Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte.
ABSTRACT: The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.
Project description:The synthesis and properties of an oxygen reduction catalyst based on a unique 3-dimensional (3D) nitrogen doped (N-doped) carbon composite are described. The composite material is synthesised via a two-step hydrothermal and pyrolysis method using bio-source low-cost materials of galactose and melamine. Firstly, the use of iron salts and galactose to hydrothermally produceiron oxide (Fe?O?) magnetic nanoparticle clusters embedded carbon spheres. Secondly, magnetic nanoparticles diffused out of the carbon sphere when pyrolysed in the presence of melamine as nitrogen precursor. Interestingly, many of these nanoparticles, as catalyst-grown carbon nanotubes (CNTs), resulted in the formation of N-doped CNTs and N-doped carbon spheres under the decomposition of carbon and a nitrogen environment. The composite material consists of integrated N-doped carbon microspheres and CNTs show high ORR activity through a predominantly four-electron pathway.
Project description:Transitional metal-nitrogen-carbon system is a promising candidate to replace the Pt-based electrocatalyst due to its superior activity, durability and cost effectiveness. In this study, we have designed a simple strategy to fabricate carbon nanotubes-supported binary-nitrogen-carbon catalyst via wet-chemical method. Palladium and transitional metals (M, i.e. manganese cobalt and copper) nanoparticles are anchored through four-nitrogen system onto carbon nanotubes (denoted as PdM-N<sub>4</sub>/CNTs). This material has been used as bifunctional electrocatalyst for electrochemical ethanol oxidation reaction and hydrogen evolution reaction for the first time. The N<sub>4</sub>-linked nanoparticles onto carbon nanotubes plays a crucial role in intrinsic catalytic activity for both reactions in 1 M KOH electrolyte. Among three PdM-N<sub>4</sub>/CNTs catalysts, the PdMn-N<sub>4</sub>/CNTs catalyst exhibits higher catalytic activity in terms of current density, mass activity and stability compared to the benchmark Pt/C. The robust electrocatalysis are inherited from the better attachment of PdMn through N<sub>4</sub>-system onto carbon nanotubes, comparatively smaller particles formation with better dispersion and higher electrical conductivity.
Project description:Operating fuel cells in alkaline environments permits the use of platinum-group-metal-free (PGM-free) catalysts and inexpensive bipolar plates, leading to significant cost reduction. Of the PGM-free catalysts explored, however, only a few nickel-based materials are active for catalyzing the hydrogen oxidation reaction (HOR) in alkali; moreover, these catalysts deactivate rapidly at high anode potentials owing to nickel hydroxide formation. Here we describe that a nickel-tungsten-copper (Ni<sub>5.2</sub>WCu<sub>2.2</sub>) ternary alloy showing HOR activity rivals Pt/C benchmark in alkaline electrolyte. Importantly, we achieved a high anode potential up to 0.3 V versus reversible hydrogen electrode on this catalyst with good operational stability over 20 h. The catalyst also displays excellent CO-tolerant ability that Pt/C catalyst lacks. Experimental and theoretical studies uncover that nickel, tungsten, and copper play in synergy to create a favorable alloying surface for optimized hydrogen and hydroxyl bindings, as well as for the improved oxidation resistance, which result in the HOR enhancement.
Project description:Core/shell nanostructured carbon materials with carbon nanofiber (CNF) as the core and a nitrogen (N)-doped graphitic layer as the shell were synthesized by pyrolysis of CNF/polyaniline (CNF/PANI) composites prepared by in situ polymerization of aniline on CNFs. High-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared and Raman analyses indicated that the PANI shell was carbonized at 900°C. Platinum (Pt) nanoparticles were reduced by formic acid with catalyst supports. Compared to the untreated CNF/PANI composites, the carbonized composites were proven to be better supporting materials for the Pt nanocatalysts and showed superior performance as catalyst supports for methanol electrochemical oxidation. The current density of methanol oxidation on the catalyst with the core/shell nanostructured carbon materials is approximately seven times of that on the catalyst with CNF/PANI support. TEM tomography revealed that some Pt nanoparticles were embedded in the PANI shells of the CNF/PANI composites, which might decrease the electrocatalyst activity. TEM-energy dispersive spectroscopy mapping confirmed that the Pt nanoparticles in the inner tube of N-doped hollow CNFs could be accessed by the Nafion ionomer electrolyte, contributing to the catalytic oxidation of methanol.
Project description:The sintering of supported metal nanoparticles is a major route to the deactivation of industrial heterogeneous catalysts, which largely increase the cost and decrease the productivity. Here, we discover that supported palladium/gold/platinum nanoparticles distributed at the interface of oxide supports and nitrogen-doped carbon shells would undergo an unexpected nitrogen-doped carbon atomization process against the sintering at high temperatures, during which the nanoparticles can be transformed into more active atomic species. The in situ transmission electron microscopy images reveal the abundant nitrogen defects in carbon shells provide atomic diffusion sites for the mobile atomistic palladium species detached from the palladium nanoparticles. More important, the catalytic activity of sintered and deactivated palladium catalyst can be recovered by this unique N-doped carbon atomization process. Our findings open up a window to preparation of sintering-resistant single atoms catalysts and regeneration of deactivated industrial catalysts.
