Project description:The alteration of surface functional properties via incorporation of foreign atoms is supposed to be a key strategy for the enhanced catalytic performance of noble-metal based nanocatalysts (NCs). In the present study, carbon-supported palladium (Pd)-based NCs including Pd, PdPt and PdRuPt have been prepared via a polyol reduction method under the same reduction conditions as for formic acid oxidation reaction (FAOR) applications. By cross-referencing the results of the microscopic, spectroscopic and electrochemical analysis we demonstrated that adding a small amount of platinum (Pt) into Pd NCs (i.e. PdPt NCs) significantly promotes the FAOR performance as compared to that of Pd NCs via weakening the COads bond strength at a lower voltage (0.875 V vs. NHE) than Pd (0.891 V vs. NHE). Of special relevance, the PdPt NC shows a mass activity (MA) of 1.0 A mg-1 and 1.9 A mg-1, respectively, in the anodic and cathodic scan. These values are ∼1.7-fold (0.6 A mg-1) and ∼4.8-fold (0.4 A mg-1) higher than those of Pd NC. Moreover, PdPt NC retains a higher MA (54 mA mg-1) than that of Pd NC (9 mA mg-1) after chronoamperometric (CA) stability tests over 2000 s. Meanwhile, further addition of ruthenium (Ru) (i.e. PdRuPt NCs) outstandingly enhances the CO tolerance during the CA test via removal of adsorbed COads and thus shows the highest MA (62 mA mg-1) after CA testing, which is higher than that of PdPt (54 mA mg-1) and Pd (9 mA mg-1) NCs. The intriguing results obtained in this study have great significance to provide further strategic opportunities for tuning the surface electronic properties of Pd-based NCs to design Pd-based NCs with improved electrochemical performance.
Project description:While Ru owns superior catalytic activity toward hydrogen oxidation reaction and cost advantages, the catalyst deactivation under high anodic potential range severely limits its potential to replace the Pt benchmark catalyst. Unveiling the deactivation mechanism of Ru and correspondingly developing protection strategies remain a great challenge. Herein, we develop atomic Pt-functioned Ru nanoparticles with excellent anti-deactivation feature and meanwhile employ advanced operando characterization tools to probe the underlying roles of Pt in the anti-deactivation. Our studies reveal the introduced Pt single atoms effectively prevent Ru from oxidative passivation and consequently preserve the interfacial water network for the critical H* oxidative release during catalysis. Clearly understanding the deactivation nature of Ru and Pt-induced anti-deactivation under atomic levels could provide valuable insights for rationally designing stable Ru-based catalysts for hydrogen oxidation reaction and beyond.
Project description:The exact mechanism behind the cation-assisted hydrogen oxidation reaction (HOR) on platinum electrodes in alkaline media remains disputed. We show that the cation effects at platinum display a remarkable structure sensitivity: not only the H adsorption but also the HOR activity on (111) terrace sites are independent of the nature of cation and cation concentration. On (110) step sites, at low cation concentration and mildly alkaline media, cations promote the HOR, whereas at more alkaline pH and consequently higher near-surface cation concentrations, the HOR is inhibition by the cations. Moreover, the role of the cation on terrace-OHad is different from that on step-OHad, as can also be observed from the inhibition of the HOR current by terrace-OHad at higher potentials. These results suggest that near the onset potential, HOR mainly takes place on steps, but under diffusion-limited conditions at higher overpotential, HOR mainly takes place on terraces.
Project description:Anion exchange membrane fuel cells (AEMFCs) are one of the ideal energy conversion devices. However, platinum (Pt), as the benchmark catalyst for the hydrogen oxidation reaction (HOR) of AEMFCs anodes, still faces issues of insufficient performance and susceptibility to CO poisoning. Here, we report the Joule heating-assisted synthesis of a small sized Ru1Pt single-atom alloy catalyst loaded on nitrogen-doped carbon modified with single W atoms (s-Ru1Pt@W1/NC), in which the near-range single Ru atoms on the Ru1Pt nanoparticles and the long-range single W atoms on the support simultaneously modulate the electronic structure of the active Pt-site, enhancing alkaline HOR performance of s-Ru1Pt@W1/NC. The mass activity of s-Ru1Pt@W1/NC is 7.54 A mgPt+Ru-1 and exhibits notable stability in 1000 ppm CO/H2-saturated electrolyte. Surprisingly, it can operate stably in H2-saturated electrolyte for 1000 h with only 24.60 % decay. Theoretical calculations demonstrate that the proximal single Ru atoms and the remote single W atoms synergistically optimize the electronic structure of the active Pt-site, improving the HOR activity and CO tolerance of the catalyst.
Project description:Anion exchange membrane fuel cells are limited by the slow kinetics of alkaline hydrogen oxidation reaction (HOR). Here, we establish HOR catalytic activities of single-atom and diatomic sites as a function of *H and *OH binding energies to screen the optimal active sites for the HOR. As a result, the Ru-Ni diatomic one is identified as the best active center. Guided by the theoretical finding, we subsequently synthesize a catalyst with Ru-Ni diatomic sites supported on N-doped porous carbon, which exhibits excellent catalytic activity, CO tolerance, and stability for alkaline HOR and is also superior to single-site counterparts. In situ scanning electrochemical microscopy study validates the HOR activity resulting from the Ru-Ni diatomic sites. Furthermore, in situ x-ray absorption spectroscopy and computational studies unveil a synergistic interaction between Ru and Ni to promote the molecular H2 dissociation and strengthen OH adsorption at the diatomic sites, and thus enhance the kinetics of HOR.
