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The oxygen reduction reaction (ORR) that occurs on the outermost layer of electrocatalysts is significantly affected by the composition and structure of the electrocatalysts. During the preparation of PtM alloy electrocatalysts, high-temperature annealing in an inert or reducing atmosphere could promote the segregation of M toward the core, forming a highly active Pt-skin structure. However, under fuel cell operating conditions, the adsorption of oxygen-containing groups could stimulate the easily dissolved M to segregate to the surface, reducing the activity and stability of the electrocatalysts. In this work, we conducted segregation energy calculation of PtM (M = Cu, Pd, Au) electrocatalysts under specific adsorption (SA), aqueous solution (AS) and an external electric field (EEF) with a density functional theory method. It was found that different factors have different effects on the segregation energy: ΔΔESA ≫; ΔΔEEEF > ΔΔEAS. The coupling effects have also been considered and compared: ΔΔESA+EEF > ΔΔESA+AS > ΔΔEEEF+AS. When including all three factors, the change of segregation energy could reach 1.63 eV. Therefore, operating conditions have a noteworthy influence on the segregation behavior of PtM ORR electrocatalysts, which should be considered in the further design of PtM ORR electrocatalysts. [ABSTRACT FROM AUTHOR]

Due to the enhanced tolerance of CO‐containing species under elevated operation temperature around 150–220 °C, high‐temperature polymer electrolyte fuel cells (HT‐PEFCs) have drawn extensive interest in the recent decades. One of the major challenges remaining for HT‐PEFCs is the inferior cell performance ascribed to poor catalytic activity and mass transport, which are mainly determined by the electrochemical interface structure involving phosphoric acid electrolyte. Herein, the electrochemical interfaces are investigated and optimized by adjusting the hydrophilic phases within the catalyst layer (CL) to modulate phosphoric acid redistribution in the cathode. The electrochemical surface area and interfacial oxygen transport resistance in the CL are optimized by balancing the coverage of polytetrafluoroethylene (PTFE) and phosphoric acid on the catalyst surface, thus achieving an enhanced cell performance of the HT‐PEFC of up to 328.12 mW cm−2. This balancing strategy for optimizing the electrochemical interfacial structure could shed light on the development of electrode architecture design for energy conversion and storage devices. [ABSTRACT FROM AUTHOR]

Iron‐nitrogen‐doped carbon (Fe‐NC) is an ideal candidate to replace Pt‐based oxygen reduction reaction (ORR) electrocatalysts due to its low cost and comparably high intrinsic activity. To further enhance the ORR performance of Fe‐NC electrocatalysts, efforts have been focused on two main methods. One is to enhance the intrinsic activity of FeNx sites through electronic and geometric regulation, and the other is to increase the density of active sites by introducing high‐nitrogen‐containing precursors or co‐doping methods. Herein, we report a strategy to further increase the Fe loading through the introduction of a trace amount of Cu atoms. Significant enhancement of the electrocatalytic ORR property is observed in the as‐prepared Fe and Cu co‐doped electrocatalyst with superior half‐wave potential (E1/2) in both alkaline and acid electrolyte. Experimental and theoretical study reveals that the introduction of a trace amount of Cu atoms is beneficial for the formation of FeN4 sites, owing to the reduced formation energy. This work opens up a wide avenue to further increase the Fe loading in Fe‐NC electrocatalysts through bimetal co‐doping method. [ABSTRACT FROM AUTHOR]

The strain effect on oxygen reduction reaction (ORR) activity and stability of FeNC electrocatalysts has been studied using density functional theory in this work. Based on the reaction free energy results, the rate-determining step (RDS) of ORR on FeNC is *OH → H2O, and the reaction proceeds with the pathway O2 → *OOH → *O → *OH → H2O on the Fe site. Tensile stress is favorable to enhance the ORR activity, and the highest ORR activity is obtained on the 6%-FeNC electrocatalyst. On the other hand, when the whole oxygen reduction process needs synergy between Fe and adjacent C atoms and proceeds with the pathway O2 → *OOH → *TS → *O & #OH → *O → *OH → H2O, the applied stress will decrease the ORR activity of the FeNC electrocatalyst. We further constructed a Cu@FeNC core–shell model to simulate strained FeNC. However, the adsorption energy of ORR intermediates on Cu@FeNC (1.9%-FeNC) is much weaker than on the corresponding 2%-FeNC, mainly due to the coordination between the Cu substrate and Fe atom. In addition, the formation energy and binding energy indicate that neither tensile nor compressive stress is conducive to the stability of the FeNC electrocatalyst. In summary, tensile stress could enhance the ORR activity of FeNC electrocatalysts when ORR occurs on the Fe atom only. What's more, we should pay more attention to the influence of interface interaction if utilizing a M@FeNC model to achieve strained FeNC. [ABSTRACT FROM AUTHOR]

