Highly Active and Stable Pt-Pd Alloy Catalysts Synthesized by Room-Temperature Electron Reduction for Oxygen Reduction Reaction.
ABSTRACT: Carbon-supported platinum (Pt) and palladium (Pd) alloy catalyst has become a promising alternative electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. In this work, the synthesis of highly active and stable carbon-supported Pt-Pd alloy catalysts is reported with a room-temperature electron reduction method. The alloy nanoparticles thus prepared show a particle size around 2.6 nm and a core-shell structure with Pt as the shell. With this structure, the breaking of O-O bands and desorption of OH are both promoted in electrocatalysis of ORR. In comparison with the commercial Pt/C catalyst prepared by conventional method, the mass activity of the Pt-Pd/C catalyst for ORR is shown to increase by a factor of ?4. After 10 000-cycle durability test, the Pt-Pd/C catalyst is shown to retain 96.5% of the mass activity, which is much more stable than that of the commercial Pt/C catalyst.
Project description:Improving the performance of oxygen reduction reaction (ORR) electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs). Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C) prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mgPt-1 at 0.9 V versus the reversible hydrogen electrode (RHE), which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications. The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing) are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mgPt-1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s-1), maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS) analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.
Project description:Hierarchical structures in shell with transition metal underneath is a promising design for high-performance and low-cost heterogeneous nanocatalysts (NCs). Such a design enables the optimum extent of synergetic effects in NC surface. It facilitates intermediate reaction steps and, therefore, boosts activity of NC in oxygen reduction reaction (ORR). In this study, carbon nanotube (CNT)-supported ternary metallic NC comprising Cucluster-in-Pdcluster nanocrystal and surface decoration of atomic Pt clusters (14 wt %) is synthesized by using the wet chemical reduction method with sequence and reaction time controls. By annealing in H2 environment (H2/N2 = 9:1, 10 sccm) at 600 K for 2 h, specific activity of Cu@Pd/Pt is substantially improved by ?2.0-fold as compared to that of the pristine sample and commercial Pt catalysts. By cross-referencing results of electron microscopic, X-ray spectroscopic, and electrochemical analyses, we demonstrated that reduction annealing turns ternary NC into complex of Cu3Pt alloy and Cu x Pd1-x alloy. Such a transition preserves Pt and Pd in metallic phases, therefore improving the activity by ?29% and the stability of NC in an accelerated degradation test (ADT) as compared to those of pristine Cu@Pd/Pt in 36?000 cycles at 0.85 V (vs RHE). This study presents robust H2 annealing for structure stabilization of NC and systematic characterizations for rationalization of the corresponding mechanisms. These results provide promising scenarios for facilitation of heterogeneous NC in ORR applications.
Project description:Bimetallic Pt-Ni with Pt on the outermost layer and an innermost layer enriched in Ni, referred to as Pt3Ni(Pt-skin), is a promising configuration of an electrocatalyst for the oxygen reduction reaction (ORR) in fuel cells. We prepare a core (Pd)/shell (Pt3Ni(Pt-skin)) catalyst (Pt3Ni(Pt-skin)/Pd/C) from Zn underpotential deposition (UPD) on a Ni UPD modified Pd/C catalyst, facilitating Pt atomic layer-by-layer growth on the Ni surface through the galvanic replacement process. Pt3Ni(Pt-skin)/Pd/C shows the best ORR performance, with a Pt specific activity of 16.7 mA cm-2 and Pt mass activity of 14.2 A mgPt-1, which are 90- and 156- fold improvements over commercial Pt/C catalysts. The Pt3Ni(Pt-skin) structure effectively inhibits Ni leaching to improve the durability in two accelerated durability test modes mimicking the catalyst lifetime and start-up/shut-down cycles.
Project description:A carbon-supported, dealloyed platinum-copper (Pt-Cu) oxygen reduction catalyst was prepared using a multi-step synthetic procedure. Material produced at each step was characterized using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), electron energy loss spectroscopy (EELS) mapping, x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and cyclic voltammetry (CV), and its oxygen reduction reaction (ORR) activity was measured by a thin-film rotating disk electrode (TF-RDE) technique. The initial synthetic step, a co-reduction of metal salts, produced a range of poorly crystalline Pt, Cu, and Pt-Cu alloy nanoparticles that nevertheless exhibited good ORR activity. Annealing this material alloyed the metals and increased particle size and crystallinity. TEM shows the annealed catalyst to include particles of various sizes, large (>25 nm), medium (12-25 nm), and small (<12 nm). Most of the small and medium-sized particles exhibited a partial or complete coreshell (Cu-rich core and Pt shell) structure with the smaller particles typically having more complete shells. The appearance of Pt shells after annealing indicates that they are formed by a thermal diffusion mechanism. Although the specific activity of the catalyst material was more than doubled by annealing, the concomitant decrease in Pt surface area resulted in a drop in its mass activity. Subsequent dealloying of the catalyst by acid treatment to partially remove the copper increased the Pt surface area by changing the morphology of the large and some medium particles to a "Swiss cheese" type structure having many voids. The smaller particles retained their core-shell structure. The specific activity of the catalyst material was little reduced by dealloying, but its mass activity was more than doubled due to the increase in surface area. The possible origins of these results are discussed in this report.