Project description:Electrochemical hydrogen evolution is a highly efficient way to produce hydrogen, but since it is limited by high-cost electrocatalysts, the preparation of high-efficiency electrocatalysts with fewer or free noble metals is important. Here, Ta3N5 nanobelt (NB)-loaded Ru nanoparticle (NP) hybrids with various ratios, including 1~10 wt% Ru/Ta3N5, are constructed to electrocatalyze water splitting for a hydrogen evolution reaction (HER) in alkaline media. The results show that 5 wt% Ru/Ta3N5 NBs have good HER properties with an overpotential of 64.6 mV, a Tafel slope of 84.92 mV/dec at 10 mA/cm2 in 1 M of KOH solution, and good stability. The overpotential of the HER is lower than that of Pt/C (20 wt%) at current densities of 26.3 mA/cm2 or more. The morphologies and structures of the materials are characterized by scanning electron microscopy and high-resolution transmission electron microscopy, respectively. X-ray photoelectron energy spectroscopy (XPS) demonstrates that a good HER performance is generated by the synergistic effect and electronic transfer of Ru to Ta3N5. Our electrochemical analyses and theoretical calculations indicate that Ru/Ta3N5 interfaces play an important role as real active sites.
Project description:We evaluated the activities of well-defined Ru@Pt core-shell nanocatalysts for hydrogen evolution and oxidation reactions (HER-HOR) using hanging strips of gas diffusion electrode (GDE) in solution cells. With gas transport limitation alleviated by micro-porous channels in the GDEs, the charge transfer resistances (CTRs) at the hydrogen reversible potential were conveniently determined from linear fit of ohmic-loss-corrected polarization curves. In 1 M HClO4 at 23 °C, a CTR as low as 0.04 Ω cm(-2) was obtained with only 20 μg cm(-2) Pt and 11 μg cm(-2) Ru using the carbon-supported Ru@Pt with 1:1 Ru:Pt atomic ratio. Derived from temperature-dependent CTRs, the activation barrier of the Ru@Pt catalyst for the HER-HOR in acids is 0.2 eV or 19 kJ mol(-1). Using the Ru@Pt catalyst with total metal loadings <50 μg cm(-2) for the HER in proton-exchange-membrane water electrolyzers, we recorded uncompromised activity and durability compared to the baseline established with 3 mg cm(-2) Pt black.
Project description:Electrochemical water splitting via a cathodic hydrogen evolution reaction (HER) is an advanced technology for clean H2 generation. Ru nanoparticle is a promising candidate for the state-of-the-art Pt catalyst; however, they still lack the competitiveness of Pt in alkaline and neutral media. Herein, a ternary HER electrocatalyst involving nano Ru and Cr2O3 as well as N-doped graphene (NG) that can work in alkaline and neutral media is proposed. Cr2O3 and NG feature strong binding energies for hydroxyl and hydrogen, respectively, which can accelerate the dissociation of water, whereas Ru has weak hydrogen binding energy to stimulate hydrogen coupling. The HER activity of Ru is greatly enhanced by the promoted water-dissociation effect of NG and Cr2O3. To achieve a current density of 10 mA cm-2, the as-obtained Ru-Cr2O3/NG only needs a very low overpotential of 47 mV, which outperforms the activity of Pt/C in alkaline media. The strategy proposed here, multi-site acceleration of water dissociation, provides new guidance on the design of a highly efficient, inexpensive, and biocompatible HER catalyst in nonacidic condition.
Project description:Due to the potential application in the future energy conversion system, there is an increasing demand for efficient, stable and cheap platinum-free catalysts for hydrogen evolution. However, it is still a great challenge to develop electrocatalysts with high activity similar to platinum or even higher, especially those that can work under alkaline conditions. Ruthenium (Ru), as a cheap substitute for platinum, has been studied as a feasible substitute for (HER) catalyst for hydrogen evolution reaction. In this paper, we designed and developed a novel Ru catalyst (Ru@CNT) supported on nitrogen-doped carbon nanotubes. Electrochemical tests show that even under alkaline conditions (1 M KOH), Ru@CNT still shows excellent catalytic performance and good durability. It only needs 36.69 mV overpotential to reach a current density of 10 mA cm-2, and its Tafel slope is 28.82 mV dec-1. The catalytic performance of the catalyst is comparable to that of 20% Pt/C. The significant activity is mainly attributed to the chelation of highly dispersed ruthenium atoms on nitrogen-doped carbon nanotubes. Secondly, the one-dimensional pore structures supported by nitrogen heterocarbon nanotubes can provide more opportunities for active centers. Excellent HER performance makes Ru@CNT electrocatalyst have a broad application prospect in practical hydrogen production.
Project description:Exploring an active and cost-effective electrocatalyst alternative to carbon-supported platinum nanoparticles for alkaline hydrogen evolution reaction (HER) have remained elusive to date. Here, we report a catalyst based on platinum single atoms (SAs) doped into the hetero-interfaced Ru/RuO2 support (referred to as Pt-Ru/RuO2), which features a low HER overpotential, an excellent stability and a distinctly enhanced cost-based activity compared to commercial Pt/C and Ru/C in 1 M KOH. Advanced physico-chemical characterizations disclose that the sluggish water dissociation is accelerated by RuO2 while Pt SAs and the metallic Ru facilitate the subsequent H* combination. Theoretical calculations correlate with the experimental findings. Furthermore, Pt-Ru/RuO2 only requires 1.90 V to reach 1 A cm-2 and delivers a high price activity in the anion exchange membrane water electrolyzer, outperforming the benchmark Pt/C. This research offers a feasible guidance for developing the noble metal-based catalysts with high performance and low cost toward practical H2 production.