Direct methanol fuel cells (DMFCs) have drawn extensive interest for the past two decades both in scientific research and industrial engineering circles for their advantages of high energy density, environmental friendliness, and easy fuel handling. However, their excessively high costs, especially derived from the massive use of precious metal catalysts in both their anodes and cathodes, hamper the commercialization of this technology to the general public. Though the production of inexpensive catalysts of methanol oxidation remains challenging, non-precious-metal-based catalysts of the oxygen reduction reaction have seen considerable technical progress, yielding remarkable performance levels in hydrogen-fueled polymer electrolyte membrane fuel cells (PEMFCs). Due to the particularities of the electrochemical reactions and mass transport for methanol fuel in DMFC electrodes, highly active non-precious metal catalysts have not yielded sufficiently satisfactory single-cell performances for practical applications. In the current work, rather than exploring the cathodic designs with advanced electrode materials and structures, we estimated the mass transport of methanol and its effects on cathode performance, and then redesigned the anode architecture with ultrathin gas diffusion layers based on carbon nanotube composite materials. By using such an alternative strategy focused on anodic engineering to accelerate methanol transport combined with the use of a methanol-inert cathode, an ultrahigh cell performance, comparable to those of Pt–C-containing cathodes, was achieved even at a low methanol concentration. The peak power density obtained was 141 mW cm−2, a value among the highest obtained from DMFCs with non-precious-metal catalyst cathodes to the best of our knowledge. A wider avenue of DMFC technologies for practical applications might be opened with further development of this work. [ABSTRACT FROM AUTHOR]

The oxygen evolution reaction (OER) plays a critical role in efficient conversion and storage of renewable energy sources, whereas the active sites for the most representative electrocatalysts, Ni–Fe compounds, remain under debate. In this work, we have developed polymeric carbon nitride (PCN) with atomically dispersed N-coordinated Ni–Fe sites to investigate the OER process. The Ni–Fe dual sites consist of adjacent Ni and Fe atoms coordinated with N atoms in the PCN matrix. NiFe-codoped PCN exhibits higher electrocatalytic activity than monometal-doped catalysts, showing a lower overpotential (310 mV at 10 mA cm−2) and smaller Tafel slope (38 mV dec−1) in 1 M KOH, indicating that Ni–Fe dual-metal sites significantly favor the OER process. According to density functional theory calculations based on the oxidized-NiFe@PCN model, it was found that adjacent Ni and Fe atoms co-participate in the OER process for NiFe-codoped PCN, leading to a much lower energy barrier (0.10 or 0.22 eV for U = 1.58 V), while the effect of electronic modification of the single metal active sites by the other component (Ni sites by Fe sites or vice versa) contributes less to activity enhancement, thus leading to a rational explanation on the synergistic effect of the NiFe-based OER catalysts. [ABSTRACT FROM AUTHOR]

The fabrication of a novel electrode architecture with multi-scale orderliness is an effective strategy to enhance Pt utilization and decrease the mass transport polarization loss of proton exchange membrane fuel cells (PEMFCs). Here we report a hierarchically well-defined electrode with Pt nanowhiskers on aligned nanowires by a magnetron sputtering method. With the crystallographically preferential growth of Pt (111) facets, in association with the electron modification effects of PANI on Pt nanowhiskers, the electrode achieves outstanding electrochemical activity towards the oxygen reduction reaction (ORR) with a 2.19-fold enhancement of the specific activity and a similar mass specific activity at 0.9 V (vs. the RHE), compared to the state-of-the-art Pt–C electrode. The PEMFC fabricated with the Pt–PANI-GDL electrode shows excellent performance with a peak power density of 542 mW cm−2, and a cathode mass specific power density of 5.7 W mgPt−1, which is 39% greater than that of PEMFCs equipped with a Pt–C electrode for enhanced electrochemical activity and mass transport. [ABSTRACT FROM AUTHOR]

Carbon black nanoparticles localized in-between liposomal bi-layers provide a unique reaction environment that permits one-step synthesis of carbon-supported foam-like platinum (Pt foam/C) in aqueous solution under ambient conditions. The obtained Pt foam/C was readily purified by simple washing with water and chloroform at room temperature. Unlike commercial Pt/C composed of quasi-spherical nanoparticles, Pt foam/C consists of convoluted dendritic nanosheets. Interestingly, Pt foam/C demonstrated both improved durability and activity toward oxygen reduction reaction (ORR). The improved durability is because of the formation of metastable nano-holes among dendritic branches of Pt foam/C under ripening, preserving the surface area. The activity enhancement of Pt foam/C can be attributed to predominantly exposed Pt {1,1,0} planes that possess the highest ORR activity among all low-indexed Pt crystalline planes. Nano-scale Pt primarily enclosed by {1,1,0} planes has not been reported previously. [ABSTRACT FROM AUTHOR]

