catalyst showed a reasonable long-term catalytic stability along with a significant lowering in onset potential of direct FAO that ultimately reduces the polarization and amplifies the fuel cell's voltage. The observed catalytic enhancement was believed to originate bifunctionally; while nano-Pt represented the base for the FA adsorption, nanostructured copper oxide (nano-Cu2O) behaved as a catalytic mediator facilitating the charge transfer during FAO and providing the oxygen atmosphere inspiring the poison's (CO) oxidation at relatively lower potential. Surprisingly, moreover, nano-Cu2O induced a surface retrieval of nano-Pt active sites by capturing the poisoning CO via "a spillover mechanism" to renovate the Pt surface for the direct FAO. Finally, the catalytic tolerance of the developed catalyst toward halides' poisoning was discussed.

Fabrication and electrochemical application of three-dimensional gold nanoparticles: self-assembly.

Multilayers film of nanostructured citrate-stabilized gold particles (AuNPs) has been fabricated based on the layer-by-layer (LBL) technique using a self-assembled monolayer of 1,4-benzenedimethanethiol (BDMT). The formation of AuNPs and BDMT self-assemblies as alternative multilayers was confirmed by transmission electron microscopy (TEM), X-ray photoelectron spectroscope (XPS), and quartz crystal microbalance (QCM). The formation of uniform AuNP layers with an average monolayer thickness of 5-6 nm was obvious in the TEM images. The existence of BDMT molecules as cross linkers for the AuNPs' layers was proved by XPS measurements. The greater affinity of AuNPs' layers to bind BDMT molecules in comparison with the bare Au bulk electrode was revealed by QCM measurements. Electrochemically, the AuNPs' layers on the electrode surface did not only catalyze the reduction of oxygen (ca. 100-mV positive shift of the reduction peak potential compared with that at the bare Au bulk electrode) but also showed a fascinating nature of working as a renewed activated-electrode surface; a zigzag response was observed for oxygen reduction during alternative immobilization of BDMT and the AuNP layer. The self-assembly of a new AuNPs layer restored the catalytic activity that was entirely blocked by the preceding BDMT layer.