Project description:The search for high-performance non-platinum (Pt) electrocatalysts is the most challenging issue for fuel cell technology. Creating bimetallic non-Pt nanocrystals (NCs) with core/shell structures or alloy features has widely been explored as the most effective way for enhancing their electrochemical properties but still suffered from undesirable performance due to the limited interactions between the different components. By addressing the above issue, we report on a new class of active and stable bimetallic non-Pt electrocatalysts with palladium (Pd) icosahedra as the core and nickel (Ni) decorating the surface toward cathodic oxygen reduction reaction (ORR) under alkaline conditions. The optimized Pd6Ni icosahedra with unique interaction between an icosahedral Pd core and surface Ni yield the highest ORR activity with a mass activity of 0.22 A mgPd-1, which is better than those of the conventional Pd6Ni icosahedra with alloy surfaces or Pd-rich surfaces, and even two times higher than that of the commercial Pt/C (0.11 A mgPt-1), representing one of the best non-Pt electrocatalysts. Simulations reveal that the Pd icosahedra decorated with Ni atoms emerged in the subsurface can weaken the interaction between the adsorbed oxygen and Pd (111) facet and enhance the ORR activities due to an obvious shift of d-band center. More significantly, under electrochemical accelerated durability test, the Pd6Ni icosahedra can endure at least 10,000 cycles with negligible activity decay and structural change. The present work demonstrates an important advance in surface tuning of bimetallic NCs as high-performance non-Pt catalysts for catalysis, energy conversion, and beyond.
Project description:Next generation cathode catalysts for direct methanol fuel cells (DMFCs) must have high catalytic activity for the oxygen reduction reaction (ORR), a lower cost than benchmark Pt catalysts, and high stability and high tolerance to permeated methanol. In this study, palladium catalysts supported on titanium suboxides (Pd/TinO2n-1) were prepared by the sulphite complex route. The aim was to improve methanol tolerance and lower the cost associated with the noble metal while enhancing the stability through the use of titanium-based support; 30% Pd/Ketjenblack (Pd/KB) and 30% Pd/Vulcan (Pd/Vul) were also synthesized for comparison, using the same methodology. The catalysts were ex-situ characterized by physico-chemical analysis and investigated for the ORR to evaluate their activity, stability, and methanol tolerance properties. The Pd/KB catalyst showed the highest activity towards the ORR in perchloric acid solution. All Pd-based catalysts showed suitable tolerance to methanol poisoning, leading to higher ORR activity than a benchmark Pt/C catalyst in the presence of low methanol concentration. Among them, the Pd/TinO2n-1 catalyst showed a very promising stability compared to carbon-supported Pd samples in an accelerated degradation test of 1000 potential cycles. These results indicate good perspectives for the application of Pd/TinO2n-1 catalysts in DMFC cathodes.
Project description:High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp(2) carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700?°C. The catalyst shows onset potentials of 0.92?V in 0.1?M HClO4 and in 0.1?M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69?mA cm(-2) at 0.55?V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.
Project description:Voltammetric dealloying is a typical method to synthesize Pt-shell/less-noble metal (M) alloy core nanoparticles (NPs) toward the oxygen reduction reaction (ORR). The pristine nanostructures of the Pt-M alloy NPs should determine the ORR activity of the dealloyed NPs. In this study, we investigated the voltammetric dealloying behavior of the Pt-Co and nitrogen-introduced Pt-Co alloy NPs generated by synchronous arc-plasma deposition of Pt and Co. The results showed that the dealloying behavior is sensitive to cobalt nitride in the pristine NPs, leading to the preferential generation of a Pt-rich shell/Pt-Co alloy core architecture having enhanced ORR activity.
Project description:To realize the large-scale application of fuel cells, it is still a great challenge to improve the performance and reduce the cost of cathode catalysts towards oxygen reduction reaction (ORR). In this work, carbon-supported ordered Pt3Mn intermetallic catalysts were prepared by thermal annealing electrospun polyacrylonitrile nanofibers containing Platinum(II) acetylacetonate/ Manganese(III) acetylacetonate. Compared with its counterparts, the ordered Pt3Mn intermetallic obtained at 950 °C exhibits a more positive half-potential and higher kinetic current density during the ORR process. Benefiting from their defined stoichiometry and crystal structure, the Mn atoms in Pt3Mn intermetallic can modulate well the geometric and electronic structure of surface Pt atoms, endowing Pt3Mn catalyst with an enhanced ORR catalytic activity. Moreover, it also has a better catalytic stability and methanol tolerance than commercial Pt/C catalyst. Our study provides a new strategy to fabricate a highly active and durable Pt3Mn intermetallic electrocatalyst towards ORR.
Project description:Doping carbon materials have proved to be the front runners to substitute for Pt as oxygen reduction reaction (ORR) catalysts. Fluorine-doped graphene (FG) has rarely been used as ORR catalyst because of the difficulty in preparation. Herein, we report FG sheets prepared by a thermal pyrolysis graphene oxide (GO) process in the presence of zinc fluoride (ZnF2) as an efficient electrocatalyst for ORR in the alkaline medium. The results show that the pyrolysis temperature seriously affected the doped fluoride amount and morphology of catalyst. It is found that the FG-1100 catalyst possesses a more positive onset potential, higher current density and better four-electron process for ORR than other FG samples. FG-1100 displays an outstanding ORR catalytic activity that is comparable to that of the commercial Pt/C catalyst. Also, its durability and methanol tolerance ability are superior to those of the commercial Pt/C. The excellent ORR catalytic performance is closely related to its higher doped fluorine amount and wrinkle morphology. The FG catalyst can be developed as a low-cost, efficient and durable catalyst as a viable replacement for the Pt/C catalyst, promoting the commercialization of fuel cells.