Non-noble metal (NNM) electrocatalysts with performances comparable with or superior to Pt are highly desirable for fuel cells and metal-air batteries, but remain rare. Herein, we report a new NNM electrocatalyst derived from reduced graphene oxide (rGO), dual nitrogen-containing ligands, and iron and cobalt salts. Remarkably, the onset potential and half-wave potential (E1/2) of the obtained electrocatalyst shifts 5 and −23 mV, respectively, relative to commercial Pt/C at a standard loading of 20 μgpt cm−2 toward an oxygen reduction reaction (ORR) in alkaline solutions. Additionally, the electrocatalyst is much better than the Pt/C in terms of durability and tolerance to methanol. [ABSTRACT FROM AUTHOR]

Abstract: Performance characteristics of a three electrolyte rechargeable acid–alkaline hybrid battery using a PbO2 positive plate and a nickel metal hydride (NiMH x ) negative electrode in separate electrolyte of H2SO4 and KOH were studied. This hybrid battery has three electrolytes in a single cell. A neutral K2SO4 salt solution was placed between the acid and alkaline compartments of the cell, in which a cation exchange membrane and an anion exchange membrane, were employed to separate these three electrolytes. The open circuit voltage of this hybrid cell was found to be 2.64V in an electrolyte configuration of 1M H2SO4|0.2MK2SO4|2M KOH electrolyte configuration, compared to 1.92V in the conventional lead-acid cell in 1M H2SO4 and 1.40V in a NiMH x cell in 2M KOH. This hybrid acid–alkaline PbO2/NiMH x battery was shown to operate with a voltage 20% higher than the conventional lead acid battery and 110% higher than nickel–metal hydride battery at 1/3C discharging rate. The concentrations of the three electrolytes, the dimension of the electrolyte chamber, and other cell/operation parameters with impacts on the hybrid cell performance were investigated. [Copyright &y& Elsevier]

Abstract: Vulcan XC-72R carbon supported Pd nanoparticles was obtained in a NH3-mediated polyol process without any protective agent and characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM) techniques. The added NH3 species is found to have a strong complex ability to Pd, which not only avoids the formation of Pd hydroxide precipitate resulted from Pd hydrolysis, but also restrains the further complete reduction of Pd. Temperature-programmed reduction equipped with a mass spectrometry (TPR-MS) is employed to study the reductive behavior of unreduced Pd complex in Pd/C catalyst and the results show that the post-treatment in a reductive atmosphere at higher temperature is needed to ensure the complete reduction of Pd. XRD patterns show the heat-treated Pd/C sample in a reductive atmosphere has a face centered cubic crystal structure and TEM image indicates that the dispersion of Pd nanoparticles on the carbon support is uniform and in a narrow particle size range. Thermodynamic data analysis is carried out to elucidate the possible reaction pathway for the preparation of Pd/C catalyst in this process. The obtained Pd/C catalyst shows high activity to formic acid oxidation and high selectivity to oxygen reduction reaction (ORR) with the presence of methanol. [Copyright &y& Elsevier]

Abstract: Well dispersed PtSn/C, PtRu/C and Pt/C electrocatalysts were synthesized by a modified polyol process and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and inductively coupled plasma-atomic emission spectrometry techniques. XRD patterns show that Ru induces the contraction of Pt lattice parameter while Sn makes the Pt crystal lattice extended. Ethanol oxidation activities on the catalysts were studied via cyclic voltammetry (CV) and chronoamperometry (CA) methods at room temperature. It is found that the electrode potential plays an important role in the electrochemical behavior of ethanol oxidation on PtRu/C and PtSn/C catalysts. In the lower potential region, PtSn/C possesses higher performance for ethanol oxidation, while in the higher potential region PtRu/C is more active. The different promotion effects of PtSn/C and PtRu/C to ethanol oxidation can be explained by the structural effect and modified bi-functional mechanism in different potential region. Single cell test of a direct ethanol fuel cell (DEFC) was also carried out to elucidate the promotion effect of PtRu/C and PtSn/C catalysts on the ethanol oxidation at 90°C. [Copyright &y& Elsevier]