Project description:Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.
Project description:Single-site catalysts feature high catalytic activity but their facile construction and durable utilization are highly challenging. Herein, we report a simple impregnation-adsorption method to construct platinum single-site catalysts by synergic micropore trapping and nitrogen anchoring on hierarchical nitrogen-doped carbon nanocages. The optimal catalyst exhibits a record-high electrocatalytic hydrogen evolution performance with low overpotential, high mass activity and long stability, much superior to the platinum-based catalysts to date. Theoretical simulations and experiments reveal that the micropores with edge-nitrogen-dopants favor the formation of isolated platinum atoms by the micropore trapping and nitrogen anchoring of [PtCl6]2-, followed by the spontaneous dechlorination. The platinum-nitrogen bonds are more stable than the platinum-carbon ones in the presence of adsorbed hydrogen atoms, leading to the superior hydrogen evolution stability of platinum single-atoms on nitrogen-doped carbon. This method has been successfully applied to construct the single-site catalysts of other precious metals such as palladium, gold and iridium.
Project description:Metal-air batteries and fuel cells have attracted much attention as powerful candidates for a renewable energy conversion system for the last few decades. However, the high cost and low durability of platinum-based catalysts used to enhance sluggish oxygen reduction reaction (ORR) at air electrodes prevents its wide application to industry. In this work, we applied a plasma process to synthesize cobalt nanoparticles catalysts on nitrogen-doped carbon support with controllable quaternary-N and amino-N structure. In the electrochemical test, the quaternary-N and amino-N-doped carbon (Q-A)/Co catalyst with dominant quaternary-N and amino-N showed the best onset potential (0.87 V vs. RHE) and highest limiting current density (-6.39 mA/cm2). Moreover, Q-A/Co was employed as the air catalyst of a primary zinc-air battery with comparable peak power density to a commercial 20 wt.% Pt/C catalyst with the same loading, as well as a stable galvanostatic discharge at -20 mA/cm2 for over 30,000 s. With this result, we proposed the synergetic effect of transitional metal nanoparticles with controllable nitrogen-bonding can improve the catalytic activity of the catalyst, which provides a new strategy to develop a Pt-free ORR electrocatalyst.
Project description:Hydroxide exchange membrane fuel cells offer possibility of adopting platinum-group-metal-free catalysts to negotiate sluggish oxygen reduction reaction. Unfortunately, the ultrafast hydrogen oxidation reaction (HOR) on platinum decreases at least two orders of magnitude by switching the electrolytes from acid to base, causing high platinum-group-metal loadings. Here we show that a nickel-molybdenum nanoalloy with tetragonal MoNi<sub>4</sub> phase can catalyze the HOR efficiently in alkaline electrolytes. The catalyst exhibits a high apparent exchange current density of 3.41 milliamperes per square centimeter and operates very stable, which is 1.4 times higher than that of state-of-the-art Pt/C catalyst. With this catalyst, we further demonstrate the capability to tolerate carbon monoxide poisoning. Marked HOR activity was also observed on similarly designed WNi<sub>4</sub> catalyst. We attribute this remarkable HOR reactivity to an alloy effect that enables optimum adsorption of hydrogen on nickel and hydroxyl on molybdenum (tungsten), which synergistically promotes the Volmer reaction.
Project description:Nitrogen-doped, bamboo-like carbon nanotubes (BCNTs) were synthesized from butylamine by catalytic chemical vapor deposition (CCVD method). The nanotubes were oxidized by H<sub>2</sub>SO<sub>4</sub>/HNO<sub>3</sub> treatment and used to prepare calcium alginate gelled BCNT spheres. These beads were first carbonized and then Pd, Rh and Ni nanoparticles were anchored on the surface of the spheres. These systems were then applied as catalysts in CO<sub>2</sub> hydrogenation. The BCNT support was examined by Raman spectroscopy, dynamic light scattering (DLS) and X-ray photoelectron spectroscopy (XPS). The prepared catalysts were characterized by HRTEM and SEM. The oxidation pretreatment of BCNTs was successful, with the electrokinetic potential of the water-based dispersion of BCNTs measuring -59.9?mV, meaning the nanotube dispersion is stable. Pyridinic and graphitic types of incorporated nitrogen centers were identified in the structure of the nanotubes, according to the XPS measurements. The Pd-containing BCNT sphere catalyst was the most efficient in the catalytic studies. The highest conversion was reached on the Pd catalyst at 723?K, as well as at 873?K. The difference in the formation rate of CO was much less at 873?K between the Pd and Rh compared to the 723?K values. Accordingly, the application of Pd-containing BCNT/carbon-supported catalyst favored the generation of CO. However, the Ni-BCNT/carbon catalyst leads to the formation of CH<sub>4</sub> as the major product.