Abstract: Carbon supported PtSn alloy and PtSnO x particles with nominal Pt:Sn ratios of 3:1 were prepared by a modified polyol method. High resolution transmission electron microscopy (HRTEM) and X-ray microchemical analysis were used to characterize the composition, size, distribution, and morphology of PtSn particles. The particles are predominantly single nanocrystals with diameters in the order of 2.0–3.0nm. According to the XRD results, the lattice constant of Pt in the PtSn alloy is dilated due to Sn atoms penetrating into the Pt crystalline lattice. While for PtSnO x nanoparticles, the lattice constant of Pt only changed a little. HRTEM micrograph of PtSnO x clearly shows that the change of the spacing of Pt (111) plane is neglectable, meanwhile, SnO2 nanoparticles, characterized with the nominal 0.264nm spacing of SnO2 (101) plane, were found in the vicinity of Pt particles. In contrast, the HRTEM micrograph of PtSn alloy shows that the spacing of Pt (111) plane extends to 0.234nm from the original 0.226nm. High resolution energy dispersive X-ray spectroscopy (HR-EDS) analyses show that all investigated particles in the two PtSn catalysts represent uniform Pt/Sn compositions very close to the nominal one. Cyclic voltammograms (CV) in sulfuric acid show that the hydrogen ad/desorption was inhibited on the surface of PtSn alloy compared to that on the surface of the PtSnO x catalyst. PtSnO x catalyst showed higher catalytic activity for ethanol electro-oxidation than PtSn alloy from the results of chronoamperometry (CA) analysis and the performance of direct ethanol fuel cells (DEFCs). It is deduced that the unchanged lattice parameter of Pt in the PtSnO x catalyst is favorable to ethanol adsorption and meanwhile, tin oxide in the vicinity of Pt nanoparticles could offer oxygen species conveniently to remove the CO-like species of ethanolic residues to free Pt active sites. [Copyright &y& Elsevier]

Ultrahigh mass transport resistance and excessive coverage of the active sites introduced by phosphoric acid (PA) are among the major obstacles that limit the performance of high-temperature polymer fuel cells, especially compared to their low-temperature counterparts. Here, an alternative strategy of electrode design with fibrous networks is developed to optimize the redistribution of acid within the electrode. Via structural tailoring with varied electrospinning parameters, uneven migration of PA with dispersed droplets is observed, subverting the immersion model of conventional porous electrode. Combining with experimental and calculation results, the microscaled uneven PA interfaces could not only provide extra diffusion pathways for oxygen but also minimize the thickness of PA layers. This electrode architecture demonstrates enhanced electrochemical performance of oxygen reduction within the PA phase, resulting in a 28% enhancement of the maximum power density for the optimally designed electrode as cathode compared to that of a conventional one.

The oxygen reduction reaction (ORR) that occurs on the outermost layer of electrocatalysts is significantly affected by the composition and structure of the electrocatalysts. During the preparation of PtM alloy electrocatalysts, high-temperature annealing in an inert or reducing atmosphere could promote the segregation of M toward the core, forming a highly active Pt-skin structure. However, under fuel cell operating conditions, the adsorption of oxygen-containing groups could stimulate the easily dissolved M to segregate to the surface, reducing the activity and stability of the electrocatalysts. In this work, we conducted segregation energy calculation of PtM (M = Cu, Pd, Au) electrocatalysts under specific adsorption (SA), aqueous solution (AS) and an external electric field (EEF) with a density functional theory method. It was found that different factors have different effects on the segregation energy: ΔΔESA ≫ ΔΔEEEF > ΔΔEAS. The coupling effects have also been considered and compared: ΔΔESA+EEF > ΔΔESA+AS > ΔΔEEEF+AS. When including all three factors, the change of segregation energy could reach 1.63 eV. Therefore, operating conditions have a noteworthy influence on the segregation behavior of PtM ORR electrocatalysts, which should be considered in the further design of PtM ORR electrocatalysts.

Monomorphic Pt octapod and tripod nanocrystals have been successfully synthesized by an iron nitrate modified polyol process, in which iron nitrate has been proven to be vitally important for slowing down the reduction rate of Pt precursors., (This journal is © The Royal Society of Chemistry 2011)

Size-controllable tin oxide nanoparticles are prepared by heating ethylene glycol solutions containing SnCl(2) at atmospheric pressure. The particles were characterized by means of transmission electron microscopic (TEM), X-ray diffraction (XRD) studies. TEM micrographs show that the obtained material are spherical nanoparticles, the size and size distribution of which depends on the initial experimental conditions of pH value, reaction time, water concentration, and tin precursor concentration. The XRD pattern result shows that the obtained powder is SnO(2) with tetragonal crystalline structure. On the basis of UV/vis and FTIR characterization, the formation mechanism of SnO(2) nanoparticles is deduced. Moreover, the SnO(2) nanoparticles were employed to synthesize carbon-supported PtSnO(2) catalyst, and it exhibits surprisingly high promoting catalytic activity for ethanol electrooxidation.

A novel carbon-supported palladium-rich Pd3Pt1/C catalyst prepared by a modified polyol process showed a better cell performance than Pt/C in direct methanol fuel cells, which may be attributed to palladium's inactivity to methanol electro-oxidation while exhibiting good performance to oxygen reduction reaction.